CN115770567A - Manganese oxide catalyst and preparation method and application thereof - Google Patents
Manganese oxide catalyst and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention provides a manganese oxide catalyst and a preparation method and application thereof, the manganese oxide catalyst comprises active carbon and amorphous manganese oxide loaded on the active carbon, and the mass ratio of the amorphous manganese oxide to the active carbon is (0.1-1): 1. the preparation method of the manganese oxide catalyst comprises the following steps: dispersing amorphous manganese oxide and activated carbon in a first solvent, uniformly stirring and mixing, performing solid-liquid separation to obtain a solid phase, and performing first drying treatment on the solid phase to obtain a manganese oxide catalyst; wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1. the preparation method of the manganese oxide catalyst has the advantages of easily obtained raw materials, simple process and convenience for industrial large-scale production; the manganese oxide catalyst has high catalytic activity and good stability for harmful gases (such as formaldehyde).
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a manganese oxide catalyst and a preparation method and application thereof.
Background
With the aggravation of global environmental problems, the discussion degree of indoor air pollution topics in various countries around the world is high. Related researches also point out that the attention on indoor air pollution is an important link for constructing a national epidemic prevention system in the post epidemic situation era. Formaldehyde, the most common indoor air pollutant, is identified as a carcinogen and a teratogen due to its high toxicity, wide source, long release cycle, and the like.
Among the existing various formaldehyde removal means, the catalytic oxidation method can completely convert formaldehyde into carbon dioxide and water, has the advantages of low energy consumption, no pollution and the like, and is known as a technology with the most application prospect. The development of efficient and safe formaldehyde oxidation catalysts is the key to promote the application of catalytic oxidation technology.
Currently, there are two types of formaldehyde oxidation catalyst materials commonly used. One of the supported noble metal catalysts is a supported noble metal catalyst with excellent formaldehyde catalytic activity, represented by Pt, au, pd and Ag, which can realize the complete conversion of formaldehyde at low temperature even at room temperature, but the high cost of noble metals severely restricts the practical application thereof. Thus, researchers have turned their attention to another class, non-noble metal catalysts based on transition metal oxides.
In recent years, the design of increasing the catalytic activity of non-noble metal catalysts to obtain materials with application value has become a mainstream trend in the development of formaldehyde catalytic oxidation technology. Manganese oxide is a non-noble metal catalyst which can be used for oxidizing and catalyzing formaldehyde, and has better catalytic activity on formaldehyde. The catalytic activity of the conventional manganese oxide catalyst is still to be further improved.
Disclosure of Invention
Based on the above, it is necessary to provide a manganese oxide catalyst with high catalytic activity, and a preparation method and applications thereof.
The technical scheme provided by the invention is as follows:
according to a first aspect of the present invention, there is provided a manganese oxide catalyst, comprising activated carbon and an amorphous manganese oxide supported on the activated carbon, wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1 to 1): 1.
in some embodiments, the mass ratio of the amorphous manganese oxide to the activated carbon is (0.3-1): 1.
further preferably, the mass ratio of the amorphous manganese oxide to the activated carbon is 0.3:1.
according to a second aspect of the present invention, there is provided a method for preparing a manganese oxide catalyst, comprising the steps of:
mixing amorphous manganese oxide, activated carbon and a first solvent to prepare a mixed solution;
carrying out solid-liquid separation on the mixed solution to obtain a solid phase, and carrying out first drying treatment on the solid phase to obtain the manganese oxide catalyst;
wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1.
in some embodiments, the mass ratio of the amorphous manganese oxide to the activated carbon is (0.3-1): 1.
further preferably, the mass ratio of the amorphous manganese oxide to the activated carbon is 0.3:1.
in some embodiments, the method for preparing the amorphous manganese oxide comprises the following steps:
and dissolving permanganate and a reducing agent in a second solvent for reaction, performing solid-liquid separation after the reaction is finished, taking a solid phase, and performing second drying treatment on the solid phase to obtain the amorphous manganese oxide.
