CN105107520B - double-perovskite type metal oxide catalyst and preparation method thereof - Google Patents
double-perovskite type metal oxide catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of double-perovskite type metal oxide catalyst and preparation method thereof, is related to catalyst technical field, for solving existing LaMnO3Catalytic activity low and high temperature stability difference problem.The general formula of double-perovskite type metal oxide catalyst of the present invention is：La1‑xMxD1‑yMnyO3, wherein x=0~0.6, y=0.7~1, M are alkali metal ion or alkaline-earth metal ions, and D is+1 valence ,+divalent or+trivalent metal ion.In double-perovskite type metal oxide catalyst provided by the invention, pass through the introducing of M ions and D ions, so that the component and structure of perovskite metal oxides are adjusted, its specific surface area are made to increase, to improve the catalytic activity and high-temperature stability of catalyst.In burning present invention is mainly applied to the catalysis of methane.
Description
Technical field
The present invention relates to catalyst technical field more particularly to a kind of double-perovskite type metal oxide catalyst and its systems
Preparation Method.
Background technology
The pay attention to day by day of the problems such as with to energy shortage and environmental pollution, the energy it is clean and efficient using increasingly by
To the concern and attention of society.Wherein, main component of the methane as petroleum resources such as natural gas, shale gas and combustible ices,
Efficiently use even more focus of attention.The catalysis burning of methane as a kind of novel methyl hydride combustion technology, because its is efficient and
Avoid NOxThe formation of the environmental contaminants such as (nitrogen oxides) and CO (carbon monoxide), it has also become the hot research in the field
Direction, and catalyst is even more research emphasis as the critical material of the catalysis burning of methane.
Currently, since perovskite type metal oxide catalyst is in thermal stability, chemical stability and structural stability side
Face has certain superiority, therefore is widely used in the catalysis burning of methane.Perovskite type metal oxide is catalyzed
The general formula of agent is ABO3, usual A is rare earth metal, and B is transition metal；Such as LaMnO3(lanthanum manganate), LaMnO3(lanthanum manganate) has
Have the advantages that preparation method is simple, cheap, therefore more and more interested to researchers.
However, present inventor has found：Due to LaMnO3The catalytic activity of catalyst depends on Mn in catalyst3+
The Mn that ion and crystal structure defects are formed4+The oxidation of ion, and LaMnO3In the Mn that is formed by crystal defect4+Ion contains
Measure low, the energy of oxidation force difference of manganese ion, so as to cause LaMnO3Catalytic activity it is relatively low.
Invention content
It is existing for solving the purpose of the present invention is to provide a kind of double-perovskite type metal oxide catalyst
LaMnO3Catalytic activity low and high temperature stability difference problem.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of double-perovskite type metal oxide catalyst, the general formula of the double-perovskite type metal oxide catalyst
For：La1-xMxD1-yMnyO3, wherein x=0~0.6, y=0.7~1, M are alkali metal ion or alkaline-earth metal ions, and D is+1
Valence ,+divalent or+trivalent metal ion.
In double-perovskite type metal oxide catalyst provided by the invention, by the introducing of M ions and D ions, so that
The component and structure of perovskite metal oxides are adjusted.On the one hand, the introducing of M ions and D ions can improve catalyst
Specific surface area, while can make part Manganic ion generate tetravalence manganese ion, improve the oxidability of manganese ion, and be conducive to
Reversible oxidation-reduction process is formed between different valence state manganese ion, to improve the catalytic performance of catalyst；On the other hand, lead to
After crossing introducing D ion elements, due to D+And D2+Or D2+And D3+Reversible ionic process and D, Mn double ion synergistic effect,
The catalytic activity of catalyst can also be improved.
