CN115106098A - Transition metal oxide catalyst and preparation method and application thereof - Google Patents
Transition metal oxide catalyst and preparation method and application thereof Download PDFInfo
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- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J37/00—Baking; Roasting; Grilling; Frying
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- B01D53/34—Chemical or biological purification of waste gases
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a transition metal oxide catalyst and a preparation method and application thereof. The transition metal oxide catalyst can be directly prepared by an oxidation-reduction method, and due to the simple preparation method and short reaction time, all metal elements in the obtained catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for pollutants such as VOCs (volatile organic chemicals) and grease, and simultaneously shows good stability, and the catalyst can be used for indoor air purification, oven self-cleaning and other scenes. The invention also relates to a preparation method and application of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalytic decomposition of organic matters, and particularly relates to a transition metal oxide catalyst and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs for short) are important components of air pollution, and the variety of the volatile Organic Compounds is various, and the volatile Organic Compounds contain various complex components such as aldehydes, ketones, alkane olefins and benzenes, so that the volatile Organic Compounds greatly harm human health. Especially formaldehyde in aldehydes and toluene in benzenes, have been clearly defined by the world health organization as "class 1 carcinogens", having teratogenic and carcinogenic effects on the human body. Therefore, the technology for efficiently removing various VOCs pollutants has important significance.
In the related art, there are two common methods for removing VOCs: physical and chemical methods. Among them, the physical methods include adsorption, absorption, condensation, membrane separation, etc., and the chemical methods include direct combustion, catalytic oxidation, photocatalysis, low-temperature plasma, etc.
The catalytic oxidation method completely decomposes VOCs into carbon dioxide and water by using a catalyst at a relatively low temperature, and has the advantages of high efficiency, no secondary pollution, no toxicity, no harm and the like. Catalytic oxidation processes use mainly two types of catalysts: noble metals such as Pt and Pd, and transition metal oxides. The noble metal catalyst has excellent performance, but the cost is too high, and the large-scale industrial application is difficult; the transition metal oxide catalyst has the advantages of simple preparation method, low cost and the like, and has higher commercial application possibility. Currently, the most widely used transition metal oxide catalyst is the manganese oxide system, but its catalytic ability is limited. In the related art, the transition metal oxide catalyst is mainly prepared by a high-temperature calcination method, a direct precipitation method, an isometric impregnation method and the like, so that the doping of elements is realized, but the methods have some defects. For example, the high-temperature calcination method requires high-temperature treatment, so that the energy consumption is high, the crystallinity of the obtained catalyst is high, and few catalytic active sites are caused; the direct precipitation method has the advantages that due to the fact that different metal elements have large difference in precipitation speed in the reaction process, element doping is easy to be uneven, and meanwhile the specific surface area of the catalyst is small; the isovolumetric impregnation method is limited by the solubility of metal salt, and element doping in a large range is difficult to realize; the above disadvantages all have certain influence on the performance of the catalyst. In particular, for the preparation of the trimetal oxide catalyst, it is very difficult to simultaneously obtain the characteristics of large-range adjustability of doping elements, high specific surface area, uniform element doping and the like. Therefore, there is a need to develop a transition metal oxide catalyst that is easily prepared.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a transition metal oxide catalyst which has the characteristics of large-range adjustable doping elements, high specific surface area and uniform element doping and can be prepared through simple redox reaction.
The invention also provides a preparation method of the transition metal oxide catalyst.
The invention also provides the application of the transition metal oxide catalyst in the catalytic degradation of organic matters.
The invention also provides a household appliance containing the transition metal oxide catalyst.
The first aspect of the invention provides a transition metal oxide catalyst, which comprises a cobalt-cerium-manganese ternary metal oxide catalyst, an iron-cerium-manganese ternary metal oxide catalyst, a cobalt-iron-manganese ternary metal oxide catalyst, a cobalt-cerium-iron ternary metal oxide catalyst or a cobalt-cerium-iron-manganese quaternary metal oxide catalyst, wherein the cobalt-cerium-manganese ternary metal oxide catalyst has a chemical formula of Co x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.05 and less than or equal to 0.6, y is more than or equal to 0.05 and less than or equal to 0.6, and z is more than or equal to 1.0 and less than or equal to 2.0.
The invention relates to a technical scheme of a transition metal oxide catalyst, which at least has the following beneficial effects:
the transition metal oxide catalyst can be directly prepared by an oxidation-reduction method, and due to the simple preparation method and short reaction time, all metal elements in the obtained catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for pollutants such as VOCs (volatile organic chemicals) and grease, and simultaneously shows good stability, and the catalyst can be used for indoor air purification, self-cleaning ovens and other scenes.
According to some embodiments of the invention, the Co is x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.2 and less than or equal to 0.6, y is more than or equal to 0.2 and less than or equal to 0.6, and z is more than or equal to 1.2 and less than or equal to 2.0.
According to some embodiments of the invention, the Co is x Ce y Mn 1-(x+y) O z Wherein x is 0.2, y is 0.2, and z is 1.4.
According to some embodiments of the invention, the Co is x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.1 and less than or equal to 0.6, y is more than or equal to 0.5 and less than or equal to 0.6, and z is more than or equal to 1.5 and less than or equal to 2.0.
According to some embodiments of the invention, the Co is x Ce y Mn 1-(x+y) O z Wherein x is 0.1, y is 0.5, and z is 1.8.
According to some embodiments of the invention, the cobalt cerium manganese ternary metal oxide catalyst has a concentration of 1000ppm or less and a space velocity of 50000h or less at 200 ℃ -1 The degradation efficiency of the toluene is more than 90 percent.
According to some embodiments of the invention, the cobalt-cerium-manganese ternary metal oxide catalyst has a decomposition efficiency of greater than 95% for animal and vegetable fats at 270 ℃.
According to some embodiments of the invention, the animal or vegetable fat comprises a common animal or vegetable fat.
According to some embodiments of the invention, the animal or vegetable fat comprises animal oil and vegetable oil.
