CN113117736B - Catalytic wet oxidation catalyst and preparation method thereof - Google Patents
Catalytic wet oxidation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN113117736B CN113117736B CN201911417792.1A CN201911417792A CN113117736B CN 113117736 B CN113117736 B CN 113117736B CN 201911417792 A CN201911417792 A CN 201911417792A CN 113117736 B CN113117736 B CN 113117736B
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- Prior art keywords
- oxidation catalyst
- wet oxidation
- catalytic wet
- preparing
- catalyst according
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 71
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004927 clay Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 73
- 239000002351 wastewater Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
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- 239000003245 coal Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
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- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002674 hyaluronan Polymers 0.000 claims description 2
- 229960003160 hyaluronic acid Drugs 0.000 claims description 2
- FZWBNHMXJMCXLU-BLAUPYHCSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-BLAUPYHCSA-N 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 5
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- 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 12
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- 238000010521 absorption reaction Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7807—A-type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
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Abstract
The invention discloses a catalytic wet oxidation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) The method comprises the steps of (1) enabling silicon-aluminum clay, activated carbon and alkali-soluble fiber to be in short filament cutting, enabling a binder to be in contact with each other in the presence of water, and then obtaining a material A through molding and high-temperature heat treatment; (2) The material A is contacted with caustic soda solution and subjected to hydrothermal treatment, and solid phase material obtained after cooling washing and solid-liquid separation is further subjected to drying treatment to obtain a material B; (3) Introducing the material B into an active component, and drying and roasting to obtain a material C; (4) And (3) feeding the material C into a mixed solution of the modifier and the nano oxide sol for soaking treatment, and then separating out the organic solvent to obtain the catalyst.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a catalytic material for wastewater treatment and a preparation method thereof.
Background
The chemical wastewater mainly comes from organic matters discharged in the production process of chemical products (especially fine chemical products such as pharmacy, printing and dyeing, daily chemicals and the like), and is mainly characterized by complex water quality components, high COD (chemical oxygen demand) and a large amount of toxic and harmful substances, contains a large amount of organic matters difficult to biodegrade and the like, and has stronger polarity and great treatment difficulty.
At present, the treatment methods of organic pollutants in chemical wastewater are mostly flocculation, electrolysis and adsorption conventional physical and chemical methods and biochemical methods, such as SBR, A/O technology and the like. However, due to the complex components of the chemical wastewater, the water quality and the water quantity change greatly, and a good treatment effect is difficult to obtain. The advanced oxidation technology can generate free radical species with high oxidability, mineralizes various organic pollutants in the wastewater into carbon dioxide and water almost without selectivity, has strong tolerance to water quality and water quantity fluctuation, and is a treatment method with great prospect. However, the conventional catalyst is limited by the adsorption reaction step, the initial driving force of the reaction is insufficient, and the effect is not ideal. The supported catalyst prepared from the composite carrier with the multistage controllable pore structure is used for carrying out real-time oxidative degradation on organic pollutants in chemical wastewater, has wide applicability, can effectively shorten the treatment period, improves the treatment effect and the economy, and has wide application prospect in practical application.
CN201310200060.3 discloses a process method for advanced treatment of petrochemical wastewater by ozone catalytic oxidation, which is characterized in that: petrochemical wastewater sequentially flows through a pre-oxidation tower, a catalytic oxidation tower I and a catalytic oxidation tower II, and the three towers are respectively filled with high-pore inert filler, an active alumina-based catalyst and granular active carbon, wherein the pre-oxidation tower operates under pressure.
CN201810118624.1 discloses a catalyst for ozone catalytic oxidation treatment of chemical wastewater and a preparation method, the catalyst comprises a carrier and active components, wherein the carrier is alumina, a molecular sieve, ceramsite and zirconia, and the active components are oxides of copper, iron, nickel, manganese and cerium.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalytic wet oxidation catalyst, a preparation method thereof and a method for treating wastewater by adopting the prepared catalyst for catalytic oxidation, which solve the problem that the traditional physical and chemical methods are difficult to treat and reach the emission standard.
