CN108671937A - A kind of preparation method and applications of copper-manganese composite oxide catalysts - Google Patents
A kind of preparation method and applications of copper-manganese composite oxide catalysts Download PDFInfo
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- CN108671937A CN108671937A CN201810470823.9A CN201810470823A CN108671937A CN 108671937 A CN108671937 A CN 108671937A CN 201810470823 A CN201810470823 A CN 201810470823A CN 108671937 A CN108671937 A CN 108671937A
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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
- 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
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- 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
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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
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention discloses a kind of preparation method and applications of copper-manganese composite oxide catalysts, are based on Mn2+Metal organic framework be with Mn2+For metal node, using trimesic acid as organic ligand, by the three-dimensional porous metal-organic framework materials being self-assembly of, the crystal structure of Mn BTC belongs to trigonal system, space groupCopper from acetylacetone copper is evenly distributed on above-mentioned three-dimensional porous metal-organic framework materials.Existing control is complicated during preparing copper-manganese composite oxide catalysts the present invention overcomes conventional method, it is less reproducible, the shortcomings of being not suitable for large-scale production, and the catalyst prepared by the method for the present invention is to the degradation efficiency of organic dyestuff in waste water from dyestuff up to 100%, reusing is good, has good commercial application value.
Description
Technical field
The invention belongs to wastewater treatment catalyst technical fields, and in particular to a kind of system of copper-manganese composite oxide catalysts
Preparation Method and its application.
Background technology
Commercial dyes type in China's is up to tens thousand of kinds at present, and 60% or more the global dyestuff total output that dyestuff yield accounts for occupies
First place in the world.About 80,000 tons of dyestuffs of discharge enter water body environment (Journal of Chemical Industry and Engineering, 2013,64,84) every year in China according to statistics.Therefore,
Waste water from dyestuff not only causes considerable damage, but also seriously threaten as a kind of important pollutant in water body environment to ecological environment
China's residents ' health.Include both at home and abroad mainly Physical, chemistry in the research method in dye wastewater treatment field for the problem
Method, bioanalysis etc..Wherein chemical method possesses stronger oxidability, and organic dyestuff may make quickly thoroughly to degrade.Based on urging
The advanced oxidation treatment technology (Advanced oxidation process, AOP) of agent is in chemical Treatment waste water from dyestuff
A kind of new technology, the hydroxyl radical free radical (OH) of strong oxidizing property can be generated, have high efficiency, universality is easy to operate, no
Generate the advantages such as secondary pollution.These advantages make the technology rapidly become the research hotspot in dye wastewater treatment field.And it opens
Hair efficient stable and the catalyst of low cost are one of the key factors that the commercialization of AOP technologies is promoted.
Have numerous studies have shown that copper-manganese composite oxide catalysts can be widely used for the reaction of hexamethylene deep oxidation, benzene
Phenol deep oxidation reacts, toluene catalytic combustion reaction, the reaction of benzene deep oxidation, organic exhaust gas (VOCs) catalyst combustion reaction, NOx
Catalytic oxidation, CO low-temperature catalytic oxidations reaction etc. (Journal of Physical Chemistry C, 2012,116,
12066).Currently, copper-manganese composite oxide catalysts generally use coprecipitation, secondary precipitation, sol-gal process, oxidation is also
Prepared by the methods of former method, need that highly basic or strong acid, and the microstructure of catalyst and activity and catalyst is added in preparation process
Preparation technology parameter is closely related.For example, presoma selects, and mixed liquor pH value, precipitating reagent type, dropwise addition mode, precipitation temperature,
Ageing time, calcination temperature, the factors such as roasting time significantly affect the microstructure and activity (Journal of of catalyst
Molecular Catalysis A：Chemical, 2009,305,121).Therefore, conventional method prepares copper-manganese composite oxides
Catalyst process control is complicated, less reproducible, limits the large-scale production of the catalyst material, and after calcination process
Material crystalline phase is complicated, and the distribution of crystal grain easy-sintering, especially copper in composite structure is unable to get Effective Regulation.Example
Such as, technical solution disclosed in CN1660491 A makees precipitating reagent with inorganic base, two kinds of components of manganese salt and mantoquita is precipitated simultaneously, so
By obtaining copper-manganese composite oxide catalysts after drying and roasting, the existing way of the catalytic component be metal oxide,
Acid oxide or basic oxide.In addition, technical solution disclosed in CN101574662 B is same by manganese salt, mantoquita and precipitating reagent
When mixing be added be pre-loaded in the reaction vessel of carrier, reacted between 7-10 in pH value, then through precipitation, aging,
Copper-manganese composite oxide catalysts are obtained after dry, calcination process.