According to some embodiments of the invention, the animal oil comprises lard, chicken oil, beef tallow, mutton fat or fish oil.
According to some embodiments of the invention, the vegetable oil comprises peanut oil, rapeseed oil, corn oil, soybean oil or sunflower oil.
According to some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is more than or equal to 100m 2 /g。
According to some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is 150m or more 2 /g。
According to some embodiments of the invention, the cobalt cerium manganese ternary metal oxide catalyst has a specific surface area of 150m 2 /g～300m 2 /g。
According to some embodiments of the invention, the cobalt cerium manganese ternary metal oxide catalyst has a specific surface area of 150m 2 /g～250m 2 /g。
A second aspect of the present invention provides a method for preparing a transition metal oxide catalyst, the method comprising: the catalyst is prepared by oxidation-reduction reaction of an oxidant containing transition metal elements and a reducing agent.
The invention relates to a technical scheme in a preparation method of a transition metal oxide catalyst, which at least has the following beneficial effects:
the invention relates to a preparation method of a transition metal oxide catalyst, which can be prepared by carrying out redox reaction on an oxidant containing a transition metal element and a reducing agent, and has the advantages of easier preparation method compared with the prior art, short reaction time, non-harsh reaction conditions, uniform distribution of all metal elements in the prepared catalyst, high specific surface area and high catalytic activity, excellent catalytic decomposition performance for pollutants such as VOCs (volatile organic chemicals), grease and the like, good stability, and applicability to indoor air purification, oven self-cleaning and other scenes.
The invention relates to a preparation method of a transition metal oxide catalyst, which effectively overcomes the defects of methods such as a high-temperature calcination method, a direct precipitation method, an isometric immersion method and the like.
The preparation method of the transition metal oxide catalyst has the advantages of simple method, short reaction time, high catalyst yield (close to 100 percent), no heavy metal ion emission pollution and environmental friendliness.
The invention relates to a preparation method of a transition metal oxide catalyst, and the obtained cobalt-cerium-manganese trimetal oxide catalyst powder can be finally dried at low temperature without high-temperature calcination treatment, and has the advantages of simple process, low carbon and energy saving.
According to some embodiments of the invention, the oxidizing agent comprises potassium permanganate or ferric salt and the reducing agent comprises at least two of ferrous salt, cerium salt, cobalt salt, iron salt, manganese salt.
According to some embodiments of the invention, the ferrous salt comprises at least one of ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous chloride.
According to some embodiments of the invention, the cerium salt comprises a cerium salt in a lower valence state.
According to some embodiments of the invention, the cerium salt in a reduced valence state comprises at least one of cerium sulfate, cerium nitrate, cerium acetate and cerium chloride.
According to some embodiments of the invention, the cobalt salt comprises a cobalt salt in a reduced valence state.
According to some embodiments of the invention, the lower valent cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate, cobalt acetate, and cobalt chloride.
According to some embodiments of the invention, the manganese salt comprises a low valence manganese salt.
According to some embodiments of the invention, the low-valent manganese salt comprises at least one of manganese sulfate, manganese nitrate, manganese acetate, and manganese chloride.
According to some embodiments of the present invention, potassium permanganate is used as an oxidant, and a cobalt salt and a cerium salt in a low valence state are both used as a reducing agent, and the uniformly doped cobalt-cerium-manganese trimetal oxide catalyst can be prepared by performing an oxidation-reduction reaction.
According to some embodiments of the present invention, potassium permanganate is used as an oxidant, and ferric salt and cerium salt in low valence state are both used as reducing agents, and the uniformly doped iron-cerium-manganese trimetal oxide catalyst is prepared by performing redox reaction.
According to some embodiments of the present invention, potassium permanganate is used as an oxidizing agent, and both a cobalt salt and an iron salt in a low valence state are used as reducing agents, and the uniformly doped cobalt-iron-manganese trimetal oxide catalyst is prepared by performing redox reaction.
According to some embodiments of the present invention, potassium permanganate is used as an oxidant, and lower valence cobalt salt, cerium salt and iron salt are used as reducing agents, and the uniformly doped cobalt-cerium-iron-manganese four-metal oxide catalyst is prepared by performing redox reaction.
According to some embodiments of the present invention, a uniformly doped cobalt-cerium-iron trimetal oxide catalyst is prepared by performing an oxidation-reduction reaction with a high-valence iron salt as an oxidant and a low-valence cobalt salt and cerium salt as a reductant.
According to some embodiments of the present invention, a uniformly doped cobalt-iron-manganese trimetal oxide catalyst is prepared by taking a high-valence iron salt as an oxidizing agent and taking a low-valence cobalt salt and manganese salt as a reducing agent through an oxidation reduction reaction.
According to some embodiments of the present invention, a uniformly doped fe-ce-mn trimetal oxide catalyst is prepared by performing an oxidation-reduction reaction with a high-valence ferric salt as an oxidant and a low-valence cerium salt and manganese salt as a reducing agent.
According to some embodiments of the present invention, a uniformly doped cobalt-cerium-iron-manganese four-metal oxide catalyst is prepared by performing a redox reaction by using a high-valence iron salt as an oxidant and using low-valence cobalt, cerium and manganese salts as a reductant.
According to some embodiments of the present invention, when the transition metal oxide catalyst is a cobalt-cerium-manganese ternary metal oxide catalyst, the preparation raw materials include an oxidizing agent, a reducing agent and a co-reactant, the oxidizing agent is potassium permanganate, and the reducing agent includes a cobalt salt and a cerium salt.
The reaction assistant is alkaline matter, the solution is acid before adding the reaction assistant, and the pH value of the solution is regulated to proper range for fast reaction and high yield. If no auxiliary reactant is added, the reaction process is slow, the required reaction time is long, and the product yield in the same time is low.
According to some embodiments of the invention, the cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt chloride.
According to some embodiments of the invention, the cerium salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, and cerium chloride.
According to some embodiments of the invention, the co-reactant comprises at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia, and urea.
