CN108940301B - Preparation method of copper-based wet oxidation catalyst - Google Patents
Preparation method of copper-based wet oxidation catalyst Download PDFInfo
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- CN108940301B CN108940301B CN201710366542.4A CN201710366542A CN108940301B CN 108940301 B CN108940301 B CN 108940301B CN 201710366542 A CN201710366542 A CN 201710366542A CN 108940301 B CN108940301 B CN 108940301B
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- wet oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 53
- 239000010949 copper Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 34
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 45
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 20
- 239000008188 pellet Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 230000010355 oscillation Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- 238000010009 beating Methods 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DLNAGPYXDXKSDK-UHFFFAOYSA-K cerium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ce+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O DLNAGPYXDXKSDK-UHFFFAOYSA-K 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- -1 heterophenol Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a wet oxidation catalyst and a preparation method thereof, wherein the method comprises the following steps: (1) pulping the activated alumina; (2) dissolving a copper source precursor to form a solution, and mixing the (1) and the (2); (3) uniformly mixing the solution obtained in the step (2), adjusting the pH value to form a precipitate, filtering and washing; (4) adding deionized water into the filter cake obtained in the step (3), mixing into slurry, adding a cerium source precursor solution, uniformly mixing, drying, and roasting to form powder; (5) and (4) mixing the powder in the step (4) and a manganese source precursor solution into slurry, stirring, adding a pore-forming agent, stirring for the second time, sealing, standing, drying and roasting to form the wet oxidation catalyst. The wet oxidation catalyst prepared by the invention is used for high-concentration organic wastewater, and has the characteristics of low cost, stable performance and the like.
Description
Technical Field
The invention relates to a catalyst in the field of metal materials and a preparation method thereof, in particular to a preparation method of a wet oxidation catalyst.
Background
Wet Air Oxidation (WAO) for treating high-concentration refractory organic wastewater usually requires high temperature and pressure (200-3 l5 ℃, 2-21 MPa) and long retention time, and the reaction conditions are very harsh. Catalytic wet oxidation, CWAO) can reduce the reaction temperature and pressure under the condition of keeping the treatment effect, and greatly promote the development and application of wet oxidation. Therefore, the development of a catalyst with high activity and stability and suitable for CWAO has become a major and difficult point of current research. The oil refining or ethylene waste alkali liquor (caustic sludge) contains a large amount of high-concentration Na in addition to free alkali (NaOH) with different concentrations2S, organic acidic substances (existing in the form of sodium salt, such as heterophenol, naphthenic acid, mercaptan, thiophenol and the like), thioether, thiophene and other organic sulfides are malodorous and toxic, the COD content is as high as 10000-150000 mg/L, and the problems of catalyst poisoning, loss of metal active ingredients, low COD removal efficiency and the like are easy to occur in the catalytic wet oxidation process, so that the problems become difficult to study.
CN1358567 discloses 'a copper-based catalyst for catalytic wet oxidation treatment of industrial wastewater and a preparation method thereof', a preparation method and application of the copper-based catalyst for catalytic wet oxidation treatment of industrial wastewater. The catalyst mainly comprises copper, zinc, nickel, magnesium, aluminum, chromium, iron and a part of rare earth metal oxide, wherein the content of CuO is 20-55% calculated by the content of the oxide; 20-55% of ZnO, NiO or MgO; cr (chromium) component2O3、Al2O3Or Fe2O310-40%; 0-10% of rare earth metal oxide. The catalyst is catalyzed by coprecipitation of salts containing various metals to obtain a hydrotalcite-like structurePrecursor agent and roasting to obtain the catalyst. The catalyst is prepared by one-time coprecipitation and roasting, can effectively treat poisonous and nondegradable industrial organic wastewater containing phenol, sulfosalicylic acid, H-acid, surfactant and the like, has low copper loss, is difficult to adapt to the requirement of treating wastewater containing various toxic and harmful substances, and particularly has low COD removal efficiency in the treatment of oil refining or ethylene waste alkali liquor.
