CN116920853A - Wet oxidation catalyst and preparation method and application thereof - Google Patents
Wet oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN116920853A CN116920853A CN202210337005.8A CN202210337005A CN116920853A CN 116920853 A CN116920853 A CN 116920853A CN 202210337005 A CN202210337005 A CN 202210337005A CN 116920853 A CN116920853 A CN 116920853A
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- oxidation catalyst
- wet oxidation
- metal
- biochar
- based carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 32
- 238000000197 pyrolysis Methods 0.000 claims description 31
- 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 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 238000001994 activation Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 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 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 30
- 238000011282 treatment Methods 0.000 abstract description 25
- 239000002699 waste material Substances 0.000 abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000002893 slag Substances 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- 238000002791 soaking Methods 0.000 abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011273 tar residue Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/83—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 rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2103/38—Polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention provides a wet oxidation catalyst, a preparation method and application thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, a first metal and a second metal; the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues, wherein the first metal comprises Fe and/or Cu, and the second metal comprises Mn and/or Ce; the invention uses the traditional Chinese medicine slag as the raw material of the biochar-based carrier, loads the first metal and the second metal through soaking and self-heating deactivation in sequence, has wide sources and low cost, can realize the recycling of waste resources by preparing the traditional Chinese medicine slag into the catalyst, can break carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds and the like of organic pollutants in ABS waste water in waste water treatment, and can degrade the carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds and the like into micromolecular substances, thereby realizing the treatment of waste by waste.
Description
Technical Field
The invention belongs to the field of solid waste recycling and wastewater treatment, and particularly relates to a wet oxidation catalyst and a preparation method and application thereof.
Background
China is a large country for producing and using traditional Chinese medicines, and a large amount of traditional Chinese medicine waste residues are generated in the processes of producing Chinese patent medicines, processing and processing traditional Chinese medicines and the like. It is reported that the Chinese averagely discharges three tens of millions of tons of Chinese medicine waste residues each year, and the Chinese medicine waste residues are main solid wastes of Chinese medicine enterprises. Because the water content of the Chinese medicine slag is high, the Chinese medicine slag is easy to rot and deteriorate, resources can be wasted, and the environment can be polluted.
Along with the vigorous development of the traditional Chinese medicine industry, the disposal of a large amount of medicine residues generated by the traditional Chinese medicine preparation also becomes a troublesome problem. At present, the treatment method of the Chinese medicine residues mainly comprises incineration, landfill, composting, edible fungus cultivation, livestock and poultry feed and the like, but the traditional treatment method of the Chinese medicine residues not only needs a great deal of funds, but also can cause the waste of resources, and the recycling of the Chinese medicine residues is an important strategy for energy conservation, emission reduction and green recycling economy.
CN107096500B discloses a method for preparing magnetic biochar from Chinese medicinal residues, magnetic biochar and application, wherein the method comprises the steps of immersing and pre-treating the Chinese medicinal residues and sodium carbonate, and then carrying out treatments such as ferric salt immersion, high-temperature anaerobic activation, washing and drying to obtain the magnetic biochar. The method has the characteristics of simple production process, easily obtained raw materials, high solid-liquid efficiency of the product and the like, realizes the recycling of the traditional Chinese medicine residues, can be widely applied to the field of water treatment, and has good economic and social benefits.
CN113233457a discloses a method for preparing nitrogen-doped porous carbon material by using Chinese medicinal residues, which comprises the following steps: (1) Adding urea serving as a nitrogen source into a high-concentration salt solution, uniformly mixing the urea serving as a nitrogen source to obtain a hydrothermal solution, fully mixing the traditional Chinese medicine residues with the hydrothermal solution, adding the mixture into a high-temperature high-pressure reaction kettle for hydrothermal reaction, and directly filtering to obtain a nitrogen-doped hydrothermal carbon precursor; (2) And (3) placing the nitrogen-doped hydrothermal carbon precursor in a tube furnace for direct carbonization to realize modification and activation of the hydrothermal carbon precursor, and fully washing and drying the modified and activated product to obtain the nitrogen-doped porous carbon material. The method can provide an activating agent for high-temperature activation in a tube furnace in the later period while the high-salt environment is used for pore making and stable aperture growth, salt in the filtrate of the hydrothermal product can be recovered, the process is greatly simplified, the cost is reduced, the obtained nitrogen-doped porous carbon material has high nitrogen content and porosity, and the method can be used for adsorbent raw materials and capacitor electrodes and has a wide application range.