According to some embodiments of the present invention, a method for preparing a cobalt-cerium-manganese ternary metal oxide catalyst comprises the steps of:
preparing a mixed solution of potassium permanganate, cobalt salt and cerium salt, adding the reaction promoter into the mixed solution for reaction, and after the reaction, carrying out solid-liquid separation to obtain a solid component, namely the cobalt-cerium-manganese ternary metal oxide catalyst.
According to some embodiments of the invention, the molar ratio of cobalt in the cobalt salt, cerium in the cerium salt and manganese in the potassium permanganate is x: y: 1- (x + y), wherein x is more than or equal to 0.05 and less than or equal to 0.6, y is more than or equal to 0.05 and less than or equal to 0.6, and z is more than or equal to 1.0 and less than or equal to 2.0.
According to some embodiments of the invention, the concentration of potassium permanganate is between 0.02 and 1.60 mol/L.
According to some embodiments of the invention, the cobalt salt has a concentration of 0.05mol/L to 2.50 mol/L.
According to some embodiments of the invention, the cobalt salt has a concentration of 0.1mol/L to 0.5 mol/L.
According to some embodiments of the invention, the cobalt salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, cerium chloride.
According to some embodiments of the invention, the cerium salt has a concentration of 0.05mol/L to 1.50 mol/L.
According to some embodiments of the invention, the cerium salt has a concentration of 0.1mol/L to 0.5 mol/L.
According to some embodiments of the invention, the cerium salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, cerium chloride.
According to some embodiments of the invention, the preparation method of the cobalt-cerium-manganese ternary metal oxide catalyst further comprises adjusting the pH of the mixed solution to 5-14 by adding the co-reactant before the reaction.
According to some embodiments of the invention, the preparation method of the cobalt-cerium-manganese ternary metal oxide catalyst further comprises adjusting the pH of the mixed solution to 7-10 by adding the co-reactant before the reaction.
The pH value of the mixed solution is adjusted to a proper range, so that the reaction speed can be accelerated, and the yield can be improved.
According to some embodiments of the invention, the temperature of the reaction is between 20 ℃ and 100 ℃.
According to some embodiments of the invention, the temperature of the reaction is between 50 ℃ and 80 ℃.
According to some embodiments of the invention, the reaction time is between 1h and 24 h.
According to some embodiments of the invention, the reaction time is between 3h and 8 h.
According to some embodiments of the invention, in order to facilitate the reaction, stirring may be performed during the reaction.
According to some embodiments of the invention, the stirring speed is 300rpm to 3000 rpm.
According to some embodiments of the invention, the stirring speed is between 500rpm and 1500 rpm.
According to some embodiments of the invention, the co-reactant is added to the mixed solution at a rate of 5mL/min to 50 mL/min.
According to some embodiments of the invention, the co-reactant is added to the mixed solution at a rate of 10mL/min to 30 mL/min.
According to some embodiments of the present invention, the preparation method of the cobalt-cerium-manganese ternary metal oxide catalyst further comprises drying the solid component after water washing after solid-liquid separation.
According to some embodiments of the present invention, the number of times the solid component is subjected to water washing may be multiple times.
According to some embodiments of the invention, the apparatus for solid-liquid separation comprises one of a vacuum filter, a high speed centrifuge, a plate and frame machine.
According to some embodiments of the invention, the drying process comprises a forced air oven.
According to some embodiments of the invention, the temperature of the drying process is between 80 ℃ and 250 ℃.
According to some embodiments of the invention, the temperature of the drying process is between 100 ℃ and 150 ℃.
According to some embodiments of the invention, the drying process is performed for a time period of 4 to 48 hours.
According to some embodiments of the invention, the drying process is performed for 6 to 12 hours.
According to some embodiments of the present invention, the cobalt-cerium-manganese ternary metal oxide catalyst obtained after the drying treatment is a powdered cobalt-cerium-manganese ternary metal oxide catalyst.
The third aspect of the invention provides the application of the transition metal oxide catalyst in the catalytic degradation of organic matters.
The invention relates to a technical scheme of application of a transition metal oxide catalyst in catalytic degradation of organic matters, which at least has the following beneficial effects:
according to the transition metal oxide catalyst, metal elements in the catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for organic pollutants such as VOCs (volatile organic compounds), grease and the like, and simultaneously shows good stability, so that the catalyst is suitable for indoor air purification, oven self-cleaning and other scenes.
According to some embodiments of the invention, the organic contaminants comprise volatile organics and grease.
According to some embodiments of the invention, the transition metal oxide catalyst is added in the catalytic decomposition of fats and oils in an amount of 5mg to 10mg of the catalyst per 100g of fats and oils.
According to some embodiments of the invention, the transition metal oxide catalyst is added in the catalytic decomposition of fats and oils in an amount of 5mg to 7.5mg of catalyst per 100g of fats and oils.
According to some embodiments of the invention, the transition metal oxide catalyst is added in the catalytic decomposition of fats and oils in an amount of 7.5mg to 10mg of catalyst per 100g of fats and oils.
In a fourth aspect of the present invention, there is provided a home appliance comprising the transition metal oxide catalyst.
The invention relates to a technical scheme in household appliances, which at least has the following beneficial effects:
according to the household appliance, due to the fact that the transition metal oxide catalyst is used, all metal elements in the catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for organic pollutants such as VOCs and grease, and the catalyst also shows good stability, and therefore the household appliance can better decompose the organic pollutants such as VOCs and grease in the air due to the fact that the transition metal oxide catalyst is arranged in the household appliance.
According to some embodiments of the invention, the household appliance comprises an air purifier, an oven, an oil heater or a range hood.
Drawings
FIG. 1 is Co of example 1 0.1 Ce 0.5 Mn 0.4 O z -a micro-topography of R1.
FIG. 2 is Co of example 6 0.2 Ce 0.2 Mn 0.6 O z -a micro-topography of R1.
FIG. 3 is Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z -a micro-topography of C1.