The first aspect of the invention provides a method for preparing a catalytic wet oxidation catalyst, which comprises the following steps:
(1) The method comprises the steps of (1) enabling silicon-aluminum clay, activated carbon and alkali-soluble fiber to be in short filament cutting, enabling a binder to be in contact with each other in the presence of water, and then obtaining a material A through molding and high-temperature heat treatment;
(2) The material A obtained in the step (1) is contacted with caustic soda solution and subjected to hydrothermal treatment, and solid phase material obtained after cooling washing and solid-liquid separation is further subjected to drying treatment to obtain a material B;
(3) Introducing the material B obtained in the step (2) into an active component, and drying and roasting to obtain a material C;
(4) And (3) feeding the material C into a mixed solution of the modifier and the nano oxide sol for soaking treatment, and then separating out the organic solvent to obtain the catalyst.
In the preparation method of the catalytic wet oxidation catalyst, the silicon-aluminum clay in the step (1) is firstly roasted for 3-8 hours at a high temperature of 600-1000 ℃.
In the preparation method of the catalytic wet oxidation catalyst, the activated carbon in the step (1) can be selected from commercial activated carbon according to the requirement or prepared by itself according to the existing preparation method, such as wood activated carbon, shell activated carbon and coal-based activated carbon. The activated carbon preferably used in the invention is powdery activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m 2 And/g, wherein the average pore diameter is 0.5-4.0 nm, and the pore volume of pores with the pore diameter of 1.5-3.5 nm accounts for more than 90% of the total pore volume.
In the preparation method of the catalytic wet oxidation catalyst, the silicon dioxide and the silicon aluminum clay in the step (1) are mixedThe mass ratio of the alumina is 1-1.5:1, and the sum of the mass of the silicon dioxide and the alumina is more than 80% of the total mass of the silicon aluminum clay. Further preferably, the silica-alumina clay used in the present invention is a powdery solid having a particle size of 300 to 2000 mesh, an average pore diameter of 3.0 to 25.0nm, and a specific surface area in the range of 5 to 500m 2 /g。
In the preparation method of the catalytic wet oxidation catalyst, in the step (1), the alkali-soluble fiber has a chopped filament length of 2-5 mm and a filament diameter of 10-70 nm, and specifically, the alkali-soluble fiber can be one or a combination of more than one of alkali-soluble polyester fiber, alkali-soluble carboxymethyl cellulose fiber and alkali-soluble hydroxyethyl cellulose fiber.
In the preparation method of the catalytic wet oxidation catalyst, the binder in the step (1) is an inorganic binder, preferably one or more of silicate inorganic binders and phosphate inorganic binders; the silicate inorganic binder is one or more of tricalcium silicate, dicalcium silicate, calcium silicate, aluminum silicate and sodium silicate, preferably aluminum silicate or sodium silicate; the phosphate inorganic binder is one or more of aluminum dihydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium tripolyphosphate, sodium pyrophosphate and sodium hexametaphosphate, preferably sodium tripolyphosphate and aluminum dihydrogen phosphate.
In the preparation method of the catalytic wet oxidation catalyst, in the step (1), the mass percentage of the activated carbon, the silicon-aluminum clay and the binder is 10-40%: 50-80%: 2-10% of the alkali-soluble fiber is mixed, and the consumption of the alkali-soluble fiber chopped filaments is 3-15% of the total mass of the carrier.
In the method for preparing the catalytic wet oxidation catalyst, the hydrothermal treatment in the step (2) is carried out at 80-220 ℃ (preferably 85-160 ℃) for 2-8 hours (preferably 3-6 hours).
In the preparation method of the catalytic wet oxidation catalyst, the molar ratio of Na in the caustic soda solution to Si in the silicon-aluminum clay in the step (2) is 3-3.4: 1, the mass concentration of the caustic soda solution is 7.5-10%.
In the method for preparing the catalytic wet oxidation catalyst, the drying in the step (2) is drying treatment for 3-24 hours (preferably 6-8 hours) at a temperature of 50-100 ℃ (preferably 60-70 ℃).
In the preparation method of the catalytic wet oxidation catalyst, the active component in the step (3) is one or more of transition metal and rare earth metal; preferably one or more of copper, manganese and cerium; further preferred are cerium and optionally copper and/or manganese. The mass of the active component accounts for 5-20% of the total mass of the catalyst.
In the method for preparing the catalytic wet oxidation catalyst according to the present invention, the method for introducing the active component in the step (3) may be any one of methods existing in the art, such as impregnation, kneading, etc., and preferably an impregnation method is adopted according to practical, and when an impregnation method is adopted, the method includes preparing an active component precursor solution, and then contacting the solution with the material B obtained in the step (2) to perform an impregnation treatment, where the active component precursor may be one or more of nitrate, sulfate, acetate and chloride of an active metal component.