In some of these embodiments, the reducing agent comprises one or more of oleic acid, oxalic acid, ammonium oxalate, citric acid, ascorbic acid.
Further preferably, the reducing agent is oxalic acid.
In some of these embodiments, the permanganate salt is one or both of potassium permanganate and sodium permanganate.
In some embodiments, in the mixed liquid of the second solvent, the permanganate and the reducing agent, the concentration of the permanganate is 0.01-0.03 mol/L, and the concentration of the reducing agent is 0.02-0.05 mol/L.
In some embodiments, the reaction time is 0.5-10 h, and the reaction temperature is 25-80 ℃.
In some embodiments, the temperature of the second drying treatment is 40-120 ℃, and the time of the second drying treatment is 4-12 h.
In some embodiments, the step of mixing the amorphous manganese oxide, the activated carbon and the first solvent is performed under stirring, and the stirring and mixing time is 1 to 6 hours.
In some embodiments, the temperature of the first drying treatment is 40-100 ℃, and the time of the first drying treatment is 4-8 h.
According to a third aspect of the present invention, there is provided use of the manganese oxide catalyst of the first aspect of the present invention or the manganese oxide catalyst prepared by the preparation method of the second aspect of the present invention for purification of harmful gases.
In some of these embodiments, the hazardous gas comprises formaldehyde.
In some of these embodiments, the oxides of manganese catalyst is used to catalytically decompose the harmful gases.
Compared with the prior art, the invention has the following beneficial effects:
in the manganese oxide catalyst, the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1, so that the amorphous manganese oxide is loaded on the active carbon; a large number of oxygen vacancies are effectively introduced into the amorphous manganese oxide to serve as active sites, and the introduction of the active carbon with a specific proportion further improves the specific surface area of the manganese oxide catalyst, improves the dispersion degree of the manganese oxide, ensures that the active components of the catalyst are highly dispersed and serve as adsorption sites to adsorb harmful gases, thereby effectively improving the activity and stability of the manganese oxide catalyst in decomposing harmful gases. The manganese oxide catalyst can continuously and efficiently catalyze formaldehyde to be oxidized and decomposed at 80 ℃, has no harmful byproducts, and has better catalytic activity than the traditional manganese-based non-noble metal catalyst.
The preparation method of the manganese oxide catalyst adopts a two-step method, firstly, the amorphous manganese oxide is prepared by a simple oxidation-reduction method, the calcination step in the traditional manganese oxide preparation method is not needed, the crystallization of the manganese oxide is avoided, the sintering and aggregation phenomena of particles in the calcination process are avoided, the catalytic activity of the manganese oxide catalyst is higher, the utilization rate of active components is higher, and the long-term stability of the manganese oxide catalyst is better; the subsequent introduction of active carbon via impregnation process can further raise the dispersivity of the active component and provide more harmful gas adsorbing sites, so as to further raise the catalytic activity of the catalyst. In addition, the preparation method has the advantages of easily available raw materials and simple process, and is convenient for industrial large-scale production.
Drawings
FIG. 1 is a graph showing formaldehyde conversion curves of manganese oxide catalysts and activated carbon according to examples of the present invention and comparative examples.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings, which illustrate embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Non-noble metal catalysts based on transition metal oxides have the advantage of lower cost compared to noble metal catalysts. Among them, the manganese oxide catalyst is a commonly used non-noble metal catalyst. However, the catalytic activity of the conventional manganese oxide catalyst against harmful gases such as formaldehyde is to be improved.
In order to solve the above problems, an embodiment of the present invention provides a method for preparing a manganese oxide catalyst, which includes the following steps S100 and S200.
Step S100: synthesis of amorphous manganese oxides
Dissolving permanganate and a reducing agent in a second solvent for reaction, performing solid-liquid separation after the reaction is finished to obtain a solid phase, and performing second drying treatment on the solid phase to obtain amorphous manganese oxide (a-MnO) x Wherein x is the number of oxygen atoms).