FIG. 4 is a BET specific surface area test curve of a cerium manganese trimetallic oxide catalyst.
Fig. 5 is an XRD pattern of cobalt cerium manganese trimetallic oxide catalyst.
FIG. 6 is a toluene decomposition performance test curve of a cobalt cerium manganese trimetallic oxide catalyst.
FIG. 7 is a test curve of the performance stability of cobalt cerium manganese trimetallic oxide catalyst in toluene decomposition at 200 ℃ for 48 hours.
FIG. 8 is a TGA test curve of the decomposition of chicken fat by Co-Ce-Mn trimetal oxide catalyst.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the present invention, the present invention provides a transition metal oxide catalyst comprising a cobalt-cerium-manganese ternary metal oxide catalyst, an iron-cerium-manganese ternary metal oxide catalyst, a cobalt-iron-manganese ternary metal oxide catalyst, a cobalt-cerium-iron ternary metal oxide catalyst, or a cobalt-cerium-iron-manganese quaternary metal oxide catalyst, the cobalt-cerium-manganese ternary metal oxide catalyst having the chemical formula Co x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.05 and less than or equal to 0.6, y is more than or equal to 0.05 and less than or equal to 0.6, and z is more than or equal to 1.0 and less than or equal to 2.0.
The transition metal oxide catalyst can be directly prepared by a redox method, and due to the simple preparation method and short reaction time, all metal elements in the obtained catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for pollutants such as VOCs (volatile organic chemicals), grease and the like, and simultaneously shows good stability, and the catalyst can be used for indoor air purification, oven self-cleaning and other scenes.
Specifically, Co x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.2 and less than or equal to 0.6, y is more than or equal to 0.2 and less than or equal to 0.6, and z is more than or equal to 1.2 and less than or equal to 2.0.
Further, Co x Ce y Mn 1-(x+y) O z Wherein x is 0.2, y is 0.2, and z is 1.4.
Specifically, theSaid, Co x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.1 and less than or equal to 0.6, y is more than or equal to 0.5 and less than or equal to 0.6, and z is more than or equal to 1.5 and less than or equal to 2.0.
Further, Co x Ce y Mn 1-(x+y) O z Wherein x is 0.1, y is 0.5, and z is 1.8.
In some embodiments of the invention, the cobalt cerium manganese ternary metal oxide catalyst has a concentration of 1000ppm or less and a space velocity of 50000h or less at 200 deg.C -1 The degradation efficiency of the toluene is more than 90 percent.
The "space velocity" refers to the amount of gas treated per unit volume of catalyst per unit time under a predetermined condition. In some embodiments of the invention, the space velocity is the flow rate of toluene divided by the volume of catalyst.
In some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is less than or equal to 300m 2 /g。
In some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is 280m or less 2 /g。
In some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is less than or equal to 250m 2 /g。
In some embodiments of the invention, the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is more than or equal to 150m 2 /g。
In some embodiments of the invention, the cobalt-cerium-manganese ternary metal oxide catalyst has a decomposition efficiency of greater than 95% for animal and vegetable fats and oils at 270 ℃.
The animal or vegetable fat includes common animal or vegetable fats.
It is conceivable that the animal or vegetable fat and oil includes animal oil and vegetable oil.
Specifically, the animal oil includes lard, chicken oil, beef tallow, mutton fat, and fish oil.
Specifically, the vegetable oil comprises peanut oil, rapeseed oil, corn oil, soybean oil and sunflower seed oil.
In some other embodiments of the present invention, the present invention provides a method for preparing a transition metal oxide catalyst, where the transition metal oxide catalyst includes a cobalt-cerium-manganese ternary metal oxide catalyst, an iron-cerium-manganese ternary metal oxide catalyst, a cobalt-iron-manganese ternary metal oxide catalyst, a cobalt-cerium-iron ternary metal oxide catalyst, or a cobalt-cerium-iron-manganese quaternary metal oxide catalyst, and the preparation method includes: the catalyst is prepared by oxidation-reduction reaction of an oxidant containing transition metal elements and a reducing agent.
The preparation method of the transition metal oxide catalyst is easier than the prior art, has short reaction time and mild reaction conditions, can uniformly distribute the metal elements in the prepared catalyst, has high specific surface area and high catalytic activity, can show excellent catalytic decomposition performance on pollutants such as VOCs, grease and the like, simultaneously shows good stability, and can be used for scenes such as indoor air purification, oven self-cleaning and the like.
It can also be understood that the preparation method of the transition metal oxide catalyst of the present invention effectively overcomes the disadvantages of the methods such as the high temperature calcination method, the direct precipitation method, the equal volume impregnation method, etc.
It can be understood that the preparation method of the transition metal oxide catalyst of the invention has the advantages of simple method, short reaction time, high catalyst yield (close to 100 percent), no heavy metal ion emission pollution and environmental protection.
The preparation method of the transition metal oxide catalyst can be understood that the obtained cobalt-cerium-manganese trimetal oxide catalyst powder can be finally dried at low temperature without high-temperature calcination treatment, and the preparation method is simple in process, low-carbon and energy-saving.
In some embodiments of the invention, the oxidizing agent comprises potassium permanganate or ferric salt and the reducing agent comprises at least two of ferrous salt, cerium salt, cobalt salt, ferric salt, manganese salt.
In some embodiments of the present invention, the ferrous salt comprises at least one of ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous chloride.
In some embodiments of the invention, the cerium salt comprises a lower valence cerium salt.
Further, the cerium salt in a lower valence state includes at least one of cerium sulfate, cerium nitrate, cerium acetate, and cerium chloride.
In some embodiments of the invention, the cobalt salt comprises a cobalt salt in a reduced valence state.
Further, the cobalt salt in a lower valence state includes at least one of cobalt sulfate, cobalt nitrate, cobalt acetate, and cobalt chloride.
In some embodiments of the invention, the manganese salt comprises a low valence manganese salt.
Further, the low valence manganese salt includes at least one of manganese sulfate, manganese nitrate, manganese acetate, and manganese chloride.