Invention content
It is an object of the invention to overcome prior art defect, a kind of preparation side of copper-manganese composite oxide catalysts is provided
Method.
Another object of the present invention is to provide the applications of above-mentioned copper-manganese composite oxide catalysts.
Technical scheme is as follows：
A kind of preparation method of copper-manganese composite oxide catalysts, includes the following steps：
(1) by Mn2+Soluble-salt, trimesic acid, acetylacetone copper, surfactant and stirring solvent mixing it is equal
It is even, obtain mixed solution, above-mentioned surfactant and Mn2+Soluble-salt molar ratio be 0~1: 1 (preferably 0.0025~1:
1)；
(2) above-mentioned mixed solution is reacted into 5~20h in 25~80 DEG C of atmospheric agitations, or in in high pressure sealing reaction kettle
6~12h is reacted at 105~120 DEG C；
(3) the material separating, washing, drying obtained by step (2) is urged with roasting to get the copper-manganese composite oxides
Agent.
In a preferred embodiment of the invention, the Mn2+Soluble-salt be manganese nitrate, manganese acetate, manganese chloride
At least one of with manganese sulfate.
In a preferred embodiment of the invention, the surfactant is polyvinylpyrrolidone, cetyl
At least one of trimethylammonium bromide and hexadecyltrimethylammonium chloride.
In a preferred embodiment of the invention, the solvent is deionized water, absolute ethyl alcohol and N, N- dimethyl
At least one of formamide.
In a preferred embodiment of the invention, described to be roasted to：In air or oxygen atmosphere, in 450~650
DEG C roasting 2~10h.
It is further preferred that in the step (1), the acetylacetone copper and the Mn2+Soluble-salt molar ratio
It is 0.04~0.5: 1.
The application of copper-manganese composite oxide catalysts prepared by above-mentioned preparation method in handling waste water from dyestuff.
In a preferred embodiment of the invention, including：By the copper-manganese composite oxide catalysts with it is pending
Waste water from dyestuff mixing, appropriate hydrogen peroxide solution is added, is sufficiently stirred, 15~120min of degradation reaction waits for leading to after reaction
The copper-manganese composite oxide catalysts are recovered by filtration, gained crosses drainage and reaches industrial wastewater discharge standard.
The beneficial effects of the invention are as follows：
1, the copper-manganese composite oxide catalysts obtained by the present invention, chemical composition contain copper galaxite and three oxidations
Two two kinds of manganese active components, wherein manganese element being based on divalent manganesetion (Mn from a kind of2+) metal organic framework, and copper
From the acetylacetone copper being adsorbed on the metal organic framework, which obtains copper-manganese composite oxides by high-temperature roasting
Catalyst, wherein copper are uniformly distributed among catalyst.
2, preparation method of the invention is based on Mn2+Metal organic framework be with Mn2+For metal node, with trimesic acid
(H3BTC it is) organic ligand, passes through the three-dimensional porous metal-organic framework materials (abbreviation Mn-BTC) being self-assembly of, Mn-BTC
Crystal structure belong to trigonal system, space group
3, existing control is complicated during preparing copper-manganese composite oxide catalysts the present invention overcomes conventional method, weight
Renaturation is poor, and the shortcomings of being not suitable for mass producing, and the catalyst prepared by the method for the present invention is to organic in waste water from dyestuff
For the degradation efficiency of dyestuff up to 100%, reusing is good, has good commercial application value.
Description of the drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of 1 obtained catalyst A of the embodiment of the present invention.XRD characterization is tested
Instrument is Germany's Bruker D8 advance type x-ray powder diffraction instruments, and Cu target K alpha rays (λ=0.15406nm) are as radiation
Light source, tube voltage 40kV, tube current parameter are 30mA, 5 ° -90 ° of scanning range, 0.02 ° of step-length.
The field emission scanning electron microscope that Fig. 2 is Example 1 and Example 2 of the present invention obtained catalyst A and catalyst B shines
Piece, wherein Fig. 2 a are field emission scanning electron microscope (FESEM) photo of 1 obtained catalyst A of the embodiment of the present invention, in Fig. 2 a
Scale be 100nm；Fig. 2 b are the FESEM photos of 2 obtained catalyst B of embodiment, and the scale in Fig. 2 b is 500nm.
FESEM characterization test instruments are Jeol Ltd. JSM-6700F type cold field emission scanning electron microscope.
Fig. 3 is that Elemental redistribution is swept in face energy dispersion X-ray spectrum (EDX) of catalyst C prepared by the embodiment of the present invention 3
Scheme, the scale in figure is 500nm.EDX characterization test instruments are the INCA-7426 type energy dispersions X of England Oxford instrument company
Ray spectrometer.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode combination attached drawing.