Another object of the present invention is to provide a kind of preparation methods of double-perovskite type metal oxide catalyst, are used for
Solve existing LaMnO3Catalytic activity low and high temperature stability difference problem.In order to achieve the above objectives, the present invention is using as follows
Technical solution：
A kind of preparation method of double-perovskite type metal oxide catalyst, including：Metal salt solution is molten with precipitating reagent
Liquid mixes, and reaction generates the mixed liquor containing sediment, and sediment is isolated from the mixed liquor containing sediment；By institute
It states sediment to be dispersed in water or alcohols solvent, obtains precipitate suspension；The Plus acidic solution into the precipitate suspension,
The pH value for adjusting the precipitate suspension is 2~8, the mixed system containing the sediment is obtained, by the mixed system
It stands, filtering, and washs filtration product；Filtration product calcining after washing, then cooling are obtained into double-perovskite type metal
Oxide catalyst.
In the preparation method of double-perovskite type metal oxide catalyst provided by the invention, due to by the way that sediment is divided
It is dispersed in water or alcohols solvent, obtains precipitate suspension, and acid solution is added dropwise into precipitate suspension, adjust sediment
The pH value of suspension is 2~8, obtains the mixed system containing sediment, which is stood, mistake
Filter, and filtration product is washed, therefore the diauxic growth of catalyst particle can be regulated and controled, to enable catalyst to be formed
All or part of nanometer rods, since the micron ball micron ball more molecular than nanoparticle of nanometer rods composition compares table with higher
Area, therefore increase the specific surface area of catalyst, make it have higher catalytic activity.
Description of the drawings
Fig. 1 is a kind of flow of the preparation method of double-perovskite type metal oxide catalyst provided in an embodiment of the present invention
Figure；
Fig. 2 is the stream of the preparation method of another double-perovskite type metal oxide catalyst provided in an embodiment of the present invention
Cheng Tu.
Specific implementation mode
In order to make it easy to understand, with reference to the accompanying drawings of the specification, to double-perovskite type metal oxygen provided in an embodiment of the present invention
Compound catalyst and preparation method thereof is described in detail.
The embodiment of the present invention provides a kind of double-perovskite type metal oxide catalyst, the double-perovskite type metal oxidation
The general formula of object catalyst is：La1-xMxD1-yMnyO3, wherein x=0~0.6, y=0.7~1, M are alkali metal ion or alkaline earth gold
Belong to ion, D is+1 valence ,+divalent or+trivalent metal ion.
In double-perovskite type metal oxide catalyst provided in an embodiment of the present invention, pass through drawing for M ions and D ions
Enter, so that the component and structure of perovskite metal oxides are adjusted.On the one hand, the introducing of M ions and D ions can improve
The specific surface area of catalyst, while part Manganic ion can be made to generate tetravalence manganese ion, the oxidability of manganese ion is improved, and
Be conducive to form reversible oxidation-reduction process between different valence state manganese ion, to improve the catalytic performance of catalyst；It is another
Aspect, after introducing D ion elements, due to D+And D2+Or D2+And D3+Reversible ionic process and D, Mn double ion association
Same-action can also improve the catalytic activity of catalyst.
Wherein, in order to further make double-perovskite type metal oxide catalyst have preferable catalytic activity and high temperature it is steady
It is qualitative, above-mentioned La1-xMxD1-yMnyO3The ionic radius range of middle D ions can beX can be that 0.4, y can be with
Can be Sr for 0.8, M ions2+, D ions can be Cu2+, i.e., above-mentioned double-perovskite type metal oxide catalyst can be preferred
For La0.6Sr0.4Cu0.2Mn0.8O3。
Certainly, in above-mentioned La1-xMxD1-yMnyO3In, x may be 0.2 or 0.4, and y may be 0.8 or 0.9.
Specifically, above-mentioned double-perovskite type metal oxide catalyst can be um porous ball shape catalyst, the micron
Porous ball shape catalyst can be accumulated by nanometer rods and nano particle to be formed, so as to solve catalyst easy-sintering at high temperature
The shortcomings that reunion, further improves the high-temperature stability of catalyst.