In some embodiments of the present invention, potassium permanganate is used as an oxidant, and both low-valence cobalt salt and cerium salt are used as reducing agents, and the uniformly doped cobalt-cerium-manganese trimetal oxide catalyst can be prepared by performing redox reaction.
In some embodiments of the present invention, potassium permanganate is used as an oxidant, and ferric salt and cerium salt in low valence state are both used as reducing agents, and the uniformly doped iron-cerium-manganese trimetal oxide catalyst is prepared by performing redox reaction.
In some embodiments of the present invention, potassium permanganate is used as an oxidant, and both low-valence cobalt salt and iron salt are used as reducing agents, and the uniformly doped cobalt-iron-manganese trimetal oxide catalyst is prepared by performing redox reaction.
In some embodiments of the present invention, potassium permanganate is used as an oxidant, and a cobalt salt, a cerium salt and an iron salt in a low valence state are used as reducing agents, and the uniformly doped cobalt-cerium-iron-manganese four-metal oxide catalyst is prepared by performing an oxidation reduction reaction.
In some embodiments of the present invention, a uniformly doped cobalt-cerium-iron trimetal oxide catalyst is prepared by taking a high-valence iron salt as an oxidizing agent and taking a low-valence cobalt salt and cerium salt as a reducing agent through an oxidation-reduction reaction.
In some embodiments of the invention, a uniformly doped cobalt-iron-manganese trimetal oxide catalyst is prepared by taking a high-valence iron salt as an oxidant and taking a low-valence cobalt salt and manganese salt as a reducing agent through oxidation-reduction reaction.
In some embodiments of the present invention, a uniformly doped fe-ce-mn trimetal oxide catalyst is prepared by taking a high-valence iron salt as an oxidant and taking a low-valence cerium salt and manganese salt as a reducing agent through an oxidation-reduction reaction.
In some embodiments of the present invention, a uniformly doped cobalt-cerium-iron-manganese four-metal oxide catalyst is prepared by performing a redox reaction by using a high-valence iron salt as an oxidant and using low-valence cobalt, cerium and manganese salts as reducing agents.
In some embodiments of the present invention, when the transition metal oxide catalyst is a cobalt-cerium-manganese ternary metal oxide catalyst, the preparation raw material includes an oxidant, a reducing agent and a co-reactant, the oxidant is potassium permanganate, the reducing agent includes a cobalt salt and a cerium salt, the cobalt salt includes at least one of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride, the cerium salt includes at least one of cerium sulfate, cerium nitrate, cerium acetate and cerium chloride, and the co-reactant includes at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia water and urea.
It should be noted that the reaction promoter is an alkaline substance, the solution is acidic before the reaction promoter is added, and one of the functions of the reaction promoter is to adjust the pH of the solution to a proper range, so as to accelerate the reaction and increase the yield. If no auxiliary reactant is added, the reaction process is slow, the required reaction time is long, and the product yield in the same time is low.
In some embodiments of the present invention, a method for preparing a cobalt-cerium-manganese ternary metal oxide catalyst comprises the steps of:
mixing potassium permanganate with cobalt salt and cerium salt to obtain a mixed solution, adding a reaction promoter into the mixed solution, adjusting the pH of the mixed solution, reacting, and carrying out solid-liquid separation after reaction to obtain a solid component, namely the cobalt-cerium-manganese ternary metal oxide catalyst.
In some embodiments of the invention, the concentration of potassium permanganate is between 0.02mol/L and 1.60 mol/L.
In some embodiments of the invention, the concentration of the cobalt salt is 0.05mol/L to 2.50 mol/L.
Furthermore, the concentration of the cobalt salt is 0.1 mol/L-0.5 mol/L.
In some embodiments of the invention, the cobalt salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, cerium chloride.
In some embodiments of the invention, the cerium salt is present at a concentration of 0.05mol/L to 1.50 mol/L.
Further, the concentration of the cerium salt is 0.1mol/L to 0.5 mol/L.
In some embodiments of the invention, the cerium salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, cerium chloride.
In some embodiments of the invention, the temperature of the reaction is from 20 ℃ to 100 ℃.
Further, the reaction temperature is 50-80 ℃.
In some embodiments of the invention, the reaction time is from 1 hour to 24 hours.
Further, the reaction time is 3-8 h.
In some embodiments of the invention, to facilitate the reaction, stirring may be performed during the reaction.
Specifically, the stirring speed is 300 to 3000 rpm.
Further, the stirring speed is 500rpm to 1500 rpm.
In some embodiments of the invention, the co-reactant is added to the mixed solution at a rate of 5mL/min to 50 mL/min.
Specifically, the rate of adding the co-reactant to the mixed solution is 10mL/min to 30 mL/min.
In some embodiments of the present invention, adjusting the pH of the mixed solution means adjusting the pH of the mixed solution to 5 to 14.
Further, adjusting the pH of the mixed solution means adjusting the pH of the mixed solution to 7-10.
In some embodiments of the present invention, the preparation method of the cobalt-cerium-manganese ternary metal oxide catalyst further comprises washing the solid component obtained by solid-liquid separation for multiple times with water.
In some embodiments of the invention, the apparatus for solid-liquid separation comprises one of a vacuum filter, a high speed centrifuge, a plate and frame machine.
In some embodiments of the present invention, the preparation method of the cobalt-cerium-manganese ternary metal oxide catalyst further comprises drying the product after washing.
Specifically, the drying process includes a blast oven.
Specifically, the temperature of the drying treatment is 80-250 ℃.
Further, the temperature of the drying treatment is 100-150 ℃.
In some embodiments of the present invention, the drying time is 4 to 48 hours.
Further, the drying time is 6-12 h.
In some embodiments of the present invention, the cobalt-cerium-manganese ternary metal oxide catalyst obtained after the drying treatment is a powdered cobalt-cerium-manganese ternary metal oxide catalyst.