At present, the preparation of the traditional Chinese medicine residues into biomass charcoal materials is a common recycling method, and the preparation of the catalyst by taking the traditional Chinese medicine residues as carrier loaded active components has less research.
ABS resin is a terpolymer of acrylonitrile, butadiene and styrene, and China is the largest consumer country of ABS resin, so the pollution problem of ABS waste water also faces a great challenge. The ABS production wastewater has the characteristics of high concentration of organic matters, high total nitrogen content, poor biodegradability and the like, and is typical high-concentration organic industrial wastewater difficult to degrade. Because toxic substances in ABS wastewater can produce toxic effects on microorganisms, the ABS wastewater is not suitable for direct biochemical treatment, and a high-grade oxidation method and biochemistry are generally combined, and a catalytic hydrogen peroxide oxidation method (CWPO) in the high-grade oxidation method is a green low-carbon technology capable of efficiently treating high-concentration industrial organic wastewater. Hydrogen peroxide is taken as an oxidant, and is decomposed under the action of a catalyst to generate hydroxyl free radicals (HO.) with strong oxidizing ability to degrade CO by organic pollutants 2 And H 2 O, the organic pollutant which can not be thoroughly degraded is decomposed into compounds which are small in toxicity and easy to degrade, so that the biodegradability of the wastewater is improved while COD is reduced, and the subsequent biochemical treatment is facilitated. The CWPO technology has the characteristics of mild reaction conditions, high treatment efficiency, simple and convenient operation and maintenance, wide application range, secondary pollution and the like, can be used for pretreatment of high-concentration organic wastewater, can also be used for advanced treatment of medium-low concentration sewage, and has wide development prospect in the field of water treatment. The core of CWPO technology is the development of catalyst, thus being efficient, safe and low in priceThe development of inexpensive catalysts is particularly critical.
In conclusion, the catalyst prepared from the traditional Chinese medicine residues is used in the field of environmental pollution treatment, so that the catalyst with low price can be obtained, and the treatment of waste by waste and the recycling of waste are realized. Therefore, the method for preparing the wet oxidation catalyst from the traditional Chinese medicine residues is significant in the application of the wet oxidation catalyst in the treatment of ABS wastewater.
Disclosure of Invention
The invention aims to provide a wet oxidation catalyst, a preparation method and application thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, a first metal and a second metal; the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues; the invention uses the traditional Chinese medicine slag as the raw material of the biochar-based carrier, carries the first metal and the second metal through precursor impregnation and self-heating deactivation in sequence, has wide sources and low cost, can realize the recycling of waste resources by preparing the traditional Chinese medicine slag into the catalyst, and is simultaneously used in the wastewater treatment, thereby realizing the treatment of waste by waste; the wet oxidation catalyst can break carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds and the like of organic pollutants in ABS wastewater, degrade the organic pollutants into micromolecular substances, and improve the removal rate of the organic pollutants and the biodegradability of the wastewater.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
it is an object of the present invention to provide a wet oxidation catalyst comprising a biochar-based support, a first metal and a second metal; the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues.
The wet oxidation catalyst takes Chinese medicine residues and/or plant extraction residues as raw materials of a biochar-based carrier, and further loads first metal and second metal; the first metal and the second metal catalyze organic pollutants in the ABS wastewater to degrade into micromolecular substances, so that the removal rate of the organic pollutants and the biodegradability of the wastewater are improved, and the subsequent biochemical treatment effect is improved; the wet oxidation catalyst has large surface area, large load and high treatment efficiency; the traditional Chinese medicine slag has wide sources and low price, and the catalyst prepared from the traditional Chinese medicine slag can realize the recycling of waste resources, and can be used in wastewater treatment to realize the treatment of waste by waste.
As a preferred embodiment of the present invention, the first metal includes Fe and/or Cu.