In the preparation method of the catalytic wet oxidation catalyst, the drying temperature in the step (3) is 60-150 ℃, preferably 80-110 ℃, and the drying time is 3-12 h, preferably 4-6 h. The roasting temperature is 500-1500 ℃, preferably 600-800 ℃, and the roasting time is 2-6 h, preferably 3-4 h.
In the preparation method of the catalytic wet oxidation catalyst, the sex modifier in the step (4) is a polyhydroxy compound, and can be one or a combination of more of hydrophilic chitosan, polyacrylamide, polyvinyl alcohol, dextran and hyaluronic acid.
In the preparation method of the catalytic wet oxidation catalyst, the nano oxide sol in the step (4) is alcohol-based sol of nano silicon dioxide and/or nano titanium dioxide.
In the preparation method of the catalytic wet oxidation catalyst, the solid content of the mixed solution of the modifier and the nano oxide sol in the step (4) accounts for 3-10% of the total mass of the catalyst.
The second aspect of the invention provides a catalytic wet oxidation catalyst obtained by the preparation method, wherein the catalyst comprises an active component and a carrier; the active component is one or more of transition metal and rare earth metal; preferably one or more of copper, manganese and cerium; further preferred are cerium and optionally copper and/or manganese. The mass of the active component accounts for 5% -20% of the total mass of the catalyst; the carrier is prepared by performing hydrothermal treatment on active carbon, alkali-soluble fiber chopped filaments, an inorganic binder and silica-alumina clay to prepare a formed particle precursor alkali liquor, the carrier is provided with three-stage pore channels, the pore diameter of a first-stage pore channel is 0.1-1.5 nm, the pore volume of the first-stage pore channel accounts for more than 15% of the total pore volume, preferably 20-30%, the pore diameter of a second-stage pore channel is 1.5-5 nm, the pore volume of the second-stage pore channel accounts for more than 25% of the total pore volume, preferably 35-40%, the pore diameter of a third-stage pore channel accounts for 5-50 nm, the pore volume of the third-stage pore channel accounts for less than 60% of the total pore volume, preferably 30-40%, and the three-stage pore channels are communicated by a crosslinked intercommunication pore channel formed after the alkali-soluble fiber chopped filaments in the carrier.
In the catalytic wet oxidation catalyst, the specific surface area of the catalyst is more than 200m 2 Per gram, pore volume greater than 0.20. 0.20 cm 3 /g。
In a third aspect, the present invention provides a method of catalytic oxidation of wastewater by feeding wastewater and an oxidant into a reactor filled with a catalytic wet oxidation catalyst as described above to effect catalytic oxidation.
In the wastewater catalytic oxidation treatment method, the oxidant is one or two of hydrogen peroxide and ozone, and the dosage of the oxidant is 10-100 g of oxidant added per 10g of COD.
In the wastewater catalytic oxidation treatment method, the wastewater is biochemical effluent, acrylic fiber wastewater, coking wastewater, pharmaceutical wastewater and printing and dyeing wastewater, and the COD (chemical oxygen demand) range is 40-1000 mg/L.
Compared with the prior art, the catalytic wet oxidation catalyst and the preparation method thereof provided by the invention have the following advantages:
1. according to the preparation method of the catalyst, the carrier with the surface rich in the 4A molecular sieve and the hydroxylation active carbon is prepared by using the alkali liquor post-treatment method, so that the catalyst has strong adsorption performance, the mass transfer process of organic pollutants from a water phase to the surface of the catalyst is accelerated, a micro-reaction zone with local high concentration is formed on the surface of the catalyst, and the initial driving force of the catalytic reaction is improved. The 4A molecular sieve with higher crystallinity can be obtained by alkali liquor hydro-thermal treatment, which is beneficial to increasing the specific surface area of the pore volume of the carrier and improving the adsorption catalysis performance of the carrier. And the fiber chopped filaments are used for forming the pore canal of the cross-linked intercommunication pore canal communicated molecular sieve, activated carbon and silicon aluminum clay, so that the mass transfer process of organic matters in the catalyst can be effectively improved, the contact probability of the organic matters and catalytic active sites is increased, and the catalytic activity is effectively improved. The hydrophilic modification of the catalyst improves the capacity of the catalyst to treat polar wastewater.