The embodiment of the present invention also provides a kind of preparation method of double-perovskite type metal oxide catalyst, as shown in Figure 1,
Including：
Step S1, metal salt solution is mixed with precipitant solution, reaction generate the mixed liquor containing sediment, from containing
Sediment is isolated in the mixed liquor of sediment；Wherein, metal salt solution can be nitrate solution, acetate solution, hydrochloric acid
One or more of salting liquid or sulfate liquor, precipitant solution can be the heavy of hydroxyl-containing ion or carbanion
Shallow lake agent solution, such as ammonia spirit or sodium hydroxide solution；The reaction condition that metal salt solution is mixed with precipitant solution can
Think：Reaction temperature is 0~40 DEG C, such as 20 DEG C or 30 DEG C；A concentration of 1~5mol/L of metal salt solution, such as 3mol/L
Or 4mol/L；A concentration of 0.1~5mol/L of precipitant solution, preferably 1~5mol/L, such as 3mol/L or 4mol/L.
Solvent in above-mentioned metal salt solution and precipitant solution is not limited, as long as can be molten by metal salt and precipitating reagent
Solution, preferably water or alcohol.
Step S2, sediment is dispersed in water or alcohols solvent, obtains precipitate suspension；Wherein, sediment suspends
A concentration of 0.01~1mol/L of liquid, such as 0.05mol/L, 0.1mol/L, 0.5mol/L or 1mol/L；Precipitate suspension
Temperature is 25~80 DEG C, preferably 40~60 DEG C, such as 45 DEG C or 55 DEG C.
Step S3, the Plus acidic solution into precipitate suspension, the pH value for adjusting precipitate suspension is 2~8, is contained
Mixed system containing sediment is stood, filtering, and filtration product is washed with water by the mixed system for having sediment；Wherein, sour
Property solution can be one or more of acetum, salpeter solution, acetic acid solution or hydrochloric acid solution, adjust sediment and suspend
The pH value of liquid is preferably 3~6, such as pH value is 4 or 5.
Solvent in above-mentioned acid solution is not limited, preferably water.
Step S4, the filtration product after washing is calcined, then cooling obtains double-perovskite type metal oxide catalyst.
In the preparation method of double-perovskite type metal oxide catalyst provided in an embodiment of the present invention, due to by that will sink
Starch is dispersed in water or alcohols solvent, obtains precipitate suspension, and acid solution is added dropwise into precipitate suspension, is adjusted
The pH value of precipitate suspension is 2~8, obtains the mixed system containing sediment, the mixed system that this is contained to sediment is quiet
It sets, filter, and wash filtration product, therefore the diauxic growth of catalyst particle can be regulated and controled, to enable catalyst
All or part of nanometer rods are enough formed, since the micron ball micron ball more molecular than nanoparticle of nanometer rods composition has higher
Specific surface area, therefore increase catalyst specific surface area, make it have higher catalytic activity.
The embodiment of the present invention also provides the preparation method of another double-perovskite type metal oxide catalyst, such as Fig. 2 institutes
Show, can also include between above-mentioned steps S3 and step S4：
Step S31, the filtration product after washing is mixed, ball milling with pore creating material aqueous solution or pore creating material alcoholic solution, is obtained
Slurries；Wherein, pore creating material can be one or more in starch, polyethylene glycol or polyvinylpyrrolidone.
Step S32, mist projection granulating is carried out to slurries, obtains spherical catalyst particles；Wherein, the condition of mist projection granulating can be with
For：The temperature of the air inlet of spray dryer is 150~250 DEG C, such as 175 DEG C, 215 DEG C or 245 DEG C；The temperature of air outlet is
100~150 DEG C, such as 105 DEG C, 125 DEG C or 145 DEG C；The flow velocity of peristaltic pump is 1~10mL/min, such as 2mL/min, 5mL/
Min, 6mL/min or 9mL/min；The wind speed of wind turbine is 0.5~5m3/ min, such as 0.8m3/min、1.5m3/min、3m3/min
Or 4m3/min。
In the preparation method of another kind double-perovskite type metal oxide catalyst provided in an embodiment of the present invention, due to adding
Spray drying process prilling is entered, all or part of nanometer rods can have been made further to form micron ball, therefore solve and urge
The shortcomings that easy-sintering is reunited under agent high temperature, to make it have higher high-temperature stability.
Two preferred embodiments are set forth below to double-perovskite type metal oxide oxidation catalyst provided in an embodiment of the present invention
The preparation method of agent carry out it is specific, explain in detail.