Preferably, the second metal comprises Mn and/or Ce.
It is worth to say that the first metal Fe and/or Cu can be used as the second carrier of the catalyst, and the active oxygen free radicals generated by the second metal Mn and/or Ce migrate to Fe and/or Cu to generate a large number of oxygen vacancies and reactive sites on the surface of the Fe and/or Cu, and the active oxygen and hydrogen form hydroxyl free radicals, so that carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds and the like of organic pollutants in the ABS wastewater are broken and degraded into small molecules.
Preferably, the content of the first metal is 0.5 to 8wt%, for example, 0.5wt%,1wt%,1.5wt%,2wt%,2.5wt%,3wt%,3.5wt%,4wt%,4.5wt%,5wt%,5.5wt%,6wt%,6.5wt%,7wt%,7.5wt%,8wt%, etc. but not limited to the recited values, and other non-recited values within the above range of values are equally applicable.
The content of the second metal is preferably 0.1 to 5wt%, for example, 0.1wt%,0.5wt%,1wt%,1.5wt%,2wt%,2.5wt%,3wt%,3.5wt%,4wt%,4.5wt%,5wt%, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
It is a second object of the present invention to provide a method for producing the wet oxidation catalyst according to one of the objects, comprising the steps of:
(1) Sieving the raw material of the biochar-based carrier to obtain fine biochar-based carrier materials;
wherein the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues;
(2) Mixing the precursor solution with the biochar-based carrier fine material in the step (1), then impregnating, and carrying out solid-liquid separation to obtain an impregnating material;
wherein the solute of the precursor solution comprises a first metal salt and a second metal salt;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) to obtain the wet oxidation catalyst.
The invention uses the traditional Chinese medicine slag as the raw material of the biochar-based carrier, and sequentially carries out precursor impregnation and self-heating deactivation to obtain the wet oxidation catalyst with low price, large surface area, large load and high treatment efficiency.
In a preferred embodiment of the present invention, the mesh size of the screen used in the step (1) is 50 to 200 mesh, for example, 50 mesh, 80 mesh, 100 mesh, 120 mesh, 150 mesh, 180 mesh, 200 mesh, etc., and more preferably 50 to 100 mesh, for example, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, etc., but the screen is not limited to the above-mentioned values, and other non-mentioned values in the above-mentioned value ranges are applicable.
As a preferred embodiment of the present invention, the first metal salt in step (2) includes an iron salt and/or a copper salt.
Preferably, the iron salt comprises any one or a combination of at least two of ferric nitrate, ferric chloride or ferric sulfate, typical but non-limiting examples of which include a combination of ferric nitrate and ferric chloride, a combination of ferric nitrate and ferric sulfate, and a combination of ferric chloride and ferric sulfate.
Preferably, the copper salt comprises any one or a combination of at least two of copper nitrate, copper chloride or copper sulfate, typical but non-limiting examples of which include a combination of copper nitrate and copper chloride, a combination of copper nitrate and copper sulfate, and a combination of copper chloride and copper sulfate.
Preferably, the second metal salt of step (2) comprises a manganese salt and/or a cerium salt.
Preferably, the manganese salt comprises any one or a combination of at least two of manganese nitrate, manganese chloride or manganese sulfate, typical but non-limiting examples of which include a combination of manganese nitrate and manganese chloride, a combination of manganese nitrate and manganese sulfate, and a combination of manganese chloride and manganese sulfate.
Preferably, the cerium salt comprises any one or a combination of at least two of cerium nitrate, cerium chloride or cerium sulfate, typical but non-limiting examples of which include a combination of cerium nitrate and cerium chloride, a combination of cerium nitrate and cerium sulfate, and a combination of cerium chloride and cerium sulfate.
Preferably, the solvent of the precursor solution of step (2) comprises water. As a preferable embodiment of the present invention, the concentration of the first metal salt in the precursor solution in the step (2) is 0.5 to 5mol/L, for example, 0.5mol/L,1mol/L,1.3mol/L,1.7mol/L,2mol/L,2.2mol/L,2.6mol/L,3mol/L,3.4mol/L,3.8mol/L,4mol/L,4.3mol/L,4.7mol/L,5mol/L, etc., but not limited to the values listed above, and other values not listed in the above-mentioned numerical ranges are equally applicable.