2. The organic pollutant wastewater enters the reactor and then contacts with the oxidant, the oxidant generates free radical species with strong oxidability under the action of the catalyst, and the organic matters are mineralized to generate carbon dioxide and water in a non-selective way. The defects of high selectivity and poor adaptability of the conventional method to organic species in the wastewater are avoided. The reaction is carried out at normal temperature and normal pressure, so that the equipment investment is low; the free radical species generated by the catalytic decomposition of the oxidant through the catalyst initiates the free radical chain reaction to remove the organic pollutants, and the COD removal efficiency is high.
Detailed Description
The preparation method of the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to the examples.
In the examples and comparative examples of the present invention, the relative crystallinity was obtained by an X-ray diffraction method (Xu Ruren, pang Wenqin, etc. molecular sieves and porous materials chemistry Beijing: science Press. 2014), and the pore ratio was obtained by physical adsorption data.
Example 1
Preparation of catalyst A1
328.5g of silicon aluminum clay (silicon dioxide mass fraction 47.6%, aluminum oxide mass fraction 43.8%) which is pre-baked at 850 ℃ and 300 meshes of powder shell active carbon (specific surface area 900 m) 2 Per g, average pore diameter 2.48 nm) 90g, alkali-soluble polyester staple fibers45g of the active carbon composite carrier is uniformly mixed together, 126g of 25 wt% sodium silicate inorganic binder and a proper amount of distilled water are added for continuous kneading, a bar extruder is prepared into a cylinder shape of 2.5mm, and the mixture is roasted for 6 hours at 260 ℃ to prepare a precursor of the active carbon composite carrier; 6.5g of the precursor is placed in a 100ml reaction kettle, 81.3g of sodium hydroxide solution with mass concentration of 8.2% is added, the mixture is taken out after being subjected to hydrothermal treatment at 120 ℃ for 6 hours, distilled water is used for washing until the pH value is 7.3, then centrifugal separation is carried out, the separated solid is dried at 85 ℃, and then oxygen is isolated at 800 ℃ for roasting for 5 hours, thus obtaining the composite carrier. Preparing a mixed salt solution of copper nitrate and cerium nitrate according to the water absorption rate of the carrier, wherein CuO and CeO are prepared 2 Accounting for 8.0 percent and 2.0 percent of the total weight of the catalyst respectively. Soaking a carrier for 8 hours by adopting an isovolumetric soaking method, drying at 80 ℃, then roasting for 4 hours at 650 ℃ under the protection of nitrogen in an atmosphere furnace, soaking the cooled catalyst in a hydrophilic chitosan and nano silicon dioxide methanol solution, reacting for 10 hours at 60 ℃, and then removing an organic solvent under the vacuum degree of 80% to obtain the catalyst A1.
Example 2
Preparation of catalyst A2
315g of silica alumina clay (silica mass fraction 50.9%, alumina mass fraction 45.1%) pre-baked at 850 ℃ and 200 mesh powdered wood activated carbon (specific surface area 840m 2 3.47nm of average pore diameter), 99g of alkali-soluble carboxymethyl cellulose fiber chopped filaments 36g are uniformly mixed, then 120g of 30 wt percent sodium silicate inorganic binder and a proper amount of distilled water are added for continuous kneading, a strip extruder is prepared into a 2.5mm clover shape, and the mixture is roasted for 5.5 hours at the temperature of 300 ℃ to prepare a precursor of the active carbon composite carrier; placing 7.1g of precursor in a 100ml reaction kettle, adding 89.9g of sodium hydroxide solution with mass concentration of 7.9%, taking out after hydro-thermal treatment for 4 hours at 160 ℃, washing with distilled water until the pH is 7.6, centrifuging, drying the separated solid at 80 ℃, and roasting for 5 hours at 900 ℃ with oxygen isolated, thus obtaining the composite carrier. Preparing a mixed salt solution of manganese nitrate and cerium nitrate according to the water absorption rate of the carrier, wherein MnO and CeO are prepared 2 And respectively account for 10.0 percent and 2.5 percent of the total weight of the catalyst. Soaking the carrier in the isovolumetric soaking method for 8 hr, stoving at 80 deg.c, protecting with helium in atmosphere furnace, and roasting at 750 deg.c for 4 hrSoaking the cooled catalyst in a hydrophilic chitosan and nano titanium dioxide ethanol solution, reacting for 12 hours at 70 ℃, and then removing the organic solvent at 60% vacuum degree to obtain a catalyst A2.