Embodiment 1
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, deionized water and ethyl alcohol are mixed solvent, each feed molar composition Mn (CH3COO) 2∶H3BTC: acetylacetone copper: H2O: second
Alcohol is 1: 3: 0.4: 560: 520.Various raw materials are stirred to react 15h at 25 DEG C, obtained solid obtains after filtration washing is dried
Shallow green powder shape product had both been the manganese Metal organic backbone (Cu of copper ion modification2+/Mn-BTC).By Cu2+/ Mn-BTC powder
3h is roasted at 500 DEG C in Muffle furnace and obtains copper-manganese composite oxide catalysts (catalyst number is A).XRD characterization result is such as
Fig. 1, the main chemical compositions for illustrating to have obtained the catalyst be copper galaxite (standard PDF cards number #01-070-0260) and
Manganese sesquioxide managnic oxide (standard PDF cards number #00-041-1442).FESEM characterization results such as Fig. 2 a illustrate to have obtained gained catalysis
Agent A is mainly to be made of spherical nm particles, average grain diameter 34nm.Catalyst A is applied to high-level oxidation technology (AOP)
It degrades to waste water from dyestuff, uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation efficiency of methylene blue was up to
100%.And catalyst solid is easy recycling by centrifuging, and is recycled by five times, and degradation efficiency is without under apparent
Drop, illustrates that the copper-manganese composite oxide catalysts reusing is strong.
Embodiment 2
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, polyvinylpyrrolidone (PVP) are surfactant, and deionized water and ethyl alcohol are mixed solvent, and each feed molar forms Mn
(CH3COO)2∶H3BTC: acetylacetone copper: PVP: H2O: ethyl alcohol 1: 3: 0.04: 0.005: 560: 520.By various raw materials 25
DEG C it is stirred to react 15h, obtained solid obtains shallow green powder shape product after filtration washing is dried, and has both been copper ion modification
Manganese Metal organic backbone (Cu2+/Mn-BTC).By Cu2+/ Mn-BTC powder roasts 3h acquisition copper-manganeses in Muffle furnace at 500 DEG C multiple
Close oxide catalyst (catalyst number is B).FESEM characterization results such as Fig. 2 b illustrate gained catalyst B mainly by nanometer
The big spheric granules that grade particles are self-assembled into (average grain diameter is 2 μm).It is right that catalyst B is applied to high-level oxidation technology (AOP)
Waste water from dyestuff is degraded, and uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation efficiency ＞ 90% of methyl orange.
Embodiment 3
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, cetyl trimethylammonium bromide (CTAB) are surfactant, and deionized water and ethyl alcohol are mixed solvent, each feed molar
Form Mn (CH3COO)2∶H3BTC: acetylacetone copper: CTAB: H2O: ethyl alcohol 1: 3: 0.5: 1: 560: 520.Various raw materials are existed
25 DEG C are stirred to react 20h, and obtained solid obtains shallow green powder shape product after filtration washing is dried, and are both modified for copper ion
Manganese Metal organic backbone (Cu2+/Mn-BTC).By Cu2+/ Mn-BTC powder roasts 3h in Muffle furnace and obtains copper-manganese at 500 DEG C
Composite oxide catalysts (catalyst number is C).EDX member vegetarian noodles sweeps that the results are shown in Figure 3, illustrates in gained catalyst C
In, copper and manganese element are uniformly distributed in catalyst structure.Catalyst C is applied to high-level oxidation technology (AOP) to dye
Material waste water is degraded, and uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation efficiency of methylene blue was up to
100%.
Embodiment 4
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, deionized water and ethyl alcohol are mixed solvent, each feed molar composition Mn (CH3COO) 2∶H3BTC: acetylacetone copper: H2O: second
Alcohol is 1: 3: 0.4: 560: 520.Various raw materials are stirred at 25 DEG C to be transferred in reaction kettle after 10min and are sealed, it is anti-in 120 DEG C
6h should be handled.It waits for after reaction, cooled to room temperature, products therefrom is after filtration washing is dried, 500 DEG C in Muffle furnace
Lower roasting 3h obtains copper-manganese composite oxide catalysts (catalyst number is D).Catalyst D is applied to high-level oxidation technology
(AOP) it degrades to waste water from dyestuff, uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation of methylene blue was imitated
Rate is up to 100%.