Preferably, the concentration of the second metal salt in the precursor solution in the step (2) is 0.1 to 4mol/L, for example, 0.1mol/L,0.2mol/L,0.5mol/L,0.7mol/L,1mol/L,1.3mol/L,1.7mol/L,2mol/L,2.3mol/L,2.6mol/L,3mol/L,3.4mol/L,3.8mol/L,4mol/L, etc., but not limited to the values listed, and other values not listed in the above-mentioned numerical ranges are equally applicable.
Preferably, the mass ratio of the precursor solution to the biochar-based carrier fine material in the step (2) is (20-100): 1, for example, 20:1, 26:1, 30:1, 34:1, 40:1, 45:1, 51:1, 57:1, 60:1, 68:1, 75:1, 79:1, 83:1, 87:1, 90:1, 94:1, 96:1, 100:1, etc., but not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the impregnation in the step (2) is 10 to 30 ℃, for example, 10 ℃,12 ℃,14 ℃,16 ℃,18 ℃,20 ℃,22 ℃,24 ℃,26 ℃,28 ℃,30 ℃ and the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the time of the impregnation in the step (2) is 4-8 hours, for example, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.3 hours, 5.5 hours, 5.7 hours, 6 hours, 6.2 hours, 6.5 hours, 7 hours, 7.5 hours, 7.8 hours, 8 hours, etc., but not limited to the recited values, and other non-recited values in the above range are equally applicable.
Preferably, the preparation method further comprises: and (3) carrying out first drying on the impregnating material in the step (2) before the pyrolysis self-activation reaction in the step (3).
Preferably, the temperature of the first drying is 80-120 ℃, for example, 80 ℃,85 ℃,90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃,120 ℃, etc., but not limited to the recited values, and other non-recited values within the above-recited range are equally applicable.
Preferably, the first drying time is 8-12h, for example, 8h,8.5h,9h,9.5h,10h,10.5h,11h,11.5h,12h, etc., but not limited to the recited values, and other non-recited values within the above range are equally applicable.
As a preferred technical scheme of the invention, the pyrolysis self-activation reaction in the step (3) is carried out under a nitrogen atmosphere.
Preferably, the pyrolysis self-activation reaction of step (3) comprises a heating stage and a pyrolysis stage which are sequentially performed.
Preferably, the temperature rising rate of the temperature rising stage is 1-10 ℃ per minute, for example, 1 ℃/min,2 ℃/min,3 ℃/min,4 ℃/min,5 ℃/min,6 ℃/min,7 ℃/min,8 ℃/min,9 ℃/min,10 ℃/min and the like; further preferably 5 to 10℃per minute, for example, 5℃per minute, 5.5℃per minute, 6℃per minute, 6.5℃per minute, 7℃per minute, 7.5℃per minute, 8℃per minute, 8.5℃per minute, 9℃per minute, 9.5℃per minute, 10℃per minute, etc., but not limited to the values recited, and other values not recited in the above-mentioned ranges are applicable.
Preferably, the end temperature of the warming stage is the same as the temperature of the pyrolysis stage.
Preferably, the temperature of the pyrolysis stage is 600-900 ℃, for example 600-630 ℃,650 ℃,680 ℃,700 ℃,720 ℃,750 ℃,770 ℃,800 ℃,830 ℃,850 ℃,880 ℃,900 ℃, etc.; further preferably 700 to 800 ℃, for example, 700 ℃,720 ℃,740 ℃,750 ℃,760 ℃,780 ℃,800 ℃, etc., but not limited to the values recited, and other values not recited in the above-mentioned numerical ranges are equally applicable.
Preferably, the pyrolysis stage is carried out for a period of 1-6 hours, for example 1h,2h,3h,4h,5h,6h, etc.; further preferably, the reaction time is 2 to 4 hours, and for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours and the like can be used, but the reaction time is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
As a preferable technical scheme of the invention, the preparation method further comprises the following steps: and (3) cleaning and second drying the wet oxidation catalyst obtained in the step (3).
Preferably, the cleaning agent used for the cleaning comprises pure water.
