CN116078397A - Catalytic filler and preparation method and application thereof - Google Patents
Catalytic filler and preparation method and application thereof Download PDFInfo
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- CN116078397A CN116078397A CN202310045766.0A CN202310045766A CN116078397A CN 116078397 A CN116078397 A CN 116078397A CN 202310045766 A CN202310045766 A CN 202310045766A CN 116078397 A CN116078397 A CN 116078397A
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- zinc oxide
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 57
- 239000000945 filler Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 23
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 27
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- -1 ion salt Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to a catalytic filler, and a preparation method and application thereof. The catalytic filler provided by the invention comprises an alumina carrier and an active component, wherein the active component comprises a first active component and a second active component; the first active component is cobalt oxide and zinc oxide; the second active component is selected from at least one of copper oxide, manganese oxide and sodium composite salt. According to the invention, through the compounding of the alumina carrier and the active component, the obtained catalytic filler has strong adaptability, high electron transfer rate, reduced power consumption, high catalytic efficiency and no secondary pollution.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a catalytic filler, and a preparation method and application thereof.
Background
In recent years, the new industry state and technology are upgraded, such as new energy automobile industry, fine chemical industry, pesticide, smelting and other industries, and the produced industrial wastewater has the problems of high concentration, strong toxicity, high heavy metal content and the like while meeting production standards.
Advanced oxidation process: mainly refers to the generation of strong oxidation substances with hydroxyl radical OH as a core in the strong oxidation process, and various pollutants in the rapid, non-selective and thorough oxidation environment. Including Fenton oxidation, ozone oxidation, wet oxidation, electrochemical oxidation, photocatalytic oxidation, sonochemical oxidation, etc., all belong to advanced oxidation processes, and these methods all refer to the generation of OH, are common characteristics of these processes, are important reactions of advanced oxidation processes, and differ only in the manner in which OH is generated. OH is an oxidant with extremely high oxidation capability, has extremely high oxidation-reduction potential, has no selectivity in oxidizing property, can react with almost any substance in water, and has wide application.
The electrochemical catalytic oxidation method is a common method in a plurality of advanced oxidation technologies, and utilizes the basic principle of electrolysis to remove pollutants, when the electrolysis occurs, sewage is used as electrolyte, the pollutants in the sewage are respectively subjected to oxidation and reduction reactions on the anode and cathode through the electrolysis process as electrolyte, and on the other hand, the pollutants are converted into harmless substances by utilizing the common oxidation action of hydroxyl radicals generated during the electrolysis so as to realize the purification of the sewage. However, the existing two-dimensional electrocatalytic material has low electron transfer rate, so that high electricity consumption and low catalytic efficiency are caused, and meanwhile, part of iron-carbon catalyst also has release of iron ions, so that secondary pollution of wastewater is caused. In addition, the existing catalytic materials have poor adaptability, and cannot be applied to the wastewater quality change caused by the change of weather environment, the technical process update in industrial production and the like.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of poor adaptability, low catalytic efficiency, secondary pollution caused by releasing iron ions and the like of the traditional electrocatalytic material, thereby providing a catalytic filler and a preparation method and application thereof.
The invention provides a catalytic filler, which comprises an alumina carrier and an active component, wherein the active component comprises a first active component and a second active component;
the first active component is cobalt oxide and zinc oxide;
the second active component is selected from at least one of copper oxide, manganese oxide and sodium composite salt.
The oxide forms of cobalt oxide, zinc oxide, copper oxide and manganese oxide are not particularly limited in the present invention, and for example, manganese oxide may be in the form of manganese oxide, manganous oxide, manganese dioxide, manganous oxide, and the like.
Al used in the present invention 2 O 3 The carrier belongs to standard products with the mark of A-AS-04, and the particle size is 3-12mm.
Preferably, the active component accounts for 1-10% of the mass of the alumina carrier;
and/or, the molar ratio of the metal element in the first active component to the metal element in the second active component is (1-4): (1-6).