In the preparation process of the traditional manganese oxide catalyst, a calcination step is required, the calcined manganese oxide is crystallized and particle sintering and aggregation phenomena are easy to occur, so that the catalytic activity of the manganese oxide as an active component of the catalyst is reduced, the utilization rate of the active component is reduced, and the long-term stability of the catalyst is poor.
The preparation method of the invention adopts a simple oxidation-reduction method to prepare the amorphous manganese oxide, a calcination step is not needed in the reaction process, the crystallization of the manganese oxide is avoided, the phenomena of sintering and aggregation of particles in the calcination process are avoided, the manganese oxide catalyst has higher catalytic activity, higher utilization rate of active components and better long-term stability.
In some of these embodiments, the second solvent used is deionized water. It is understood that other solvents that can dissolve the permanganate and the reducing agent well and facilitate drying removal after the reaction can be used as the second solvent.
In some of these embodiments, the permanganate is dissolved in deionized water to form a permanganate solution, and the reducing agent is dissolved in deionized water to form a reducing agent solution; and then slowly dripping the permanganate solution into the reducing agent solution under the conditions of magnetic stirring and/or ultrasound, reacting for a period of time after dripping is finished, carrying out solid-liquid separation on the reaction solution after the reaction is finished, fully cleaning the solid phase (namely the precipitate obtained after the reaction), and drying to obtain the amorphous manganese oxide.
In some embodiments, the reducing agent used is one or more of oleic acid, oxalic acid, ammonium oxalate, citric acid, ascorbic acid. The reducing agent is adopted to react with permanganate to obtain amorphous manganese oxide with good catalytic activity,
it is to be understood that any one of oleic acid, oxalic acid, ammonium oxalate, citric acid and ascorbic acid may be used as the reducing agent, and two or more of oleic acid, oxalic acid, ammonium oxalate, citric acid and ascorbic acid may be used in combination.
Further, oxalic acid is preferably used as the reducing agent. Through experimental research, oxalic acid is used as a reducing agent to react with permanganate to prepare the amorphous manganese oxide, so that the finally prepared manganese oxide catalyst has higher catalytic activity.
In some of these embodiments, the permanganate salt is one or both of potassium permanganate and sodium permanganate.
In some embodiments, the concentration of the permanganate in the reaction system is 0.01mol/L to 0.03mol/L and the concentration of the reducing agent is 0.02mol/L to 0.05mol/L in the initial stage of the reaction. The permanganate and the reducing agent are in the concentration ratio, so that the permanganate can fully react, side reactions are reduced, and the reaction yield of the amorphous manganese oxide is improved.
It is understood that the concentration of permanganate in the reaction system at the initial stage of the reaction may be, but not limited to, 0.01mol/L, 0.012mol/L, 0.015mol/L, 0.018mol/L, 0.020mol/L, 0.022mol/L, 0.025mol/L, 0.028mol/L, 0.03mol/L; the concentration of the reducing agent can be, but is not limited to, 0.02mol/L, 0.022mol/L, 0.025mol/L, 0.028mol/L, 0.030mol/L, 0.032mol/L, 0.035mol/L, 0.038mol/L, 0.04mol/L, 0.042mol/L, 0.045mol/L, 0.048mol/L, 0.05mol/L.
In some embodiments, the reaction time of the permanganate and the reducing agent is 0.5-10 h, the reaction temperature is controlled at 25-80 ℃, and the reaction system is cooled to room temperature after the reaction is completed. Under the conditions of the reaction time and the reaction temperature, the permanganate can be fully converted into the amorphous manganese oxide, side reactions are reduced, and the yield of the amorphous manganese oxide is improved.
It is understood that the time for the permanganate to react with the reducing agent can be, but is not limited to, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h; the reaction temperature can be, but is not limited to, 25 deg.C, 28 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, and 80 deg.C.