Example 3
Preparation of catalyst A3
351g of the silica alumina clay (silica mass fraction: 51.1%, alumina mass fraction: 44.8%) subjected to the pre-calcination treatment at 900 ℃ was mixed with 200 mesh powdered coconut shell activated carbon (specific surface area: 1070 m) 2 Per g, average pore diameter 3.86 nm) 81g, alkali-soluble hydroxyethyl cellulose fiber chopped filaments 22.5g, adding 24g of 75 wt% aluminum dihydrogen phosphate inorganic binder and a proper amount of distilled water, continuously kneading, preparing into a cylinder with 3.0mm by a strip extruder, and roasting at 280 ℃ for 7h to obtain a precursor of the active carbon composite carrier; placing 7.0g of precursor in a 100ml reaction kettle, adding 91.9g of sodium hydroxide solution with mass concentration of 8.1%, performing hydrothermal treatment at 90 ℃ for 7 hours, taking out, washing with distilled water until the pH is 7.2, performing centrifugal separation, drying the separated solid at 85 ℃, and then performing roasting at 900 ℃ with oxygen isolated for 4 hours to obtain the composite carrier. Preparing a mixed salt solution of copper nitrate, manganese nitrate and cerium nitrate according to the water absorption rate of the carrier, wherein CuO, mnO and CeO are prepared 2 Accounting for 5.0 percent, 5.0 percent and 2.0 percent of the total weight of the catalyst respectively. Soaking a carrier for 12 hours by adopting an isovolumetric soaking method, drying at 70 ℃, then protecting by helium in an atmosphere furnace, roasting at 650 ℃ for 6 hours, soaking the cooled catalyst in polyacrylamide and nano titanium dioxide ethanol solution, reacting at 70 ℃ for 12 hours, and then removing the organic solvent under 80% vacuum degree to obtain the catalyst A3.
Example 4
Preparation of catalyst A4
342g of 1000 ℃ pre-baked silica alumina clay (silica mass fraction 52.2%, alumina mass fraction 46.1%) and 300 mesh powdered coal-based activated carbon (specific surface 780m 2 Per gram, average pore diameter 4.36 nm), 72g, 27g of alkali-soluble polyester fiber chopped filaments, and then adding 46.7g of 75 wt% aluminum dihydrogen phosphate inorganic binder and a proper amount of distilled water, continuously kneading, preparing into a cylinder with 3.0mm by a extruder, and roasting at 310 ℃ for 5 DEG Ch, preparing a precursor of the active carbon composite carrier; 6.8g of the precursor is placed in a 100ml reaction kettle, 91.2g of sodium hydroxide solution with mass concentration of 8.2% is added, the mixture is taken out after being subjected to hydrothermal treatment at 150 ℃ for 5 hours, distilled water is used for washing until the pH value is 7.6, then centrifugal separation is carried out, the separated solid is dried at 80 ℃, and then oxygen is isolated at 750 ℃ for roasting for 4 hours, thus obtaining the composite carrier. Preparing a mixed salt solution of copper nitrate and cerium nitrate according to the water absorption rate of the carrier, wherein CuO and CeO are prepared 2 And respectively account for 6.5 percent and 4.5 percent of the total weight of the catalyst. Soaking a carrier for 10 hours by adopting an isovolumetric soaking method, drying at 75 ℃, then roasting for 4 hours at 750 ℃ in an atmosphere furnace under the protection of nitrogen, soaking the cooled catalyst in a polyacrylamide and nano silicon dioxide methanol solution, reacting for 10 hours at 75 ℃, and then removing an organic solvent under the vacuum degree of 70% to obtain the catalyst A4.
Comparative example 1
Comparative catalyst DA1
Selecting commercial columnar active carbon as a catalyst carrier, measuring the water absorption rate of the columnar active carbon, and determining the water absorption rate according to MnO and CeO 2 The mixed solution of manganese nitrate and cerium nitrate is prepared in a proportion of 6.0 percent and 2.5 percent of the total weight of the catalyst respectively. Impregnating the activated carbon strips for 8 hours by an isovolumetric impregnation method, drying at 80 ℃, roasting at 600 ℃ under helium atmosphere for 4 hours, cooling to room temperature, and taking out to obtain the catalyst DA1.