CN1669643 discloses a rare earth composite oxide catalyst which is solid powder and comprises ZrO2And CeO, wherein the molar ratio of Zr to Ce is 1: 1-1: 11. The invention also discloses a preparation method of the catalyst, which comprises the following steps: mixing zirconium salt and cerium salt solution, and drying and roasting once by adopting a one-step precipitation method to obtain the catalyst. The catalyst prepared by the invention has good activity and higher stability only for wastewater containing high-concentration non-degradable small molecular organic acid, and is difficult to adapt to the requirement of treating wastewater containing various toxic and harmful substances, especially the treatment of oil refining or ethylene waste lye.
CN104667934 discloses "a method for preparing a catalytic wet oxidation catalyst", which adopts transition rare earth metals as active metal components, impregnates them on a carrier, and realizes the preparation of the catalyst after primary impregnation and primary calcination.
In conclusion, the preparation of the precipitation wet oxidation catalyst is prepared by one-time precipitation and one-time roasting, the prepared catalyst has a certain effect of removing COD and organic matters in wastewater in the catalytic wet oxidation process, but in the process of treating the waste alkali liquor, the catalyst is easy to be poisoned, the COD removal efficiency is low, the active component copper is easy to be lost, and the performance of the catalyst is influenced.
Disclosure of Invention
The invention provides an improved wet oxidation catalyst preparation method, which can resist the problems of poisoning, inactivation and active ingredient loss in a multi-pollutant coexistence system, improve the stability and activity and achieve good waste caustic sludge treatment effect.
The invention relates to a preparation method of a wet oxidation catalyst, which comprises the following steps:
(1) pulping the activated alumina to form a slurry;
(2) dissolving a copper source precursor, and mixing the copper source precursor with the solution in the step (1);
(3) uniformly mixing the solution obtained in the step (2), adjusting the pH value to form a precipitate, filtering and washing;
(4) adding deionized water into the filter cake obtained in the step (3), mixing into slurry, adding a cerium source precursor, uniformly mixing, and directly drying and roasting to form powder;
(5) and (4) mixing the powder in the step (4) and a manganese source precursor solution into slurry, stirring, adding a pore-forming agent, mixing for the second time, sealing, standing, drying and roasting to form the wet oxidation catalyst.
The preparation method of the wet oxidation catalyst adopts the active alumina, and the interior of the active alumina is provided with rich nano-scale micropores, thereby being more beneficial to the dispersion and adsorption of active substances. After the active aluminum oxide and the ionic copper are mixed, amorphous copper oxide can be promoted to be better dispersed and adsorbed inside the active aluminum oxide, and meanwhile, the copper oxide and the active aluminum oxide are more tightly wrapped, so that the loss of the copper in the catalysis process can be effectively reduced, the strength of the catalyst is improved, the specific surface area and the porosity of the catalyst are improved, the active sites inside the catalyst are increased, and the efficiency of the catalyst is improved.
The preparation method of the wet oxidation catalyst comprises the step (1) of pulping the active alumina to form the Al-containing product2O3The content of the slurry is preferably 200-500 g/L, and the slurry is 50-600 g/L.
According to the preparation method of the wet oxidation catalyst, the copper source precursor in the step (2) is a soluble copper salt, preferably copper nitrate, and the content of the solution formed by dissolving the copper source precursor is preferably 15-40 g/L calculated by CuO.
The preparation method of the wet oxidation catalyst comprises the steps of (3) mixing for 0.5-3 h, stirring for 10-60 min, and sealing and standing for 8-30 h in the step (5).
In the invention, the pH value in the step (3) can be adjusted by adopting ammonia water, sodium hydroxide and other acid-base regulators, preferably ammonia water, and the pH value is 4-13, preferably 8-11.
According to the preparation method of the wet oxidation catalyst, the cerium source precursor in the step (4) is cerium nitrate, cerium acetate or cerium citrate, preferably cerium nitrate, and the content of the formed material in the step (4) is preferably 15-40 g/L in terms of CeO.
According to the preparation method of the wet oxidation catalyst, the manganese source precursor in the step (5) is soluble manganese salt, preferably manganese nitrate, and the content of the material formed in the step (5) is preferably 15-40 g/L calculated by MnO.