In some embodiments, in the step of slowly and dropwise adding the permanganate solution into the reducing agent solution under the conditions of magnetic stirring and/or ultrasound, the ultrasound time is 1-2 h, and the stirring time is 0.5-2 h. Under the condition, the permanganate solution is slowly dripped into the reducing agent solution, so that the permanganate and the reducing agent can be fully and uniformly mixed, and side reactions are reduced.
It can be understood that the time of ultrasound in the process of slow dripping can be but is not limited to 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours and 2 hours; the stirring time can be, but is not limited to, 0.5h, 0.6h, 0.8h, 1h, 1.2h, 1.4h, 1.5h, 1.8h, 2h.
In some of these embodiments, the solid phase is washed after the reaction is complete and the solid-liquid separation is performed, and before the second drying treatment is performed. Specifically, the solid phase is sufficiently washed with ultrapure water and anhydrous ethanol in this order to remove unreacted reaction raw materials and some other impurities in the solid phase.
In some embodiments, the temperature of the second drying treatment is 40-120 ℃, and the time of the second drying treatment is 4-12 h. It is understood that the temperature of the second drying process may be, but not limited to, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C; the time of the second drying treatment may be, but is not limited to, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.
Step S200: synthesis of manganese oxide/activated carbon catalyst
Dispersing the amorphous manganese oxide synthesized in the step S100 and activated carbon in a first solvent, uniformly stirring and mixing, performing solid-liquid separation to obtain a solid phase, and performing first drying treatment on the solid phase to obtain the manganese oxide catalyst.
The invention introduces the active carbon into the amorphous manganese oxide by the impregnation method, the specific surface area of the catalyst can be improved by introducing the active carbon by the impregnation method, so that the active component (the amorphous manganese oxide) of the catalyst is highly dispersed, and the active carbon can be used as an adsorption site for adsorbing harmful gas, thereby improving the activity and stability of the manganese oxide catalyst for decomposing the harmful gas.
In some examples, the mass ratio of the amorphous manganese oxide to the activated carbon in the prepared manganese oxide catalyst is (0.1-1): 1. through experimental research, the quality of the amorphous manganese oxide and the quality of the active carbon can obtain good catalytic activity of harmful gases under the condition of the mixture ratio.
It can be understood that the mass ratio of the amorphous manganese oxide to the activated carbon in the manganese oxide catalyst can be, but is not limited to, 0.1.
In some preferred embodiments, the mass ratio of the amorphous manganese oxide to the activated carbon in the manganese oxide catalyst is (0.3-1): 1, more preferably 0.3.
The test research shows that when the mass ratio of the amorphous manganese oxide to the activated carbon is (0.3-1): 1, the prepared manganese oxide catalyst has better catalytic performance. Particularly, when the reducing agent used in preparing the amorphous manganese oxide is oxalic acid, and the mass ratio of the amorphous manganese oxide to the activated carbon is 0.3; it can realize the complete oxidative decomposition of formaldehyde at 80 ℃.
In some of these embodiments, the first solvent is deionized water. It is understood that the first solvent may be any other solvent that can disperse the amorphous manganese oxide and the activated carbon well and facilitate the drying removal.
In some embodiments, the time for dispersing the amorphous manganese oxide and the activated carbon in the deionized water and stirring and mixing is 1-6 h. It is understood that the time for stirring and mixing the amorphous manganese oxide and the activated carbon can be, but is not limited to, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.
In some embodiments, after the amorphous manganese oxide and the activated carbon are mixed and stirred and solid-liquid separated, the temperature of the solid phase is 40-100 ℃, and the time of the first drying treatment is 4-8 h. It is understood that the temperature of the first drying process may be, but is not limited to, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃; the time of the first drying treatment may be, but is not limited to, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h.