In further embodiments of the present invention, the present invention provides the use of a transition metal oxide catalyst for the catalytic degradation of organic matter.
It is easy to understand that, in the transition metal oxide catalyst, all metal elements in the catalyst can be uniformly distributed, the specific surface area is high, the catalytic activity is high, the catalyst can show excellent catalytic decomposition performance for organic pollutants such as VOCs (volatile organic chemicals) and grease, and simultaneously shows good stability, and the catalyst is suitable for indoor air purification, oven self-cleaning and other scenes.
In still other embodiments of the present invention, there is provided a home appliance comprising the transition metal oxide catalyst.
It is not hard to think that, because the transition metal oxide catalyst is used in the household appliances of the invention, each metal element in the catalyst can be evenly distributed, the specific surface area is high, the catalytic activity is high, and the catalyst can show excellent catalytic decomposition performance and good stability for organic pollutants such as VOCs and grease, therefore, the household appliances can better decompose the organic pollutants such as VOCs and grease in the air because the transition metal oxide catalyst of the invention is arranged in the household appliances.
In some embodiments of the invention, the domestic appliance comprises an air purifier, an oven, an oil heater or a range hood.
The technical scheme of the invention is better understood by combining specific examples and comparative examples.
Example 1
This example prepared a cobalt cerium manganese trimetallic oxide catalyst, noted Co 0.1 Ce 0.5 Mn 0.4 O z -R1。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The co-reactant potassium hydroxide was added to the mixed solution at a dropping rate of 5mL/min until the solution pH became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 99.7%.
It is to be noted that the yield is calculated as the actual mass of reaction product divided by the theoretical mass of catalyst.
Example 2
This example prepares a cobalt cerium manganese trimetal oxideCatalyst, noted as Co 0.1 Ce 0.5 Mn 0.4 O z -R2。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 80 ℃ with stirring at 500 rpm.
The co-reactant potassium hydroxide was added to the mixed solution at a dropping rate of 5mL/min until the solution pH became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 99.8%.
Example 3
This example prepared a cobalt cerium manganese trimetallic oxide catalyst, noted Co 0.1 Ce 0.5 Mn 0.4 O z -R3。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The co-reactant aqueous ammonia was added to the mixed solution at a dropping rate of 5mL/min until the pH of the solution became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 99.4%.
Example 4
This example prepared a cobalt cerium manganese trimetallic oxide catalyst, noted Co 0.1 Ce 0.5 Mn 0.4 O z -R4。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The co-reactant potassium hydroxide was added to the mixed solution at a dropping rate of 20mL/min until the solution pH was 7.
After reacting for 2 hours, carrying out solid-liquid separation by a vacuum filtration method, then cleaning the solid product by water, and drying in a blast oven at 100 ℃ for 8 hours to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 99.7%.
Example 5
This example prepared a cobalt cerium manganese trimetallic oxide catalyst, noted Co 0.1 Ce 0.5 Mn 0.4 O z -R5。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt sulfate), cerium salt (cerium sulfate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt sulfate is 0.1mol/L, the concentration of the cerium sulfate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The co-reactant potassium hydroxide was added to the mixed solution at a dropping rate of 5mL/min until the solution pH became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 99.5%.
Example 6
This example prepared a cobalt cerium manganese trimetallic oxide catalyst, noted Co 0.2 Ce 0.2 Mn 0.6 O z -R1。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.2mol/L, the concentration of the cerium nitrate is 0.2mol/L, and the concentration of the potassium permanganate is 0.6 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The co-reactant potassium hydroxide was added to the mixed solution at a dropping rate of 5mL/min until the solution pH became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 97.7%.
Comparative example 1
The comparative example adopts a direct precipitation method to prepare cobaltCerium manganese trimetallic oxide catalyst, noted Co 0.1 Ce 0.5 Mn 0.4 O z -C1。
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and vacancies in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and manganese salt (manganese nitrate), wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the manganese nitrate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
The precipitant potassium hydroxide was added to the mixed solution at a dropping rate of 5mL/min until the solution pH became 7.
After reacting for 2h, carrying out solid-liquid separation by a vacuum filtration method, then washing a solid product by water, drying in a blast oven at 100 ℃ for 8h, and then calcining at 800 ℃ in a muffle furnace for 6h to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 89.6%.
The yield is calculated as the actual mass of reaction product divided by the theoretical mass of catalyst.
It should be noted that although potassium hydroxide was also added in comparative example 1, potassium hydroxide, which is a precipitant, is different from the co-reactant potassium hydroxide in example 1. The reason is that in comparative example 1, since there is no oxidizing agent (potassium permanganate), after KOH is added, cobalt nitrate, cerium nitrate, and manganese nitrate react with KOH to generate corresponding hydroxide precipitates, and then after filtration and cleaning, the oxides can be obtained by high-temperature calcination in a muffle furnace, so KOH acts as a precipitant in comparative example 1. In example 1, potassium permanganate as a strong oxidant reacts with cobalt nitrate and cerium nitrate to perform redox reaction, which is used to accelerate the reaction and increase the yield, so KOH in example 1 is used as a co-reactant.
Comparative example 2
The comparative example adopts an oxidation-reduction method to prepare a cobalt-cerium-manganese trimetal oxide catalyst which is marked as Co 0.1 Ce 0.5 Mn 0.4 O z -R0. This comparative example does not use a co-reactant in the preparation process.
Wherein the value of z is 1.2-2.0, and the specific value is related to the actual valence states of several metals and the vacancy in the material.
The preparation process comprises the following steps:
preparing a mixed solution of cobalt salt (cobalt nitrate), cerium salt (cerium nitrate) and potassium permanganate, wherein the solvent is water, the concentration of the cobalt nitrate is 0.1mol/L, the concentration of the cerium nitrate is 0.5mol/L, and the concentration of the potassium permanganate is 0.4 mol/L.
The mixed solution was heated in a water bath to 50 ℃ with stirring at 500 rpm.