Preferably, the active component is cobalt oxide, zinc oxide and manganese oxide;
and/or, the mole ratio of Co, zn and Mn elements in the cobalt oxide, the zinc oxide and the manganese oxide is (1-2): (1-2): (1-2).
Preferably, the active component is cobalt oxide, zinc oxide, and copper oxide;
and/or, the mole ratio of Co, zn and Cu elements in the cobalt oxide, the zinc oxide and the copper oxide is (1-2): (1-2): (1-2).
Preferably, the active component is a complex salt of cobalt oxide, zinc oxide, manganese oxide and sodium;
and/or, the molar ratio of Co, zn, mn and Na elements in the composite salt of cobalt oxide, zinc oxide, manganese oxide and sodium is (1-2): (1-2): (1-2): (1-2).
Preferably, the active component is cobalt oxide, zinc oxide, manganese oxide, and copper oxide;
and/or the mole ratio of Co, zn, mn and Cu elements in the cobalt oxide, zinc oxide, manganese oxide and copper oxide is (1-2): (1-2): (1-2): (1-2).
The invention provides a preparation method of the catalytic filler, which comprises the following steps:
and (3) immersing the carrier in a soluble salt solution corresponding to the active component, dehydrating and sintering to obtain the catalytic filler.
Preferably, the soaking time is 3-4 hours;
and/or the dehydration temperature is 90-105 ℃, the dehydration time is 2-3h, and the dehydration heating rate is 5-10 ℃/min;
and/or the sintering temperature is 500-1000 ℃, the sintering time is 4-8h, and the sintering heating rate is 5-10 ℃/min.
Preferably, the soluble salt in the soluble salt solution is an acid ion salt; typically, but not by way of limitation, the soluble salt may be selected from carbonates or sulfates;
and/or the total mass concentration of the soluble salt in the soluble salt solution is 8% -10%;
and/or the mass ratio of the soluble salt solution to the carrier is (0.3-1): 1, a step of;
and/or the step of cleaning after natural cooling is further included after sintering.
The invention also provides an application of the catalytic filler or the catalytic filler prepared by the method in electrocatalytic oxidation treatment of wastewater;
optionally, the wastewater is organic wastewater, salt-containing wastewater or heavy metal wastewater. The invention is especially suitable for treating high-concentration wastewater.
The technical scheme of the invention has the following advantages:
(1) The catalytic filler provided by the invention comprises an alumina carrier and an active component, wherein the active component comprises a first active component and a second active component; the first active component is cobalt oxide and zinc oxide; the second active component is selected from at least one of copper oxide, manganese oxide and sodium composite salt. According to the invention, through the compounding of the alumina carrier and three active components, particularly cobalt oxide and zinc oxide, the obtained catalytic filler is more beneficial to releasing hydroxyl free radicals OH under the action of electrocatalysis, so that the oxidation performance of the catalytic filler is enhanced. The obtained catalytic filler has strong adaptability, high catalytic efficiency and no secondary pollution.
(2) The preparation method of the catalytic filler provided by the invention comprises the following steps: soaking the carrier in soluble salt solution corresponding to the active component, dewatering and sintering to obtain the catalystAnd (3) filling. The invention is realized by stable Al 2 O 3 The carrier is compounded with soluble salt solution corresponding to the composite salt of cobalt oxide, zinc oxide, copper oxide, manganese oxide and sodium, and can be well loaded with the particle carrier, so that the catalytic filler with strong adaptability, high catalytic efficiency and no secondary pollution is obtained.
(3) The catalytic filler provided by the invention is easy to obtain, low in cost, high in electron transfer rate, low in power consumption and free of pollution.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a catalytic filler, which comprises the following steps:
500g of Al 2 O 3 The support (diameter 3-5 mm) was impregnated with 250g CoSO 4 、ZnSO 4 、MnSO 4 In the metal salt solution (the total mass concentration of the metal salt in the metal salt solution is 8%, wherein the molar ratio of Co, zn and Mn elements is 2:2:1), the dipping time is 4 hours, and the Al after the dipping is finished 2 O 3 And (3) dehydrating and sintering the carrier, wherein the dehydration temperature is 105 ℃, the dehydration time is 2 hours, the dehydration heating rate is 5 ℃/min, the sintering temperature is 1000 ℃, the sintering time is 8 hours, and the sintering heating rate is 5 ℃/min, so that the catalytic filler is obtained.