In the preparation method of the wet oxidation catalyst, the pore-forming agent in the step (5) can be one or more of citric acid, urea, trioxyacetic acid, activated carbon and sesbania powder, preferably sesbania powder, the pore-forming agent and Al2O3The mass ratio is preferably 0.5-1.5: 100.
The preparation method of the wet oxidation catalyst comprises the steps of (4) and (5), wherein the roasting temperature is 400-850 ℃, preferably 500-650 ℃, and the roasting time is not less than 1 hour, preferably 2-7 hours. The roasting temperature is too low, the metal hydroxide can not be completely decomposed and converted into oxides with catalytic activity, the crystal form of the oxides can not be fully rearranged, and the catalytic performance of the catalyst is influenced; the too high roasting temperature causes the crystal form of the oxide to change, and the catalyst is excessively sintered, so that the catalyst performance of the catalyst is also reduced.
In the method for preparing a wet oxidation catalyst according to the present invention, the mixing method in the steps (3), (4) and (5) includes various mechanical stirring, fluid mixing and ultrasonic mixing, and among them, the ultrasonic method is preferable.
The catalyst prepared by the preparation method of the wet oxidation catalyst comprises, by weight, 30-75% of active alumina, 10-30% of copper oxide, 5-20% of cerium oxide and 10-30% of manganese oxide, and the specific surface area is 60-160 m2A pore volume of 0.30-0.70 cm3The content of the active alumina is preferably 40 to 75%, the content of the copper oxide is preferably 10 to 20%, and the content of the cerium oxide is preferably 5 to 12%Manganese oxide 10-20%, and a specific surface area of 70-120 m2A pore volume of 0.40-0.60 cm/g3/g。
The wet oxidation catalyst prepared by the method takes Cu metal oxide as an active component, and Ce and Mn oxides are added as an auxiliary agent. Wherein the component CuO is used for promoting the oxidation reaction of organic matters, and the component Al is used for promoting the oxidation reaction of organic matters2O3The main function of the catalyst is to adjust the structure of the catalyst, but if the content is too high, the content of active components is insufficient, and the performance of the catalyst is also influenced; tests show that the catalyst has high conversion rate and serious loss when the CuO content is high, and the catalyst has unstable performance; the oxides of the promoters Mn and Ce mainly play a role in the removal of organic matters (a large amount of high-concentration Na)2S, organic acidic substances such as hetero phenol, naphthenic acid, mercaptan, thiophenol and the like, and organic sulfides such as thioether, thiophene and the like) deep oxidation and sulfur poisoning resistance, and the following effects are found in the test: the activity of the catalyst is obviously poor when the auxiliary agent manganese oxide is used alone, the activity of the catalyst is not ideal when the auxiliary agent cerium oxide is used alone, and when the oxides of copper, cerium, nickel and aluminum exist simultaneously, the comprehensive performance of the prepared catalyst is obviously improved compared with that of the catalyst only containing a certain component.
According to the preparation method of the wet oxidation catalyst, after the copper and cerium powder materials are roasted for one time, a layer of manganese oxide covers the surface of the copper and cerium powder materials, and meanwhile, the pore-forming agent is added, so that the surface of catalyst particles has more manganese oxide attached, and meanwhile, the catalyst particles also have rich space network-shaped nano-scale micropores and higher crushing strength, the loss of copper ions can be reduced, and high catalytic performance can be guaranteed.
The catalyst prepared by the method can be used for treating waste alkali liquor generated in the oil refining or ethylene production process, wastewater with the COD content ranging from 10000-150000 can be directly treated, the conversion rate of sulfide can reach more than 99.9 percent, the conversion rate of phenols can reach more than 90 percent, the removal rate of COD can reach more than 85.0 percent after the wastewater is treated by catalytic wet oxidation by taking excess air or enriched air as an oxidation medium under the conditions that the pressure is 1.0-5.0 MPa, the reaction temperature is 190-260 ℃ and the reaction time is 0.5-4.0 h, and the BOD/COD ratio after the wastewater treatment is increased from 0.1 to more than 0.40, thereby being beneficial to further standard treatment of the wastewater.