Preferably, the temperature of the second drying is 80-120 ℃, for example, 80 ℃,85 ℃,90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃,120 ℃, etc., but not limited to the recited values, and other non-recited values within the above-recited range are equally applicable.
Preferably, the second drying time is 8-12h, for example, 8h,8.5h,9h,9.5h,10h,10.5h,11h,11.5h,12h, etc., but not limited to the recited values, and other non-recited values within the above range are equally applicable.
It is a further object of the present invention to provide the use of a wet oxidation catalyst as defined in one of the objects for treating ABS wastewater.
The invention relates to a method for treating ABS wastewater by wet oxidation, which is characterized in that under the action of a wet oxidation catalyst, hydroxyl radicals generated in the wet catalytic oxidation process degrade macromolecular organic pollutants in wastewater into micromolecular substances and CO 2 、H 2 O, etc., and has the advantages of mild reaction condition, high efficiency, simple operation, low operation cost and no secondary pollution.
It is worth to say that the method for treating ABS wastewater by using the wet oxidation catalyst comprises the following steps:
adding hydrogen peroxide after regulating the pH value of the ABS waste water to 6-9, controlling the molar ratio of the hydrogen peroxide to COD in the ABS waste water to be (0.5-2): 1, preheating, then entering a fixed bed reactor filled with a wet oxidation catalyst, and reacting for 0.5-2h at 60-100 ℃ to finish the degradation of pollutants in the ABS waste water.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) The wet oxidation catalyst has large surface area and large load, and breaks carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds and the like of macromolecular organic pollutants in ABS wastewater through the synergistic effect of the first metal and the second metal, so as to degrade the macromolecular organic pollutants into micromolecular substances and CO 2 、H 2 O has higher wastewater treatment efficiency and low price;
(2) The preparation method of the wet oxidation catalyst takes the Chinese medicinal residues as a carrier, the Chinese medicinal residues are wide in sources and low in cost, and the catalyst prepared by the method can realize the recycling of waste resources, and can be used in wastewater treatment to realize the treatment of waste by waste; the treatment method is simple and easy to operate, high in treatment efficiency and free of secondary pollution.
Drawings
FIG. 1 is an SEM image of a wet oxidation catalyst obtained according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, fe and Mn; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 4wt% and the content of Mn is 0.5wt%; the preparation method comprises the following steps:
(1) Sieving the Chinese medicinal residues with 100 mesh sieve to obtain biochar-based carrier fine materials;
(2) Mixing the precursor solution with the biochar-based carrier fine material in the step (1) according to the mass ratio of 45:1, soaking for 6 hours at 20 ℃, performing solid-liquid separation, and performing first drying for 8 hours at 120 ℃ to obtain a soaked material;
wherein the solute of the precursor solution comprises ferric nitrate and manganese nitrate; in the precursor solution, the concentration of ferric nitrate is 3.5mol/L, and the concentration of manganese nitrate is 1mol/L;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) under the nitrogen atmosphere, and heating to 700 ℃ at a speed of 5 ℃/min for pyrolysis for 5 hours during the pyrolysis self-activation reaction, washing by pure water, and then carrying out second drying at 120 ℃ for 8 hours to obtain the wet oxidation catalyst.
As shown in the SEM diagram of the wet oxidation catalyst obtained in the embodiment as shown in FIG. 1, the surface morphology of the prepared catalyst is rough, a loose and porous fluffy three-dimensional structure is formed, and the addition of the metal catalyst does not generate agglomeration sites, so that the catalyst has good surface dispersibility.
Example 2
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, cu and Ce; the raw materials of the biochar-based carrier are Chinese medicinal residues; the Cu content is 8wt%, and the Ce content is 0.1wt%; the preparation method comprises the following steps:
(1) Sieving the Chinese medicinal residues with a 50-mesh screen to obtain biochar-based carrier fine materials;
(2) Mixing the precursor solution with the biochar-based carrier fine material in the step (1) according to the mass ratio of 100:1, soaking at 10 ℃ for 8 hours, performing solid-liquid separation, and performing first drying at 80 ℃ for 12 hours to obtain a soaked material;
wherein the solute of the precursor solution comprises cerium nitrate of copper nitrate; in the precursor solution, the concentration of copper nitrate is 5mol/L, and the concentration of cerium nitrate is 0.1mol/L;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) under the nitrogen atmosphere, and heating to 900 ℃ at a speed of 10 ℃/min for pyrolysis 1h during the pyrolysis self-activation reaction, washing by pure water, and then carrying out second drying at 80 ℃ for 12h to obtain the wet oxidation catalyst.