Comparative example 2
Comparative catalyst DA2
The silicon aluminum clay, the coconut shell activated carbon powder and the aluminum dihydrogen phosphate are uniformly mixed according to the mass ratio of 50:40:10, copper nitrate solution is added according to the proportion that CuO accounts for 8.0 percent of the total weight of the catalyst, the mixture is extruded into round bars with the diameter of 3.0mm by a bar extruder after being kneaded, and the round bars are baked at the temperature of 650 ℃ in nitrogen atmosphere to prepare the catalyst DA2.
Comparative example 3
Comparative catalyst DA3
Uniformly mixing a 4A molecular sieve, active carbon and silicon aluminum clay according to a mass ratio of 40:20:40, adding a polyvinyl alcohol binder accounting for 8% of the mass of the carrier, extruding into round strips by using a strip extruder after kneading, and roasting at 700 ℃ under the protection of nitrogen in an atmosphere furnace to prepare the composite carrier. The water absorption was measured, and mixed solutions of copper nitrate and cerium nitrate were prepared in such a manner that CuO and MnO respectively account for 10.0% and 5.0% of the total weight of the catalyst. The carrier strip is impregnated with the solution in an equal volume for 10 hours, dried at 70 ℃, baked for 4 hours under the nitrogen atmosphere at 700 ℃, cooled to room temperature and taken out, and the catalyst DA3 is obtained.
Comparative example 4
Comparative catalyst DA4
The preparation method comprises the steps of uniformly mixing coal active carbon powder, a 4A molecular sieve, silicon aluminum clay and sodium silicate according to a mass ratio of 25:40:25:10, adding copper nitrate solution according to a proportion that copper oxide accounts for 10.0% of the total weight of the catalyst, uniformly kneading in a kneader, taking out, extruding into a 2.5mm cylinder by using a strip extruder, and roasting at 700 ℃ under the protection of nitrogen to obtain the catalyst DA4.
Example 5
The catalyst A1 is filled in a circular reaction tube, an aeration head is arranged at the bottom for bubbling, ozone is used for intermittent treatment of wastewater, and the COD of the acid scarlet 3R dye wastewater solution is 78.6mg/L. 200mL of wastewater at room temperature and normal pressure, 10g of catalyst loading and 13.5g/m of ozone 3 Aeration time was 30min and the treatment results are shown in Table 1.
Example 6
The catalyst A2 is filled in a round reaction tube, an oxidant feed inlet is arranged at the bottom, hydrogen peroxide is used for carrying out intermittent treatment on wastewater, and the COD of pharmaceutical wastewater solution is 116.9mg/L. 200mL of wastewater at room temperature and normal pressure, 10g of catalyst loading and 13.5g/m of ozone 3 The hydrogen peroxide amount was 150mg, and the treatment results are shown in Table 1.
Example 7
Catalyst A3 is filled in a circular reaction tube, an aeration head is arranged at the bottom for bubbling and an oxidant feed inlet, ozone and hydrogen peroxide are used for intermittent treatment of wastewater, and the COD of the phenol formaldehyde simulated wastewater solution is 158.3mg/L. 200mL of wastewater at room temperature and normal pressure, 10g of catalyst loading and 15.5g/m of ozone 3 The aeration time was 30min, the hydrogen peroxide consumption was 100mg, and the treatment results are shown in Table 1.
Example 8
Filling catalyst A4 into round reaction tube, and bubbling with aeration head at bottom to obtain the final productOzone is used for intermittent treatment of wastewater, and COD of chemical wastewater solution is 123.7mg/L. 200mL of wastewater at room temperature and normal pressure, 10g of catalyst loading and 13.5g/m of ozone 3 Aeration time was 30min and the treatment results are shown in Table 1.
Comparative example 5
Example 7 was repeated, with catalyst A3 being replaced by comparative catalyst DA1, and the treatment results being given in Table 1.
Comparative example 6
Example 8 was repeated, with catalyst A4 being replaced by comparative catalyst DA2, and the treatment results being given in Table 1.
Comparative example 7
Example 6 was repeated, with catalyst A2 being replaced by comparative catalyst DA3, and the treatment results being given in Table 1.