Detailed Description
The following examples are specific illustrations of the present invention, and "%" described in examples and comparative examples means mass percent.
Example 1
Pulping 70g of activated alumina to form a slurry containing Al2O3Adding a copper nitrate solution containing 20g of CuO into 300g/L of slurry, oscillating for 2 hours by ultrasonic waves, gradually adding ammonia water to adjust the pH value to 8.5, and filtering and washing after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding a cerium nitrate solution accounting for 8g of CeO, stirring and carrying out ultrasonic oscillation for 1.5h, directly drying, and roasting at 620 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 10g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of citric acid-sesbania powder composite agent, stirring for 40min, sealing and standing for 24h, drying, and roasting at 650 ℃ for 7h to obtain a wet oxidation catalyst sample A.
Comparative example 1
The other conditions are not changed, and the dosage of CuO is reduced. Pulping 70g of active alumina pellets to form the Al-containing material2O3Adding a copper nitrate solution containing 2g of CuO into 300g/L slurry, oscillating for 2 hours by ultrasonic waves, gradually adding ammonia water to adjust the pH value to 8.5, and filtering and washing after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding a cerium nitrate solution accounting for 8g of CeO, stirring and carrying out ultrasonic oscillation for 1.5h, directly drying, and roasting at 620 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 10g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of citric acid-sesbania powder composite agent, stirring for 40min, sealing and standing for 24h, drying, and roasting at 650 ℃ for 7h to obtain a wet oxidation catalyst sample F.
Example 2
Beating 50g of activated alumina pellets to form Al-containing pellets2O3Adding a copper nitrate solution containing 10g of CuO into slurry of 200g/L, oscillating by ultrasonic waves for 2 hours, gradually adding ammonia water to adjust the pH value to 9.5, and filtering and washing after complete precipitation; then the washed matter is washedPreparing the slurry with the water content of 50% by using deionized water, adding 10g of cerium nitrate solution calculated by CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.5h, directly drying, and roasting at 520 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 10g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 40min, sealing and standing for 24h, drying, and roasting at 600 ℃ for 5h to obtain a wet oxidation catalyst sample B.
Comparative example 2
The other conditions were not changed, and the amount of CeO used was reduced. Beating 50g of activated alumina pellets to form Al-containing pellets2O3Adding a copper nitrate solution containing 10g of CuO into slurry of 200g/L, oscillating by ultrasonic waves for 2 hours, gradually adding ammonia water to adjust the pH value to 9.5, and filtering and washing after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding a cerium nitrate solution accounting for 2g of CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.5h, directly drying, and roasting at 520 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 10G calculated by MnO into slurry containing 30% of water, stirring, adding 1G of urea, stirring for 40min, sealing and standing for 24h, drying, and roasting at 600 ℃ for 5h to obtain a wet oxidation catalyst sample G.
Example 3
Beating 50g of activated alumina pellets to form Al-containing pellets2O3Adding a copper nitrate solution containing 16g of CuO into the slurry of 500g/L, oscillating the slurry by ultrasonic waves for 3 hours, gradually adding ammonia water to adjust the pH value to 9.0, and filtering and washing the slurry after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding 10g of cerium nitrate solution calculated by CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 550 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 10g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20h, drying, and roasting at 550 ℃ for 2h to obtain a wet oxidation catalyst sample C.
Comparative example 3
The MnO content is reduced without changing other conditions. That is, 50g of active alumina pellets are pulped to form Al-containing2O3Adding a copper nitrate solution containing 16g of CuO into the slurry of 500g/L,after ultrasonic oscillation for 3 hours, gradually adding ammonia water to adjust the pH value to 9.0, and after complete precipitation, filtering and washing; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding 10g of cerium nitrate solution calculated by CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 550 ℃ for 2 h; and preparing the roasted powder and 5g of manganese nitrate solution calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20H, drying, and roasting at 550 ℃ for 2H to obtain a wet oxidation catalyst sample H.