Another embodiment of the present invention provides a manganese oxide catalyst comprising activated carbon and amorphous manganese oxide supported on the activated carbon. Wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1.
the invention comprises the following steps of mixing amorphous manganese oxide and active carbon according to the mass ratio (0.1-1): 1, so that the amorphous manganese oxide is loaded on the active carbon; the specific surface area of the manganese oxide catalyst can be improved, active components of the catalyst are highly dispersed, and adsorption sites of harmful gases are increased, so that the activity and stability of the manganese oxide catalyst for decomposing the harmful gases can be effectively improved.
The amorphous manganese oxide in the manganese oxide catalyst may be a commercially available product, or may be an amorphous manganese oxide synthesized by the preparation method of the present invention. In some embodiments, the amorphous manganese oxide is synthesized by the preparation method of the above embodiment of the present invention.
In some preferred embodiments, the mass ratio of the amorphous manganese oxide to the activated carbon in the manganese oxide catalyst is (0.3-1): 1; more preferably 0.3.
The manganese oxide catalyst or the manganese oxide catalyst prepared by the preparation method can be used as an oxidative decomposition catalyst to be applied to purification of various harmful gases. For example, it can be used for oxidative decomposition of formaldehyde. The manganese oxide catalyst can continuously and efficiently catalyze, oxidize and decompose formaldehyde gas at 80 ℃, and the catalytic activity of the manganese oxide catalyst is superior to that of the traditional manganese-based non-noble metal catalyst. In addition, no harmful by-products are generated in the process of catalytic oxidation decomposition, and secondary pollution is avoided.
In general, the preparation method of the manganese oxide catalyst adopts a two-step method, firstly, the amorphous manganese oxide is prepared by a simple oxidation-reduction method, the calcination step in the traditional manganese oxide preparation method is not needed, the crystallization of the manganese oxide is avoided, the phenomena of sintering and aggregation of particles in the calcination process are avoided, the catalytic activity of the manganese oxide catalyst is higher, the utilization rate of active components is higher, and the long-term stability of the manganese oxide catalyst is better; the subsequent introduction of active carbon via impregnation process can further raise the dispersivity of the active component and provide more harmful gas adsorbing sites, so as to further raise the catalytic activity of the catalyst. In addition, the preparation method has the advantages of easily available raw materials and simple process, and is convenient for industrial large-scale production.
The manganese oxide catalyst has high intrinsic catalytic activity and rich active sites, a large number of oxygen vacancies are effectively introduced through the amorphous manganese oxide to serve as active sites, and the introduction of the activated carbon further improves the specific surface area of the manganese oxide catalyst, improves the dispersion degree of the manganese oxide and serves as adsorption sites for adsorbing harmful gases. The manganese oxide catalyst can continuously and efficiently catalyze formaldehyde to be oxidized and decomposed at 80 ℃, no harmful byproducts are generated, and the catalytic activity of the manganese oxide catalyst is superior to that of most of manganese-based non-noble metal catalysts reported at present.
The present invention will be further described with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the present invention.
Example 1:
a preparation method of a manganese oxide catalyst comprises the following steps:
1)a 1 -MnO x catalysisSynthesis of the Agents
15mmol of KMnO 4 Dissolving in 60mL of deionized water; 30mmol of oxalic acid (H) 2 C 2 O 4 ) Dissolving in 100mL of deionized water; KMnO prepared as above was stirred under magnetic force 4 Slowly dripping the aqueous solution into the prepared oxalic acid aqueous solution; then reacting at 25 ℃ for 1h, and naturally cooling to room temperature; carrying out solid-liquid separation on the reaction solution, sequentially washing the obtained precipitate (namely a solid phase) with ultrapure water and absolute ethyl alcohol, and then drying for 8h at the temperature of 60 ℃ to prepare a 1 -MnO x Catalyst (i.e. amorphous manganese oxide, wherein a represents amorphous state and x represents oxygen atom number).