Embodiment 5
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, deionized water and ethyl alcohol are mixed solvent, each feed molar composition Mn (CH3COO) 2∶H3BTC: acetylacetone copper: H2O: second
Alcohol is 1: 3: 0.2: 560: 520.Various raw materials are stirred at 25 DEG C to be transferred in reaction kettle after 10min and are sealed, it is anti-in 105 DEG C
12h should be handled.It waits for after reaction, cooled to room temperature, products therefrom is after filtration washing is dried, 500 in Muffle furnace
It roasts 3h at DEG C and obtains copper-manganese composite oxide catalysts (catalyst number is E).Catalyst E is applied to high-level oxidation technology
(AOP) it degrades to waste water from dyestuff, uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation of methylene blue was imitated
Rate is up to 100%.
Embodiment 6
With manganese nitrate (Mn (NO3)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper source,
Polyvinylpyrrolidone (PVP) is surfactant, and n,N-Dimethylformamide (DMF) and ethyl alcohol are mixed solvent, each raw material
Mole composition Mn (NO3)2∶H3BTC: acetylacetone copper: PVP: DMF: ethyl alcohol 1: 5: 0.1: 0.0025: 650: 1900.It will be various
Raw material is stirred to react 5h at 80 DEG C, and obtained solid obtains shallow green powder shape product after filtration washing is dried, and has both been copper ion
Manganese Metal organic backbone (the Cu of modification2+/ Mn-BTC), by Cu2+/ Mn-BTC powder roasts 3h in Muffle furnace and obtains at 500 DEG C
Copper-manganese composite oxide catalysts (catalyst number is F).It is useless to dyestuff that catalyst F is applied to high-level oxidation technology (AOP)
Water is degraded, and uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation efficiency ＞ 90% of methylene blue.
Embodiment 7
With manganese chloride (MnCl2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper source, is gathered
Vinylpyrrolidone (PVP) is surfactant, and n,N-Dimethylformamide (DMF) and ethyl alcohol are mixed solvent, and each raw material rubs
You are composition Mn (NO3)2∶H3BTC: acetylacetone copper: PVP: DMF: ethyl alcohol 1: 5: 0.25: 0.005: 650: 1900.By various originals
Material is stirred to react 10h at 60 DEG C, and obtained solid obtains shallow green powder shape product after filtration washing is dried, and has both been copper ion
Manganese Metal organic backbone (the Cu of modification2+/ Mn-BTC), by Cu2+/ Mn-BTC powder roasts 3h in Muffle furnace and obtains at 500 DEG C
Copper-manganese composite oxide catalysts (catalyst number is G).It is useless to dyestuff that catalyst G is applied to high-level oxidation technology (AOP)
Water is degraded, and uses hydrogen peroxide for oxidant, and by processing in 30 minutes, the degradation efficiency of methylene blue was up to 100%.
Embodiment 8
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, polyvinylpyrrolidone (PVP) are surfactant, and deionized water and ethyl alcohol are mixed solvent, and each feed molar forms Mn
(CH3COO)2∶H3BTC: acetylacetone copper: PVP: H2O: ethyl alcohol 1: 9: 0.5: 0.01: 560: 520.By various raw materials at 25 DEG C
It is stirred to react 20h, obtained solid obtains shallow green powder shape product after filtration washing is dried, and has both been the manganese of copper ion modification
Metal organic framework (Cu2+/Mn-BTC).By Cu2+/ Mn-BTC powder roasts 3h acquisition copper-manganeses in Muffle furnace at 600 DEG C compound
Oxide catalyst (catalyst number is H).Catalyst H drops waste water from dyestuff applied to high-level oxidation technology (AOP)
Solution, uses hydrogen peroxide for oxidant, by processing in 30 minutes, the degradation efficiency of methyl orange was up to 100%.
Embodiment 9
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, deionized water and ethyl alcohol are mixed solvent, each feed molar composition Mn (CH3COO) 2∶H3BTC: acetylacetone copper: H2O: second
Alcohol is 1: 9: 0.5: 560: 520.Various raw materials are stirred to react 15h at 25 DEG C, obtained solid obtains after filtration washing is dried
Shallow green powder shape product had both been the manganese Metal organic backbone (Cu of copper ion modification2+/Mn-BTC).By Cu2+/ Mn-BTC powder
In leading to 450 DEG C of roasting 10h of oxygen in quartz tube furnace, obtain copper-manganese composite oxide catalysts (catalyst number is I).It will
Catalyst I degrades to waste water from dyestuff applied to high-level oxidation technology (AOP), uses hydrogen peroxide for oxidant, by 30 points
The degradation efficiency of the processing of clock, methylene blue is up to 100%.