Example 3
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, fe and Ce; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 0.5wt% and the content of Ce is 5wt%; the preparation method comprises the following steps:
(1) Sieving the Chinese medicine residues through a 200-mesh screen to obtain a biochar-based carrier fine material;
(2) Mixing the precursor solution with the biochar-based carrier fine material in the step (1) according to the mass ratio of 20:1, soaking for 4 hours at 30 ℃, performing solid-liquid separation, and performing first drying at 100 ℃ for 10 hours to obtain a soaked material;
wherein the solute of the precursor solution comprises ferric nitrate and cerium nitrate; in the precursor solution, the concentration of ferric nitrate is 0.5mol/L, and the concentration of cerium nitrate is 4mol/L;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) under the nitrogen atmosphere, and heating to 600 ℃ at a speed of 1 ℃/min for pyrolysis 6h during the pyrolysis self-activation reaction, washing by pure water, and then carrying out second drying at 100 ℃ for 10h to obtain the wet oxidation catalyst.
Example 4
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, fe and Mn; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 4wt%, and the content of Mn is 0.05wt%; the preparation method is described with reference to example 1, with the only difference that: and (3) in the precursor solution in the step (2), the concentration of the manganese nitrate is 0.08mol/L.
Example 5
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, fe and Mn; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 0.2wt% and the content of Mn is 0.5wt%; the preparation method is described with reference to example 1, with the only difference that: and (3) in the precursor solution in the step (2), the concentration of ferric nitrate is 0.4mol/L.
Example 6
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, mg and Mn; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Mg is 4wt%, and the content of Mn is 0.5wt%; the preparation method is described with reference to example 1, with the only difference that: in the precursor solution in the step (2), the concentration of magnesium nitrate is 3.5mol/L, and the concentration of manganese nitrate is 1mol/L.
Example 7
The embodiment provides a wet oxidation catalyst and a preparation method thereof, wherein the wet oxidation catalyst comprises a biochar-based carrier, mg and Zn; the raw materials of the biochar-based carrier are Chinese medicinal residues; the Cu content was 4wt% and the Ni content was 0.5wt%; the preparation method is described with reference to example 1, with the only difference that: in the precursor solution in the step (2), the concentration of magnesium nitrate is 3.5mol/L, and the concentration of nickel nitrate is 1mol/L.
Comparative example 1
The present comparative example provides a wet oxidation catalyst including a biochar-based carrier, fe, and Cu, and a method of preparing the same; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 4wt%, and the content of Cu is 0.5wt%; the preparation method is described with reference to example 1, with the only difference that: the solute of the precursor solution in the step (2) comprises ferric nitrate and cupric nitrate; in the precursor solution, the concentration of ferric nitrate is 3.5mol/L, and the concentration of copper nitrate is 1mol/L.
Comparative example 2
The present comparative example provides a wet oxidation catalyst including a biochar-based carrier and Fe, and a method of preparing the same; the raw materials of the biochar-based carrier are Chinese medicinal residues; the content of Fe is 4wt%; the preparation method comprises the following steps:
(1) Sieving the Chinese medicinal residues with 100 mesh sieve to obtain biochar-based carrier fine materials;
(2) Mixing 1mol/L ferric nitrate solution with the fine charcoal-based carrier material in the step (1) according to the mass ratio of 45:1, soaking for 6 hours at 20 ℃, performing solid-liquid separation, and performing first drying for 8 hours at 120 ℃ to obtain a soaked material;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) under the nitrogen atmosphere, and heating to 700 ℃ at a speed of 5 ℃/min for pyrolysis for 5 hours during the pyrolysis self-activation reaction, washing by pure water, and then carrying out second drying at 120 ℃ for 8 hours to obtain the wet oxidation catalyst.