2)a 1 -MnO x Synthesis of/AC 1 catalyst
The target manganese oxide catalyst is prepared by adopting an immersion method. Specifically, 0.3g of a synthesized in the above step 1) was added 1 -MnO x Dispersing the catalyst in 100mL of deionized water, and then adding 1g of activated carbon into the dispersion liquid to stir and mix for 2 hours; then, the dispersion liquid is subjected to solid-liquid separation, the obtained precipitate (solid phase) is fully washed by ultrapure water and absolute ethyl alcohol in sequence, and the precipitate is dried to obtain a 1 -MnO x an/AC 1 catalyst (i.e., a manganese oxide catalyst, wherein AC represents activated carbon).
For a synthesized in step 2) 1 -MnO x The performance of the/AC 1 catalyst for catalyzing, oxidizing and decomposing formaldehyde is tested. The specific test results are shown in fig. 1.
The evaluation process of the formaldehyde catalytic decomposition performance comprises the following steps: evaluating the reaction performance of the manganese oxide catalyst and formaldehyde by adopting a continuous flowing fixed bed reactor; the fixed bed reactor mainly comprises three functional units of gas distribution, reaction and analysis. In the air distribution unit, synthetic air is taken as carrier gas and divided into three paths, wherein the two paths respectively pass through a formaldehyde solution and a water solution, and the mass flow meters on the branches are regulated, so that mixed gas consisting of dry air, wet air and formaldehyde gas is obtained. The reaction unit consists of a quartz tube and a heating device, and a proper amount of sample powder is placed in the quartz tube with the inner diameter of 4mm in a quartz cotton wrapping and clamping manner; then the quartz tube is placed in the oil bath pan and connected with the gas circuit to ensure the gas circuitAnd (4) sealing, heating to a set temperature, and introducing fully mixed reaction gas for reaction. The detection of the gaseous products and the concentration after the reaction was carried out by gas chromatography type GC-2014 equipped with FID. The test conditions were: 120ppm HCHO, 21vol.% O 2 Nitrogen as balance gas, gas flow rate 50mL min -1 The space velocity is 200L g -1 ·h -1 。
Example 2:
the preparation method of the manganese oxide catalyst of the present example is substantially the same as that of example 1 except that: in the embodiment, step 2) is carried out in the process of preparing the target manganese oxide catalyst by an immersion method 1 -MnO x Addition of catalyst in an amount of 0.1g, preparation of a 1 -MnO x a/AC 2 catalyst.
For a prepared in this example 1 -MnO x The performance of the/AC 2 catalyst in catalytic oxidative decomposition of formaldehyde was tested in the same manner as in example 1. The specific test results are shown in fig. 1.
Example 3:
the preparation method of the manganese oxide catalyst of this example is substantially the same as that of example 1 except that: in the embodiment, in the step 2) of preparing the target manganese oxide catalyst by the impregnation method, a 1 -MnO x Addition of 1g of catalyst to prepare a 1 -MnO x a/AC 3 catalyst.
For a prepared in this example 1 -MnO x The performance of the/AC 3 catalyst in catalytic oxidative decomposition of formaldehyde was tested in the same manner as in example 1. The specific test results are shown in fig. 1.
Example 4:
the preparation method of the manganese oxide catalyst of this example is substantially the same as that of example 1 except that: in the process of preparing the amorphous manganese oxide in the step 1) in the embodiment, the reducing agent is changed from oxalic acid to citric acid. Finally preparing to obtain a 2 -MnO x a/AC 1 catalyst.
For a prepared in this example 2 -MnO x The performance of the catalyst/AC 1 for catalytic oxidative decomposition of formaldehyde is tested, and the test method and the example 1 are carried outThe same is true. The specific test results are shown in fig. 1.
Comparative example 1:
the preparation method of the manganese oxide catalyst of this comparative example is substantially the same as that of example 1 except that: in this comparative example, step 2) was not carried out, i.e.a synthesized in step 1) was not present 1 -MnO x Active carbon is introduced into the catalyst. Directly using a synthesized in step 1) of example 1 1 -MnO x As a manganese oxide catalyst.