After the reaction is carried out for 12 hours, carrying out solid-liquid separation by a vacuum filtration method, then washing the solid product by water, and drying in a blast oven at 100 ℃ for 8 hours to obtain the cobalt-cerium-manganese trimetal oxide catalyst powder.
In this example, the yield of the cobalt-cerium-manganese trimetallic oxide catalyst powder was 68.3%.
Because the ratio of cobalt, cerium and manganese has the most obvious influence on the structure and performance of the catalyst, and the influence of other preparation parameters is relatively small, in examples 1 to 5, the ratio of cobalt, cerium and manganese is 0.1:0.5:0.4, so that only Co of example 1 is used 0.1 Ce 0.5 Mn 0.4 O z -R1 as representative of Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z -C1 and Co of example 6 0.2 Ce 0.2 Mn 0.6 O z R1 for comparison.
The microscopic morphology of the prepared catalyst was first observed. As shown in fig. 1-3.
FIG. 1 is Co of example 1 0.1 Ce 0.5 Mn 0.4 O z -R1. FIG. 2 is Co of example 6 0.2 Ce 0.2 Mn 0.6 O z -R1. FIG. 3 is Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z -C1。
As can be seen from FIGS. 1 and 2, examples 1 and 6 employ Co-Ce-Mn trimetal oxide catalysts prepared by a redox method 0.1 Ce 0.5 Mn 0.4 O z -R1 and Co 0.2 Ce 0.2 Mn 0.6 O z R1 is in a loose state and has a uniform and well distributed particle size.
As can be seen from FIG. 3, comparative example 1 employs Co-Ce-Mn trimetal oxide catalyst prepared by direct precipitation 0.1 Ce 0.5 Mn 0.4 C1 appears to be more compact and has less uniform particle size distribution.
Further, the Co of example 1 was tested 0.1 Ce 0.5 Mn 0.4 O z -R1, Co of example 6 0.2 Ce 0.2 Mn 0.6 O z R1 and Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z The specific surface area curve of-C1, the results are shown in FIG. 4. The specific surface area and pore volume of the resulting catalyst were calculated as shown in table 1.
TABLE 1 specific surface area and pore volume calculation results
In table 1, the ratios of cobalt, cerium and manganese were obtained by X-ray spectroscopy. As can be seen from Table 1, Co 0.1 Ce 0.5 Mn 0.4 O z - -R1 and Co 0.2 Ce 0.2 Mn 0.6 O z The specific surface area and pore volume of- -R1 are significantly higher than those of Co 0.1 Ce 0.5 Mn 0.4 O z --C1。
Further, Co of example 1 was tested 0.1 Ce 0.5 Mn 0.4 O z - -R1, Co of example 6 0.2 Ce 0.2 Mn 0.6 O z -R1 and comparisonCo of example 1 0.1 Ce 0.5 Mn 0.4 O z The XRD pattern of-C1, the result is shown in FIG. 5. From FIG. 5, it can be seen that Co in comparative example 0.1 Ce 0.5 Mn 0.4 O z The XRD spectrum of-C1 shows obvious crystallization peaks of cerium oxide and manganese oxide, no crystallization peak of cobalt oxide is seen, but the crystallization peak of manganese cobalt oxide is seen, which indicates that only cobalt element and manganese element form doping, and the catalyst exists in the form of physical mixture of cerium oxide, manganese oxide and manganese cobalt oxide, and is not a true completely uniformly-doped cobalt cerium manganese trimetal oxide catalyst.
Furthermore, Co of comparative example 1 in Table 1 was incorporated 0.1 Ce 0.5 Mn 0.4 O z The actual value of Co: Ce: Mn of-C1 was 0.18:0.37:0.45, which is greatly different from the theoretical value of 0.1:0.5:0.4, and it was found that this is due to the product constant of the solubilities of cobalt ion, cerium ion and manganese ion (K) in the solution sp ) The difference is large, after the precipitating agent is added, the precipitation speed difference of different metal ions is obvious, uneven precipitation is caused, and therefore uniform doping cannot be realized. And Co in example 1 0.1 Ce 0.5 Mn 0.4 O z -R1 and Co in example 6 0.2 Ce 0.2 Mn 0.6 O z The measured values of cobalt, cerium and manganese of R1 are substantially in full agreement with theoretical values, which further illustrates that the catalyst prepared in the examples is more uniformly doped.
Further, the catalyst was tested for its decomposition performance with respect to toluene, and the results are shown in fig. 6. Co of example 1 was found 0.1 Ce 0.5 Mn 0.4 O z - -R1 and Co of example 6 0.2 Ce 0.2 Mn 0.6 O z T of-R1 90 (T 90 Defined as the catalytic temperature corresponding to 90% decomposition rate of toluene) was significantly lower than that of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z C1, indicating that the former performs better, mainly thanks to its higher specific surface area and pore volume. Meanwhile, more active sites can be introduced into the catalyst by more uniform doping, so that the catalytic performance is improved, and the service life of the catalyst can be prolonged.
Further, the decomposition rate in toluene was continuously measured at 200 ℃ for 48 hours, and the results are shown in FIG. 7. As can be seen from FIG. 7, Co of example 1 0.1 Ce 0.5 Mn 0.4 O z -R1 and Co of example 6 0.2 Ce 0.2 Mn 0.6 O z The decomposition rate of R1 for toluene remained substantially constant, while Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z A significant drop in-C1 occurred.
Furthermore, the decomposition condition of the catalyst on the chicken oil in the animal fat is tested, and the test method comprises the steps of directly adding the catalyst into the chicken oil, uniformly mixing and then carrying out thermal gravimetric analysis. The amount of catalyst added was about 7.5mg per 5mg of chicken fat. The results are shown in FIG. 8 and Table 2.