Example 4
Beating 80g of activated alumina pellets to form pellets containing Al2O3Adding a copper nitrate solution containing 16g of CuO into the slurry of 400g/L, oscillating the slurry by ultrasonic waves for 3 hours, gradually adding ammonia water to adjust the pH value to 9.0, and filtering and washing the slurry after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding 10g of cerium nitrate solution calculated by CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 550 ℃ for 2 h; and preparing the roasted powder and 15g of manganese nitrate solution calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20h, drying, and roasting at 550 ℃ for 2h to obtain a wet oxidation catalyst sample D.
Comparative example 4
Other conditions are unchanged, and the roasting temperature is reduced. Beating 80g of active alumina pellets to form pellets containing Al2O3Adding a copper nitrate solution containing 16g of CuO into the slurry of 400g/L, oscillating the slurry by ultrasonic waves for 3 hours, gradually adding ammonia water to adjust the pH value to 9.0, and filtering and washing the slurry after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding 10g of cerium nitrate solution calculated by CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 395 ℃ for 2 h; and preparing the roasted powder and 15g of manganese nitrate solution calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20h, drying, and roasting at 395 ℃ for 2h to obtain a wet oxidation catalyst sample I.
Example 5
Beating 80g of activated alumina pellets to form pellets containing Al2O3Adding a copper nitrate solution containing 12g of CuO into the slurry of 200g/L, oscillating the slurry by ultrasonic waves for 1 hour, gradually adding ammonia water to adjust the pH value to 9.0, and filtering and washing the slurry after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding a cerium acetate solution accounting for 6g of CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 650 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 12g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20h, drying, and roasting at 650 ℃ for 2h to obtain a wet oxidation catalyst sample E.
Comparative example 5
Other conditions are unchanged, and the roasting temperature is increased. Beating 80g of active alumina pellets to form pellets containing Al2O3Adding a copper nitrate solution containing 12g of CuO into the slurry of 200g/L, oscillating the slurry by ultrasonic waves for 1 hour, gradually adding ammonia water to adjust the pH value to 9.0, and filtering and washing the slurry after complete precipitation; preparing the washed materials into slurry with the water content of 50% by using deionized water, adding a cerium acetate solution accounting for 6g of CeO, stirring and simultaneously carrying out ultrasonic oscillation for 1.0h, directly drying, and roasting at 910 ℃ for 2 h; and preparing the roasted powder and a manganese nitrate solution of 12g calculated by MnO into slurry containing 30% of water, stirring, adding 1g of urea, stirring for 30min, sealing and standing for 20h, drying, and roasting at 910 ℃ for 2h to obtain a wet oxidation catalyst sample J.
Comparative example 6
The wet oxidation catalyst was prepared by the same one-time co-precipitation and calcination method as in example 5. Beating 80g of activated alumina to form Al-containing slurry2O3The method comprises the steps of preparing slurry 200g/L, preparing a copper nitrate solution 12g in terms of CuO, a cerium acetate solution 6g in terms of CeO, and a manganese nitrate solution 12g in terms of MnO into slurry containing 30% of water, transferring 1g of urea into a beaker, carrying out ultrasonic oscillation for 1 hour, gradually adding ammonia water to adjust the pH value to 9.0, standing for 20 hours after complete precipitation, filtering, washing, directly drying, and roasting at 650 ℃ for 2 hours to obtain a wet oxidation catalyst sample K.
Comparative example 7
The wet oxidation catalyst is prepared by adopting a CN1358567 method, namely: get550ml of Na with a concentration of 1.0mol/L2CO3The solution is placed in a constant temperature water bath with a water bath temperature of 70 ℃ and heated for 20 min. Taking 1.0mol/L Cu (NO)3)2Solution 100ml, 1.0mol/L Zn (NO)3)2110ml of solution, 0.5mol/L of Al (NO)3)375ml of the solution was transferred to a beaker, mixed well and added dropwise to Na slowly using a separatory funnel2CO3The solution was stirred rapidly in a beaker. After titration, the pH of the mother liquor is guaranteed to be more than or equal to 9, and the precipitate and the mother liquor are aged for 24 hours together. After aging, vacuum filtration is adopted to separate the mother liquor from the precipitate, and deionized water is adopted to wash for four times in the filtration process. And extruding the precipitate into phi 3 strips, airing in air, drying at 110 ℃ for 2h, roasting in a muffle furnace for 8h at 700 ℃, cooling, and grinding into 70-mesh powder to obtain a catalyst sample L.