Comparative example 8
Example 5 was repeated, with catalyst A1 being replaced by comparative catalyst DA4, and the treatment results being given in Table 1.
Table 3 comparison of results of catalyst evaluation
Table 3 comparison of results of catalyst evaluation
| Catalyst | A1 | A2 | A3 | A4 | DA1 | DA2 | DA3 | DA4 |
| COD removal rate% | 78.6 | 75.3 | 80.2 | 73.6 | 50.6 | 53.4 | 56.2 | 55.7 |
Claims (31)
1. A method for preparing a catalytic wet oxidation catalyst, the method comprising the following steps:
(1) The method comprises the steps of (1) enabling silicon-aluminum clay, activated carbon and alkali-soluble fiber to be in short filament cutting, enabling a binder to be in contact with each other in the presence of water, and then obtaining a material A through molding and high-temperature heat treatment;
(2) The material A obtained in the step (1) is contacted with caustic soda solution and subjected to hydrothermal treatment, and solid phase material obtained after cooling washing and solid-liquid separation is further subjected to drying treatment to obtain a material B;
(3) Introducing the material B obtained in the step (2) into an active component, and drying and roasting to obtain a material C;
(4) Feeding the material C into a mixed solution of a modifier and nano oxide sol for soaking treatment, and then separating out an organic solvent to obtain a catalyst; the modifier is polyhydroxy compound.
2. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the active component in the step (3) is one or more of transition metal and rare earth metal; the mass of the active component accounts for 5-20% of the total mass of the catalyst.
3. A method of preparing a catalytic wet oxidation catalyst according to claim 1 or 2, characterized in that: the active component in the step (3) is one or more of copper, manganese and cerium.
4. A method of preparing a catalytic wet oxidation catalyst according to claim 3, wherein: the active components in step (3) are cerium and optionally copper and/or manganese.
5. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (1), the silicon-aluminum clay is firstly roasted for 3 to 8 hours at a high temperature of between 600 and 1000 ℃.
6. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the activated carbon in the step (1) is selected from wood activated carbon, shell activated carbon and coal-based activated carbon.
7. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (1), the mass ratio of the silicon dioxide to the aluminum oxide in the silicon-aluminum clay component is 1-1.5:1, and the sum of the mass of the silicon dioxide and the aluminum oxide component is more than 80% of the total mass of the silicon-aluminum clay.
8. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (1), the alkali-soluble fiber short cut length is 2-5 mm, and the diameter of a monofilament is 10-70 nm.
9. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (1), the alkali-soluble fiber chopped filaments are selected from one or a combination of more of alkali-soluble polyester fibers, alkali-soluble carboxymethyl cellulose fibers and alkali-soluble hydroxyethyl cellulose fibers.
10. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the adhesive in the step (1) is an inorganic adhesive, and the inorganic adhesive is one or more of silicate inorganic adhesive and phosphate inorganic adhesive; the silicate inorganic binder is one or more of tricalcium silicate, dicalcium silicate, calcium silicate, aluminum silicate and sodium silicate; the phosphate inorganic binder is one or more of aluminum dihydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium tripolyphosphate, sodium pyrophosphate and sodium hexametaphosphate.
11. The method for preparing the catalytic wet oxidation catalyst according to claim 10, wherein: the silicate inorganic binder is aluminum silicate or sodium silicate; the phosphate inorganic binder is sodium tripolyphosphate and aluminum dihydrogen phosphate.
12. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (1), the mass percentage of the activated carbon, the silicon-aluminum clay and the binder is 10-40%: 50-80%: 2-10% of the alkali-soluble fiber is mixed, and the consumption of the alkali-soluble fiber chopped filaments is 3-15% of the total mass of the carrier.
13. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the hydrothermal treatment in the step (2) is carried out for 2-8 hours at the temperature of 80-220 ℃.
14. A method of preparing a catalytic wet oxidation catalyst according to claim 1 or 13, wherein: the hydrothermal treatment in the step (2) is carried out for 3-6 hours at the temperature of 85-160 ℃.
15. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the molar ratio of Na in the caustic soda solution to Si in the silicon aluminum clay in the step (2) is 3-3.4: 1, the mass concentration of the caustic soda solution is 7.5-10%.
16. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (2), the drying is carried out for 3 to 24 hours at the temperature of 50 to 100 ℃.