Embodiment one：
Step S1, the nitrate aqueous solution or acetate aqueous solution that configuration concentration is 1~5mol/L are water-soluble as metal salt
Liquid, configuration concentration be 1~5mol/L ammonia spirit as precipitating reagent aqueous solution, by aqueous metal salt and precipitating reagent aqueous solution
Isometric rapid mixing, so that reaction can carry out rapidly and generate sediment.It can be quickly generated more nucleus in this way,
The grain size of catalyst is set to reduce, to obtain the catalyst material of high-specific surface area.Meanwhile reaction process is controlled at 0~40 DEG C
In the environment of carry out, lower temperature can inhibit the growth rate of nucleus, promote the generating rate of nucleus.
Step S2, the sediment generated in above-mentioned steps S1 is dispersed in water or alcohols solvent, obtains sediment
Suspension.Wherein, a concentration of 0.01~1mol/L of precipitate suspension is controlled, temperature is 40~60 DEG C.
Step S3, aqueous acetic acid is added dropwise in the precipitate suspension generated into above-mentioned steps S2, it is outstanding to adjust sediment
The pH value of supernatant liquid is 3~6, after stirring 2~4 minutes, stands 2~24 hours, then filters, and massive laundering is used in combination to wash filtering production
Object.
Step S31, the filtration product that will be generated in above-mentioned steps S3, with pore creating material aqueous solution or alcoholic solution made of starch
It is mixed, then ball milling 0.5~2 hour, obtains the slurries of stable homogeneous.Wherein, the dosage of pore creating material be 0.5%~
20%, the dosage of pore creating material can be the weight ratio of filtration product and pore creating material.
Step S32, mist projection granulating is carried out with spray dryer to the slurries generated in above-mentioned steps S31, obtains spherical shape and urges
Catalyst particles.Wherein, by adjusting device parameter, you can obtain the spherical catalyst particles that grain size is 1~40 micron.Specifically
The condition on ground, mist projection granulating can be：The temperature of the air inlet of spray dryer is set as 190~210 DEG C, the temperature of air outlet
It is set as 100~120 DEG C, the flow rate set of peristaltic pump is 4~8mL/min, and the wind speed of wind turbine is set as 1~2m3/min。
Step S4, by the spherical catalyst particles generated in above-mentioned steps S32 be put into Muffle furnace high temperature calcining, by 2 DEG C/
The speed of min is warming up to 600~1000 DEG C, keeps the temperature 2~5 hours, then can be obtained double-perovskite type metal oxygen after natural cooling
The powder body material of compound catalyst.
Embodiment two：
Step S1, the nitrate aqueous solution or acetate aqueous solution that configuration concentration is 1~5mol/L are water-soluble as metal salt
Liquid, configuration concentration be 1~5mol/L sodium hydroxide solution as precipitating reagent aqueous solution, aqueous metal salt is added drop-wise to precipitation
In agent aqueous solution, sediment is generated.It can make metal ion instant precipitation simultaneously in this way, generate more nucleus, make catalyst
Grain size reduce, to obtain the catalyst material of high-specific surface area.Meanwhile reaction process is controlled in the environment of 0~40 DEG C
It carries out, lower temperature can inhibit the growth rate of nucleus, promote the generating rate of nucleus.
Step S2, the sediment generated in above-mentioned steps S1 is dispersed in water or alcohols solvent, obtains sediment
Suspension.Wherein, a concentration of 0.01~1mol/L of precipitate suspension is controlled, temperature is 40~60 DEG C.
Step S3, aqueous solution of nitric acid is added dropwise in the precipitate suspension generated into above-mentioned steps S2, it is outstanding to adjust sediment
The pH value of supernatant liquid is 3~6, after stirring 2~4 minutes, stands 2~24 hours, then filters, and massive laundering is used in combination to wash filtering production
Object.
Step S31, the filtration product that will be generated in above-mentioned steps S3 is mixed and stirred for a certain amount of water, contains at this time
The concentration of the suspension of filtration product can be 5%~80%, preferably 10%~40%, and then ball milling 0.5~2 hour, obtains
To the slurries of stable homogeneous.