Example 2
The embodiment provides a preparation method of a catalytic filler, which comprises the following steps:
500g of Al 2 O 3 The support (diameter 3-5 mm) was impregnated with 150g CoSO 4 、ZnSO 4 、CuSO 4 In the metal salt solution (the total mass concentration of the metal salt is 10%, the molar ratio of Co, zn and Cu elements is 2:1:1), the dipping time is 3h, and the Al after the dipping is finished 2 O 3 And (3) dehydrating and sintering the carrier, wherein the dehydration temperature is 90 ℃, the dehydration time is 3 hours, the dehydration heating rate is 10 ℃/min, the sintering temperature is 800 ℃, the sintering time is 4 hours, and the sintering heating rate is 5 ℃/min, so that the catalytic filler is obtained.
Example 3
The embodiment provides a preparation method of a catalytic filler, which comprises the following steps:
500g of Al 2 O 3 The support (diameter 3-5 mm) was impregnated with 250g CoSO 4 、ZnSO 4 、MnSO 4 、Na 2 SO 4 In the metal salt solution (the total mass concentration of the metal salt is 10%, wherein the molar ratio of Co, zn, mn and Na elements is 1:2:1:1), the dipping time is 4 hours, and the Al after the dipping is finished 2 O 3 And (3) dehydrating and sintering the carrier, wherein the dehydration temperature is 100 ℃, the dehydration time is 2.5 hours, the dehydration heating rate is 7 ℃/min, the sintering temperature is 1000 ℃, the sintering time is 8 hours, and the sintering heating rate is 7 ℃/min, so that the catalytic filler is obtained.
Example 4
The embodiment provides a preparation method of a catalytic filler, which comprises the following steps:
500g of Al 2 O 3 The support (diameter 3-5 mm) was impregnated with 250g CoSO 4 、ZnSO 4 、MnSO 4 、CuSO 4 In the metal salt solution (total mass concentration of metal salt is 8%, wherein the mol ratio of Co, zn, mn and Cu elements is 1:2:1:1.5), the dipping time is 4h, and Al after the dipping is finished 2 O 3 And (3) dehydrating and sintering the carrier, wherein the dehydration temperature is 105 ℃, the dehydration time is 2 hours, the dehydration heating rate is 5 ℃/min, the sintering temperature is 1000 ℃, the sintering time is 8 hours, and the sintering heating rate is 5 ℃/min, so that the catalytic filler is obtained.
Comparative example 1
This comparative example provides a catalytic filler using only Al 2 O 3 The carrier is used as catalytic filler.
Comparative example 2
This comparative example provides a catalytic filler, differing from example 1 in that equimolar MnSO is used 4 Instead of ZnSO 4 The other conditions were the same.
Comparative example 3
This comparative example provides a catalytic filler, differing from example 1 in that equimolar MnSO is used 4 Instead of CoSO 4 The other conditions were the same.
Comparative example 4
This comparative example provides a catalytic filler, differing from example 1 in that equimolar MnSO is used 4 Instead of ZnSO 4 And CoSO 4 The other conditions were the same.
Comparative example 5
This comparative example provides a catalytic filler, differing from example 1 in that 250gFe is used 2 (SO 4 ) 3 、CuSO 4 、MnSO 4 In the metal salt solution (the total mass concentration of the metal salt in the metal salt solution is 8%, and the molar ratio of Fe, cu and Mn elements is 2:2:1) to replace CoSO 4 、ZnSO 4 、MnSO 4 Other conditions are the same.