The physical properties of each catalyst sample are shown in table 1:
TABLE 1 catalyst sample physical Property data
Evaluation results were as follows:
crushing the A-J catalyst, screening 5ml of 10-40-mesh particles, filling the particles into a miniature continuous flow fixed bed reactor, introducing waste alkali-containing slag to form a Chemical Oxygen Demand (COD) of 60000mg/L, a sulfide content of 5000mg/L and a phenol content of 85000mg/L, adding compressed air, and performing an evaluation test under the conditions that the reaction pressure is controlled at 3.2MPa, the temperature is 220 ℃ and the reaction time is 2.0 hours.
The conversion data of each catalyst are shown in tables 2 and 3 respectively through the evaluation test.
Table 2 evaluation results of catalysts in examples
Table 3 comparative example catalyst evaluation results
As can be seen from tables 2 and 3: the catalyst prepared by the preparation method and conditions of the invention is used for treating oil refining alkali waste residue or phenol-containing organic wastewater, the removal rate of sulfide can reach 99.9%, the removal rate of COD can reach more than 85%, and the removal rate of phenols can reach more than 90%.
The reaction time was 2 hours, the other experimental conditions were unchanged, and the concentration of copper ions in the reaction solution was measured, and the results are shown in Table 4. As can be seen from the experimental results, after the catalyst of the present invention treats the waste lye, the loss of copper ions of the catalyst D, E is better controlled and the COD removal effect is better compared with the catalyst L reported in the previous literature and the catalyst K in the comparative example 6.
TABLE 4 COD removal of spent lye and copper ion loss
The reaction time was 2 hours, other experimental conditions were unchanged, the catalyst was repeatedly used 6 times, and the concentration of copper ions in the reaction solution was measured, and the results are shown in table 5. From the experimental results, it can be seen that after the catalyst of the present invention treats the waste alkali solution, the loss of copper ions of the catalyst D, E is better controlled, the COD removal effect is higher, and the activity of the catalyst is kept stable compared with the catalyst L reported in the previous literature and the catalyst K in the comparative example 6.
TABLE 5 COD removal of spent lye and copper ion loss
Claims (8)
1. The preparation method of the copper-based wet oxidation catalyst is characterized by comprising the following steps of:
(1) pulping the activated alumina;
(2) dissolving a copper source precursor, and mixing the copper source precursor with the slurry obtained in the step (1);
(3) mixing the materials obtained in the step (2), adjusting the pH value to form a precipitate, filtering and washing;
(4) adding deionized water into the filter cake obtained in the step (3), adding a cerium source precursor, mixing, drying, and roasting to form powder;
(5) and (3) mixing the powder obtained in the step (4) and a manganese source precursor solution into slurry, adding a pore-forming agent, mixing for the second time, sealing, standing, drying and roasting to form the wet oxidation catalyst, wherein the wet oxidation catalyst contains 30-75% by weight of active alumina, 10-30% by weight of copper oxide, 5-20% by weight of cerium oxide and 10-30% by weight of manganese oxide.
2. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the copper source precursor in the step (2) is a soluble copper salt.
3. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the pH is 4 to 13.
4. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the cerium source precursor is a soluble cerium salt.
5. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the manganese source precursor in the step (5) is a soluble manganese salt.
6. The method for preparing the copper-based wet oxidation catalyst according to claim 1, wherein the pore-forming agent is one or more of citric acid, urea, trioxyacetic acid, activated carbon, and sesbania powder.
7. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the calcination temperature in the steps (4) and (5) is 400 to 850 ℃.
8. The method for preparing a copper-based wet oxidation catalyst according to claim 1, wherein the pH is 8 to 11.
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