Step S32, mist projection granulating is carried out with spray dryer to the slurries generated in above-mentioned steps S31, obtains spherical shape and urges
Catalyst particles.Wherein, by adjusting device parameter, you can obtain the spherical catalyst particles that grain size is 1~40 micron.Specifically
The condition on ground, mist projection granulating can be：The temperature of the air inlet of spray dryer is set as 190~210 DEG C, the temperature of air outlet
It is set as 100~120 DEG C, the flow rate set of peristaltic pump is 4~8mL/min, and the wind speed of wind turbine is set as 1~2m3/min。
Step S4, by the spherical catalyst particles generated in above-mentioned steps S32 be put into Muffle furnace high temperature calcining, by 2 DEG C/
The speed of min is warming up to 600~1000 DEG C, keeps the temperature 2~5 hours, then can be obtained double-perovskite type metal oxygen after natural cooling
The powder body material of compound catalyst.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
1. a kind of preparation method of double-perovskite type metal oxide catalyst, which is characterized in that including：
Metal salt solution is mixed with precipitant solution, reaction generates the mixed liquor containing sediment, contains sediment from described
Mixed liquor in isolate sediment；
The sediment is dispersed in water or alcohols solvent, precipitate suspension is obtained；
The Plus acidic solution into the precipitate suspension, the pH value for adjusting the precipitate suspension is 2~8, is contained
The mixed system is stood, filtering, and washs filtration product by the mixed system of the sediment；
The filtration product after washing is mixed, ball milling with pore creating material aqueous solution or pore creating material alcoholic solution, obtains slurries；
Mist projection granulating is carried out to the slurries, obtains spherical catalyst particles；The spherical catalyst particles are by nanometer rods and receive
Rice grain accumulates to be formed；
Filtration product calcining after washing, then cooling are obtained into double-perovskite type metal oxide catalyst.
2. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
Pore creating material is one or more in starch, polyethylene glycol or polyvinylpyrrolidone.
3. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
The condition of mist projection granulating is：The temperature of the air inlet of spray dryer is 150~250 DEG C, the temperature of air outlet is 100~150
DEG C, the flow velocity of peristaltic pump is 1~10mL/min, and the wind speed of wind turbine is 0.5~5m3/min。
4. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
Metal salt solution is one or more in nitrate solution, acetate solution, HCI solution or sulfate liquor；
The precipitant solution is the precipitant solution of hydroxyl-containing ion or carbanion.
5. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
Metal salt solution is mixed with precipitant solution, the reaction condition that reaction generates the mixed liquor containing sediment is：Reaction temperature
It is 0~40 DEG C, a concentration of 1~5mol/L of the metal salt solution, a concentration of 0.1~5mol/L of the precipitant solution.
6. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
The temperature of a concentration of 0.01~1mol/L of precipitate suspension, the precipitate suspension are 25~80 DEG C.
7. the preparation method of double-perovskite type metal oxide catalyst according to claim 1, which is characterized in that described
Acid solution is one or more in acetum, salpeter solution, acetic acid solution or hydrochloric acid solution.
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| CN105728063B (en) * | 2016-03-23 | 2018-06-12 | 新奥科技发展有限公司 | A kind of preparation method of metal substrate catalyst |
| CN106475105B (en) * | 2016-08-26 | 2019-02-05 | 西安交通大学 | A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof |
| CN107285383B (en) * | 2017-06-29 | 2018-10-23 | 宁波吉电鑫新材料科技有限公司 | A kind of one-step synthesis double-perovskite kalium ion battery negative material and preparation method thereof |
| CN108714426B (en) * | 2018-06-15 | 2021-06-08 | 武汉理工大学 | Nano cubic perovskite type catalyst and preparation method and application thereof |
| CN109939747B (en) * | 2019-04-24 | 2023-10-03 | 南京威安新材料科技有限公司 | Preparation device and method of supported perovskite catalyst for oxidative degradation of organic fuel |
| CN115353149B (en) * | 2022-09-01 | 2023-09-15 | 中国计量大学 | Perovskite manganese oxide porous nanosphere and preparation method and application thereof |
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