Comparative example 3
Comparative examples provide a wet oxidation catalyst comprising a carbon-based support, fe, and Mn, and a method of preparing the same; the raw material of the carbon-based carrier is tar residue; the content of Fe is 4wt% and the content of Mn is 0.5wt%; the preparation method comprises the following steps:
(1) Sieving the tar residues through a 100-mesh screen to obtain carbon-based carrier fine materials;
(2) Mixing the precursor solution with the carbon-based carrier fine material in the step (1) according to the mass ratio of 45:1, soaking for 6 hours at 20 ℃, performing solid-liquid separation, and performing first drying for 8 hours at 120 ℃ to obtain a soaked material;
wherein the solute of the precursor solution comprises ferric nitrate and manganese nitrate; in the precursor solution, the concentration of ferric nitrate is 3.5mol/L, and the concentration of manganese nitrate is 1mol/L;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) under the nitrogen atmosphere, and heating to 700 ℃ at a speed of 5 ℃/min for pyrolysis for 5 hours during the pyrolysis self-activation reaction, washing by pure water, and then carrying out second drying at 120 ℃ for 8 hours to obtain the wet oxidation catalyst.
The wet oxidation catalysts obtained in the above examples and comparative examples are used for treating ABS wastewater, and the treatment method comprises the steps of:
after the pH value of 100mLABS waste water is regulated to 6, the waste water is placed into a fixed bed reactor together with 4g of wet oxidation catalyst and hydrogen peroxide, the mol ratio of the hydrogen peroxide to COD in the ABS waste water is controlled to be 2:1, and after the waste water reacts for 2 hours at 100 ℃, the AB after test treatmentCOD in S wastewater is marked as C 1 The method comprises the steps of carrying out a first treatment on the surface of the Then the treatment efficiency of the wet oxidation catalyst=c 1 /C 0 X 100%, where C 0 Is COD of untreated ABS wastewater.
The treatment efficiencies of the wet oxidation catalysts obtained in the above examples and comparative examples for ABS wastewater are shown in table 1.
TABLE 1
From table 1, the following points can be found:
(1) As can be seen from examples 1 to 3, the wet oxidation catalyst of the present invention can obtain a better ABS wastewater treatment effect by the synergistic effect of the first metal (Fe and/or Cu) and the second metal (Mn and/or Ce);
(2) Comparing example 1 with examples 4 and 5, it can be seen that the catalytic efficiency is reduced due to the second metal Mn content of 0.05wt% in example 4, which is lower than the preferred 0.1 to 5wt% in the present invention; since the content of the first metal Fe in example 5 is 0.2wt% which is less than the preferred 0.5 to 8wt% of the present invention, the catalytic efficiency is lowered;
(3) Comparing example 1 with examples 6 and 7, it can be seen that the first metal in example 6 is Mg, and not the preferred Fe and/or Cu of the present invention, the catalytic efficiency is reduced compared to example 1; in example 6, the first metal is Mg, the second metal is Ni, and the preferred first metals of the invention, fe and/or Cu, and the second metals, mn and/or Ce, have lower catalytic efficiency than in example 1 and lower catalytic efficiency than in example 6;
(4) Comparing example 1 with comparative examples 1-3, it can be seen that the first metals in comparative example 1 are Fe and Cu, and no second metals, and the catalytic efficiency is lower than that of example 1; the first metal in comparative example 2 is Fe, no second metal, and its catalytic efficiency is lower than that of example 1 and lower than that of comparative example 1; the carrier raw material in comparative example 3 is tar residue, but is not the traditional Chinese medicine residue preferred by the invention, and because the composition difference between tar residue and traditional Chinese medicine residue is large, under the preferred condition of the invention, the tar residue cannot be prepared into a catalyst with excellent performance, and the catalytic efficiency is low.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A wet oxidation catalyst, characterized in that the wet oxidation catalyst comprises a biochar-based carrier, a first metal and a second metal; the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues.
2. The wet oxidation catalyst of claim 1, wherein the first metal comprises Fe and/or Cu;
preferably, the second metal comprises Mn and/or Ce;
preferably, the content of the first metal is 0.5 to 8wt%;
preferably, the content of the second metal is 0.1 to 5wt%.