For a prepared in this comparative example 1 -MnO x The performance of the catalyst in catalyzing, oxidizing and decomposing formaldehyde is tested, and the test method is the same as that of the example 1. The specific test results are shown in fig. 1.
Comparative example 2:
a preparation method of a manganese oxide catalyst comprises the following steps:
1)c 1 -MnO x synthesis of the catalyst
15mmol of KMnO 4 Dissolving in 60mL of deionized water; 30mmol of oxalic acid (H) 2 C 2 O 4 ) Dissolving in 100mL of deionized water; KMnO prepared as above was stirred under magnetic force 4 Slowly dripping the aqueous solution into the prepared oxalic acid aqueous solution; then reacting at 25 ℃ for 1h, and naturally cooling to room temperature; carrying out solid-liquid separation on the reaction solution, sequentially washing the obtained precipitate (namely a solid phase) with ultrapure water and absolute ethyl alcohol, and then drying for 8h at the temperature of 60 ℃ to prepare a 1 -MnO x A catalyst; a is to 1 -MnO x The catalyst is further calcined for 2 hours at the temperature of 350 ℃ in the air atmosphere, and crystallized c is obtained by heating 1 -MnO x (wherein c represents crystallization);
2)c 1 -MnO x synthesis of/AC 1 catalyst
The target manganese oxide catalyst is prepared by adopting an immersion method. Specifically, 0.3g of c synthesized in the above step 1) was added 1 -MnO x Dispersing the catalyst in 100mL of deionized water, and then adding 1g of activated carbon into the dispersion liquid to stir and mix for 2 hours; then, the dispersion was subjected to solid-liquid separation, and the obtained precipitate (solid phase) was successively subjected to ultrapure water-free treatmentFully washing with water ethanol, and drying to obtain c 1 -MnO x a/AC 1 catalyst.
C for this comparative example 1 -MnO x The performance of the/AC 1 catalyst for catalyzing, oxidizing and decomposing formaldehyde is tested, and the test method is the same as that of the example 1. The specific test results are shown in fig. 1.
As can be seen from the results in FIG. 1, the manganese oxide catalysts prepared in examples 1 to 4 of the present invention all had better catalytic efficiency for formaldehyde at the same temperature than the catalyst without activated carbon (a) in comparative example 1 1 -MnO x ) Also superior to the catalyst for manganese oxide crystallization in comparative example 2 (c) 1 -MnO x /AC1)。
Also, the manganese oxide catalyst of example 1 of the present invention (a) 1 -MnO x /AC 1) and manganese oxide catalyst of example 3 (a) 1 -MnO x The catalytic activity of/AC 3) is apparently due to the manganese oxide catalyst (a) of example 2 1 -MnO x The catalytic activity of/AC 2). The mass ratio of the amorphous manganese oxide to the active carbon in the manganese oxide catalyst is (0.3-1): the catalyst has higher catalytic activity at 1.
Further, under the same conditions, the catalytic activity of example 4 is obviously reduced compared with example 1 only by changing the reducing agent from oxalic acid to citric acid, which indicates that the preparation of the amorphous manganese oxide by using oxalic acid as the reducing agent is more beneficial to improving the catalytic activity of the catalyst. Similarly, in examples 2 and 3, compared with example 1, the catalytic activity is significantly reduced compared with example 1 except that the mass ratio of the amorphous manganese oxide to the activated carbon is changed, which indicates that the mass ratio of the amorphous manganese oxide to the activated carbon is in the range of 0.3: the effect is best at 1 hour. Thus, the manganese oxide catalyst of example 1 of the present invention (a) 1 -MnO x /AC 1) by taking oxalic acid as a reducing agent, wherein the mass ratio of the amorphous manganese oxide to the activated carbon is 0.3:1, the catalytic performance of the obtained manganese oxide catalyst is optimal, and the manganese oxide catalyst can realize complete oxidative decomposition of formaldehyde at the temperature of 80 ℃.