Embodiment 10
With manganese acetate (Mn (CH3COO)2) it is manganese source, trimesic acid (H3BTC it is) organic ligand, acetylacetone copper is copper
Source, deionized water and ethyl alcohol are mixed solvent, each feed molar composition Mn (CH3COO) 2∶H3BTC: acetylacetone copper: H2O: second
Alcohol is 1: 9: 0.5: 560: 520.Various raw materials are stirred to react 15h at 25 DEG C, obtained solid obtains after filtration washing is dried
Shallow green powder shape product had both been the manganese Metal organic backbone (Cu of copper ion modification2+/Mn-BTC).By Cu2+/ Mn-BTC powder
In 650 DEG C of roasting 2h of blowing air in quartz tube furnace, obtain copper-manganese composite oxide catalysts (catalyst number is J).It will
Catalyst J degrades to waste water from dyestuff applied to high-level oxidation technology (AOP), uses hydrogen peroxide for oxidant, by 30 points
The degradation efficiency of the processing of clock, methylene blue is up to 100%.
Above example is it can be found that according to copper-manganese composite oxide catalysts preparation method provided by the invention, step
Simply, easily operated control carries out industrial dye waste water processing using catalyst provided by the invention, has excellent performance, repeats profit
It is strong with property.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (8)
1. a kind of preparation method of copper-manganese composite oxide catalysts, it is characterised in that：Include the following steps：
(1) by Mn2+Soluble-salt, trimesic acid, acetylacetone copper, surfactant and stirring solvent be uniformly mixed, obtain
Obtain mixed solution, above-mentioned surfactant and Mn2+Soluble-salt molar ratio be 0~1: 1；
(2) above-mentioned mixed solution is reacted into 5~20h in 25~80 DEG C of atmospheric agitations, or in in high pressure sealing reaction kettle 105
~120 DEG C of 6~12h of reaction；
(3) by obtained by step (2) material separating, washing, drying and roasting to get the copper-manganese composite oxide catalytic
Agent.
2. preparation method as described in claim 1, it is characterised in that：The Mn2+Soluble-salt be manganese nitrate, manganese acetate,
At least one of manganese chloride and manganese sulfate.
3. preparation method as described in claim 1, it is characterised in that：The surfactant is polyvinylpyrrolidone, ten
At least one of six alkyl trimethyl ammonium bromides and hexadecyltrimethylammonium chloride.
4. preparation method as described in claim 1, it is characterised in that：The solvent is deionized water, absolute ethyl alcohol and N, N-
At least one of dimethylformamide.
5. preparation method as described in claim 1, it is characterised in that：It is described to be roasted to：In air or oxygen atmosphere, in
450~650 DEG C of 2~10h of roasting.
6. the preparation method as described in any claim in Claims 1-4, it is characterised in that：In the step (1), institute
State acetylacetone copper and the Mn2+Soluble-salt molar ratio be 0.04~0.5: 1.
7. copper-manganese composite oxide catalysts prepared by the preparation method in claim 1 to 6 described in any claim are being located
Manage the application in waste water from dyestuff.
8. the use as claimed in claim 7, it is characterised in that：Including：By the copper-manganese composite oxide catalysts with wait locating
The waste water from dyestuff of reason mixes, and appropriate hydrogen peroxide solution is added, is sufficiently stirred, 15~120min of degradation reaction is waited for after reaction
The copper-manganese composite oxide catalysts are recovered by filtration, gained crosses drainage and reaches industrial wastewater discharge standard.
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| CN111013602A (en) * | 2019-12-20 | 2020-04-17 | 广州华园科技有限公司 | Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof |
| CN113546641A (en) * | 2021-07-26 | 2021-10-26 | 安徽科浦环保科技有限公司 | Preparation method of composite catalytic material for eliminating ozone |
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
| CN114409052A (en) * | 2022-01-20 | 2022-04-29 | 合肥工业大学 | Preparation method and application of efficient and stable carbon-supported MnO @ C composite anode material |
| CN115785460A (en) * | 2022-09-30 | 2023-03-14 | 西安石油大学 | Manganese metal organic framework material and preparation method and application thereof |
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| CN111013602A (en) * | 2019-12-20 | 2020-04-17 | 广州华园科技有限公司 | Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof |
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
| CN113546641A (en) * | 2021-07-26 | 2021-10-26 | 安徽科浦环保科技有限公司 | Preparation method of composite catalytic material for eliminating ozone |
| CN114409052A (en) * | 2022-01-20 | 2022-04-29 | 合肥工业大学 | Preparation method and application of efficient and stable carbon-supported MnO @ C composite anode material |
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| CN115785460B (en) * | 2022-09-30 | 2023-08-11 | 西安石油大学 | Manganese metal organic frame material and preparation method and application thereof |
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