Test case
The catalytic devices assembled with the catalytic fillers prepared in examples and comparative examples were subjected to wastewater treatment at two concentrations, with electrodes having a surface area of 1m 2 20kg of the catalytic filler is coated on the surface of the anode, and a direct current power supply (maximum output power) is introduced: 18v 200a, wastewater flow rate: the treatment time was 60min at 1 cubic meter/hour, and the chemical oxygen demand, ammonia nitrogen content and total phosphorus content of the wastewater before and after the treatment were measured to judge the removal effect and adaptability of each catalytic filler to pollutants.
The chemical oxygen demand in the wastewater is measured according to the HJ 828-2017 standard, the ammonia nitrogen in the wastewater is measured according to the HJ 535-2009 standard, the total phosphorus in the wastewater is measured according to the HJ 671-2013 standard, and the test results are shown in Table 1.
TABLE 1
From the table: the treatment effect of the embodiment of the invention on pollutants is obviously better than that of the filler-free and other fillers in the comparative example, the chemical oxygen demand totally reflects the pollution degree of the wastewater, the higher the oxygen demand is, the higher the pollution degree is, the wastewater subjected to electrocatalytic treatment by the catalytic filler prepared by the embodiment of the invention has obviously reduced oxygen demand no matter the wastewater with high concentration 1 or the wastewater with medium and low concentration 2, which indicates that the catalytic filler has strong adaptability and high catalytic efficiency.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A catalytic filler comprising an alumina support and an active component, wherein the active component comprises a first active component and a second active component;
the first active component is cobalt oxide and zinc oxide;
the second active component is selected from at least one of copper oxide, manganese oxide and sodium composite salt.
2. The catalytic filler of claim 1, wherein the active component comprises 1-10% by mass of the alumina support;
and/or, the molar ratio of the metal element in the first active component to the metal element in the second active component is (1-4): (1-6).
3. The catalytic filler of claim 1 or 2, wherein the active component is cobalt oxide, zinc oxide, and manganese oxide;
and/or, the mole ratio of Co, zn and Mn elements in the cobalt oxide, the zinc oxide and the manganese oxide is (1-2): (1-2): (1-2).
4. The catalytic filler of claim 1 or 2, wherein the active component is cobalt oxide, zinc oxide, and copper oxide;
and/or, the mole ratio of Co, zn and Cu elements in the cobalt oxide, the zinc oxide and the copper oxide is (1-2): (1-2): (1-2).
5. The catalytic filler of claim 1 or 2, wherein the active component is a complex salt of cobalt oxide, zinc oxide, manganese oxide and sodium;
and/or, the molar ratio of Co, zn, mn and Na elements in the composite salt of cobalt oxide, zinc oxide, manganese oxide and sodium is (1-2): (1-2): (1-2): (1-2).
6. The catalytic filler of claim 1 or 2, wherein the active component is cobalt oxide, zinc oxide, manganese oxide, and copper oxide;
and/or the mole ratio of Co, zn, mn and Cu elements in the cobalt oxide, zinc oxide, manganese oxide and copper oxide is (1-2): (1-2): (1-2): (1-2).
7. A process for the preparation of a catalytic filler according to any one of claims 1 to 6, comprising the steps of:
and (3) immersing the carrier in a soluble salt solution corresponding to the active component, dehydrating and sintering to obtain the catalytic filler.
8. The method of claim 7, wherein the immersion time is 3 to 4 hours;
and/or the dehydration temperature is 90-105 ℃, the dehydration time is 2-3h, and the dehydration heating rate is 5-10 ℃/min;
and/or the sintering temperature is 500-1000 ℃, the sintering time is 4-8h, and the sintering heating rate is 5-10 ℃/min.
9. The method of claim 7 or 8, wherein the soluble salt in the soluble salt solution is an acid ion salt;
and/or the total mass concentration of the soluble salt in the soluble salt solution is 8% -10%;
and/or the mass ratio of the soluble salt solution to the carrier is (0.3-1): 1, a step of;
and/or the step of cleaning after natural cooling is further included after sintering.
10. Use of the catalytic filler according to any one of claims 1 to 6 or the catalytic filler prepared by the method according to any one of claims 7 to 9 in electrocatalytic oxidation treatment of wastewater.
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