3. A method of preparing the wet oxidation catalyst according to claim 1 or 2, comprising the steps of:
(1) Sieving the raw material of the biochar-based carrier to obtain fine biochar-based carrier materials;
wherein the raw materials of the biochar-based carrier comprise Chinese medicinal residues and/or plant extraction residues;
(2) Mixing the precursor solution with the biochar-based carrier fine material in the step (1), then impregnating, and carrying out solid-liquid separation to obtain an impregnating material;
wherein the solute of the precursor solution comprises a first metal salt and a second metal salt;
(3) And (3) carrying out pyrolysis self-activation reaction on the impregnating compound in the step (2) to obtain the wet oxidation catalyst.
4. A process for the preparation of a wet oxidation catalyst according to claim 3, wherein the mesh size of the screen used in the sieving in step (1) is 50-200 mesh, more preferably 50-100 mesh.
5. The method of preparing a wet oxidation catalyst according to claim 3 or 4, wherein the first metal salt of step (2) comprises an iron salt and/or a copper salt;
preferably, the iron salt comprises any one or a combination of at least two of ferric nitrate, ferric chloride or ferric sulfate;
preferably, the copper salt comprises any one or a combination of at least two of copper nitrate, copper chloride or copper sulfate;
preferably, the second metal salt of step (2) comprises a manganese salt and/or a cerium salt;
preferably, the manganese salt comprises any one or a combination of at least two of manganese nitrate, manganese chloride or manganese sulfate;
preferably, the cerium salt includes any one or a combination of at least two of cerium nitrate, cerium chloride or cerium sulfate;
preferably, the solvent of the precursor solution of step (2) comprises water.
6. The method for producing a wet oxidation catalyst according to any one of claims 3 to 5, wherein the concentration of the first metal salt in the precursor solution of step (2) is 0.5 to 5mol/L;
preferably, the concentration of the second metal salt in the precursor solution of step (2) is 0.1-4mol/L;
preferably, the mass ratio of the precursor solution to the biochar-based carrier fine material in the step (2) is (20-100): 1.
7. The method for producing a wet oxidation catalyst according to any one of claims 3 to 6, wherein the temperature of the impregnation in step (2) is 10 to 30 ℃;
preferably, the time of the impregnation in step (2) is 4-8 hours;
preferably, the preparation method further comprises: carrying out first drying on the impregnating material in the step (2) before the pyrolysis self-activation reaction in the step (3);
preferably, the temperature of the first drying is 80-120 ℃;
preferably, the first drying time is 8-12 hours.
8. The method for producing a wet oxidation catalyst according to any one of claims 3 to 7, wherein the pyrolysis self-activation reaction of step (3) is performed under a nitrogen atmosphere;
preferably, the pyrolysis self-activation reaction in the step (3) comprises a heating stage and a pyrolysis stage which are sequentially carried out;
preferably, the temperature rising rate of the temperature rising stage is 1-10 ℃/min, and more preferably 5-10 ℃/min;
preferably, the end temperature of the warming stage is the same as the temperature of the pyrolysis stage;
preferably, the temperature of the pyrolysis stage is 600-900 ℃, further preferably 700-800 ℃;
preferably, the pyrolysis stage is for a period of 1 to 6 hours, more preferably 2 to 4 hours.
9. The method for producing a wet oxidation catalyst according to any one of claims 3 to 8, further comprising: washing and second drying the wet oxidation catalyst obtained in the step (3);
preferably, the cleaning agent used for cleaning comprises pure water;
preferably, the temperature of the second drying is 80-120 ℃;
preferably, the second drying time is 8-12 hours.
10. Use of a wet oxidation catalyst according to claim 1 or 2, for treating ABS wastewater.
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| CN117049763A (en) * | 2023-10-11 | 2023-11-14 | 上海鸣桦环境科技有限公司 | Method for degrading sludge organic matters by wet oxidation technology |
| CN117049763B (en) * | 2023-10-11 | 2023-12-22 | 上海鸣桦环境科技有限公司 | Method for degrading sludge organic matters by wet oxidation technology |
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