Comparison of the formaldehyde conversion curves in FIG. 1 reveals that manganese oxide catalysis in the examples and comparative examplesCompared with the agent, pure activated carbon has almost no formaldehyde catalytic activity; the manganese oxide catalyst (a) of example 1 in which the activated carbon was supported 1 -MnO x The formaldehyde activity of the/AC 1) is almost that of the unsupported manganese oxide catalyst (a) of comparative example 1 1 -MnO x ) 2 times (80 ℃:100% vs.55%), which means that the introduction of the activated carbon is effective to improve the utilization rate of the active component (amorphous manganese oxide), thereby improving the catalytic activity of the manganese oxide catalyst.
As can also be seen from FIG. 1, the manganese oxide catalyst (c) crystallized in comparative example 2 1 -MnO x The catalytic activity of/AC 1) was much lower than that of the amorphous manganese oxide catalyst (a) in example 1 1 -MnO x Catalytic activity of/AC 1) (80 ℃:38% vs. 100%) due to annihilation of oxygen vacancies caused during thermal crystallization of the manganese oxide, resulting in reduction of active sites in the manganese oxide.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (13)
1. The manganese oxide catalyst is characterized by comprising activated carbon and amorphous manganese oxide loaded on the activated carbon, wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1.
2. the manganese oxide catalyst according to claim 1, wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.3 to 1): 1.
3. the preparation method of the manganese oxide catalyst is characterized by comprising the following steps of:
mixing amorphous manganese oxide, activated carbon and a first solvent to prepare a mixed solution;
carrying out solid-liquid separation on the mixed solution to obtain a solid phase, and carrying out first drying treatment on the solid phase to obtain the manganese oxide catalyst;
wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.1-1): 1.
4. the method for producing the manganese oxide catalyst according to claim 3, wherein the mass ratio of the amorphous manganese oxide to the activated carbon is (0.3 to 1): 1.
5. the method of preparing a manganese oxide catalyst according to claim 3, characterized in that said amorphous manganese oxide is prepared by the steps of:
and dissolving permanganate and a reducing agent in a second solvent for reaction, performing solid-liquid separation after the reaction is finished, taking a solid phase, and performing second drying treatment on the solid phase to obtain the amorphous manganese oxide.
6. The method of claim 5, wherein the reducing agent comprises one or more of oleic acid, oxalic acid, ammonium oxalate, citric acid, ascorbic acid.
7. The method of claim 5, wherein the concentration of the permanganate is 0.01 to 0.03mol/L and the concentration of the reducing agent is 0.02 to 0.05mol/L in the mixed solution of the second solvent, the permanganate, and the reducing agent.
8. The method for preparing the manganese oxide catalyst according to claim 5, wherein the reaction time is 0.5 to 10 hours, and the reaction temperature is 25 to 80 ℃.
9. The method for preparing a manganese oxide catalyst according to claim 5, characterized in that the temperature of said second drying treatment is 40-120 ℃ and the time of said second drying treatment is 4-12 hours.
10. The method of preparing a manganese oxide catalyst according to any one of claims 3 to 9, wherein said step of mixing the amorphous manganese oxide with the activated carbon and the first solvent is performed under stirring for a period of time of 1 to 6 hours; and/or
The temperature of the first drying treatment is 40-100 ℃, and the time of the first drying treatment is 4-8 h.
11. Use of the manganese oxide catalyst according to claim 1 or 2 or the manganese oxide catalyst prepared by the preparation method according to any one of claims 3 to 10 for purifying harmful gases.
12. Use according to claim 11, wherein the harmful gas comprises formaldehyde.
13. Use according to claim 11, wherein the manganese oxide catalyst is used for the catalytic decomposition of the harmful gases.
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