17. A method of preparing a catalytic wet oxidation catalyst according to claim 1 or 16, wherein: in the step (2), the drying is carried out for 6 to 8 hours at the temperature of 60 to 70 ℃.
18. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: in the step (3), the drying temperature is 60-150 ℃, the drying time is 3-12 h, the roasting temperature is 500-1500 ℃ and the roasting time is 2-6 h.
19. A method of preparing a catalytic wet oxidation catalyst according to claim 1 or 18, wherein: the drying temperature in the step (3) is 80-110 ℃ and the drying time is 4-6 h; the roasting temperature is 600-800 ℃ and the roasting time is 3-4 h.
20. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the modifier in the step (4) is one or a combination of more of hydrophilic chitosan, polyacrylamide, polyvinyl alcohol, dextran and hyaluronic acid.
21. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the nano oxide sol in the step (4) is an alcohol-based sol of nano silicon dioxide and/or nano titanium dioxide.
22. The method for preparing the catalytic wet oxidation catalyst according to claim 1, wherein: the solid content of the mixed solution of the modifier and the nano oxide sol in the step (4) accounts for 3-10% of the total mass of the catalyst.
23. A catalytic wet oxidation catalyst obtainable by the process of any one of claims 1 to 22, the catalytic wet oxidation catalyst comprising an active component and a support; the active component is one or more of transition metal and rare earth metal; the mass of the active component accounts for 5% -20% of the total mass of the catalyst; the carrier is prepared by performing hydrothermal treatment on active carbon, alkali-soluble fiber chopped filaments, an inorganic binder and silica-alumina clay to prepare a formed particle precursor alkali liquor.
24. The catalytic wet oxidation catalyst of claim 23, wherein: the active component is one or more of copper, manganese and cerium.
25. The catalytic wet oxidation catalyst according to claim 23 or 24, wherein: the active component is cerium and optionally copper and/or manganese.
26. The catalytic wet oxidation catalyst of claim 23, wherein: the carrier is provided with three-stage pore channels, the pore diameter of the first-stage pore channel is 0.1-1.5 nm, the pore volume of the first-stage pore channel accounts for more than 15% of the total pore volume, the pore diameter of the second-stage pore channel is 1.5-5 nm, the pore volume of the second-stage pore channel accounts for more than 25% of the total pore volume, the pore diameter of the third-stage pore channel is 5-50 nm, the pore volume of the third-stage pore channel accounts for less than 60% of the total pore volume, and the three-stage pore channels are communicated by a cross-linking intercommunication pore channel formed after dissolving alkali-soluble fiber in the carrier in a short-cut manner.
27. The catalytic wet oxidation catalyst according to claim 23 or 26, wherein: the carrier is provided with three-stage pore channels, wherein the pore diameter of the first-stage pore channel is 0.1-1.5 nm, the pore volume of the first-stage pore channel accounts for 20-30% of the total pore volume, the pore diameter of the second-stage pore channel is 1.5-5 nm, the pore volume of the second-stage pore channel accounts for 35-40% of the total pore volume, the pore diameter of the third-stage pore channel is 5-50 nm, the pore volume of the third-stage pore channel accounts for 30-40% of the total pore volume, and the three-stage pore channels are communicated by a cross-linked intercommunication pore channel formed by dissolving alkali-soluble fiber chopped filaments in the carrier.
28. The catalytic wet oxidation catalyst of claim 1, wherein:the specific surface area of the catalytic wet oxidation catalyst is more than 200m 2 Per gram, pore volume greater than 0.20. 0.20 cm 3 /g。
29. A method of catalytic oxidation treatment of wastewater by feeding wastewater with an oxidant to a reactor packed with a catalytic wet oxidation catalyst as claimed in any one of claims 23 to 28 for catalytic oxidation.
30. The catalytic oxidation process for wastewater treatment according to claim 29, wherein: the oxidant is one or two of hydrogen peroxide and ozone, and the dosage of the oxidant is 10-100 g oxidant added per 10g COD.
31. The catalytic oxidation process for wastewater treatment according to claim 29, wherein: the COD range of the wastewater is 40-1000 mg/L.
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| US5403809A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Composite inorganic supports containing carbon for bioremediation |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN108786721A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of composite adsorbing material and preparation method thereof |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
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| US5403809A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Composite inorganic supports containing carbon for bioremediation |
| CN108786721A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of composite adsorbing material and preparation method thereof |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
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