TABLE 2 decomposition test results of catalyst on chicken fat
As can be seen from FIG. 8 and Table 2, Co of example 1 0.1 Ce 0.5 Mn 0.4 -R1 and Co of example 6 0.2 Ce 0.2 Mn 0.6 O z T of R1 onset (T onset The catalytic temperature corresponding to the intersection of the reverse extensions of the two linear regions before and after the rapid weight loss of the TGA curve) is significantly lower than that of Co of comparative example 1 0.1 Ce 0.5 Mn 0.4 O z -C1. The catalyst of the invention is used for decomposing gaseous organic pollutants such as toluene and has good degradation effect on liquid animal and vegetable oil.
The test methods for the decomposition of toluene and oils and fats described above are common test methods in the literature. In particular, the decomposition temperature T of toluene 90 Defined as the catalytic temperature corresponding to 90% toluene decomposition. The decomposition temperature Tonset of the chicken oil is defined as the catalytic temperature corresponding to the intersection point of the reverse extension lines of two linear zones before and after the rapid weight loss of a TGA curve.
Under the condition of not adding a catalyst, the degradation temperature of toluene is above 500 ℃, and the decomposition temperature of chicken oil is above 400 ℃. As can be seen in FIG. 6, the toluene degradation efficiency at the highest test temperature (240 ℃ C.) is essentially 0. It can be seen in figure 8 that even at temperatures up to 300 c, the weight loss of chicken oil was less than 15%, whereas it was substantially close to 100% with the catalyst.
The above data show that the cobalt-cerium-manganese trimetal oxide catalyst prepared by the method of the invention has excellent comprehensive properties.
In still other embodiments of the present invention, there is provided a home appliance comprising the transition metal oxide catalyst.
It is not hard to think that, because the transition metal oxide catalyst is used in the household appliances of the invention, each metal element in the catalyst can be evenly distributed, the specific surface area is high, the catalytic activity is high, and the catalyst can show excellent catalytic decomposition performance and good stability for organic pollutants such as VOCs and grease, therefore, the household appliances can better decompose the organic pollutants such as VOCs and grease in the air because the transition metal oxide catalyst of the invention is arranged in the household appliances.
In some embodiments of the invention, the organic contaminants include volatile organics and greases.
In some embodiments of the invention, the domestic appliance comprises an air purifier, an oven, an oil heater or a range hood.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (18)
1. The transition metal oxide catalyst is characterized by comprising a cobalt-cerium-manganese ternary metal oxide catalyst, an iron-cerium-manganese ternary metal oxide catalyst, a cobalt-iron-manganese ternary metal oxide catalyst, a cobalt-cerium-iron ternary metal oxide catalyst or a cobalt-cerium-iron ternary metal oxide catalystThe chemical formula of the cerium-iron-manganese quaternary metal oxide catalyst is Co x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.05 and less than or equal to 0.6, y is more than or equal to 0.05 and less than or equal to 0.6, and z is more than or equal to 1.0 and less than or equal to 2.0.
2. The transition metal oxide catalyst of claim 1, wherein the Co is present in an amount sufficient to promote the catalytic activity of the catalyst x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.2 and less than or equal to 0.6, y is more than or equal to 0.2 and less than or equal to 0.6, and z is more than or equal to 1.2 and less than or equal to 2.0.
3. The transition metal oxide catalyst of claim 1, wherein the Co is present in an amount sufficient to promote the catalytic activity of the catalyst x Ce y Mn 1-(x+y) O z Wherein x is more than or equal to 0.1 and less than or equal to 0.6, y is more than or equal to 0.5 and less than or equal to 0.6, and z is more than or equal to 1.5 and less than or equal to 2.0.
4. The transition metal oxide catalyst according to any one of claims 1 to 3, wherein the specific surface area of the cobalt-cerium-manganese ternary metal oxide catalyst is not less than 100m 2 /g。
5. A process for preparing the transition metal oxide catalyst according to any one of claims 1 to 4, wherein the process is: the catalyst is prepared by oxidation-reduction reaction of an oxidant containing transition metal elements and a reducing agent.
6. The method of claim 5, wherein the oxidizing agent comprises potassium permanganate or ferric salt, and the reducing agent comprises at least two of ferrous salt, cerium salt, cobalt salt, and manganese salt.
7. The method of claim 5, wherein when the transition metal oxide catalyst is a cobalt-cerium-manganese ternary metal oxide catalyst, the raw materials for preparation comprise an oxidizing agent, a reducing agent and a co-reactant, the oxidizing agent is potassium permanganate, and the reducing agent comprises a cobalt salt and a cerium salt.
8. The method of claim 7, wherein the cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate, cobalt acetate, and cobalt chloride.
9. The method of claim 7, wherein the cerium salt comprises at least one of cerium sulfate, cerium nitrate, cerium acetate, and cerium chloride.
10. The method of claim 7, wherein the co-reactant comprises at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia, and urea.
11. Method according to any of claims 7 to 10, characterized in that it comprises the following steps: preparing a mixed solution of potassium permanganate, cobalt salt and cerium salt, adding the reaction promoter into the mixed solution for reaction, and after the reaction, carrying out solid-liquid separation to obtain a solid component, namely the cobalt-cerium-manganese ternary metal oxide catalyst.
12. The method of claim 11, wherein the molar ratio of cobalt in the cobalt salt, cerium in the cerium salt, and manganese in the potassium permanganate is x: y: 1- (x + y), wherein x is more than or equal to 0.05 and less than or equal to 0.6, y is more than or equal to 0.05 and less than or equal to 0.6, and z is more than or equal to 1.0 and less than or equal to 2.0.
13. The method according to claim 11, wherein the pH of the mixed solution is adjusted to 5 to 14 by adding the co-reactant before the reaction.
14. The method of claim 11, further comprising drying the solid component after water washing after solid-liquid separation.
15. The method of claim 11, wherein the co-reactant is added to the mixed solution at a rate of 5mL/min to 50 mL/min.
16. Use of a transition metal oxide catalyst as claimed in any one of claims 1 to 4 in the catalytic degradation of organic matter.
17. A household appliance comprising the transition metal oxide catalyst according to any one of claims 1 to 4.
18. The household appliance of claim 17, wherein the household appliance comprises an air purifier, an oven, an oil heater, or a range hood.
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