CN114054020A - Perovskite structure material and application thereof in removing formaldehyde at room temperature - Google Patents

Perovskite structure material and application thereof in removing formaldehyde at room temperature Download PDF

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CN114054020A
CN114054020A CN202111374010.8A CN202111374010A CN114054020A CN 114054020 A CN114054020 A CN 114054020A CN 202111374010 A CN202111374010 A CN 202111374010A CN 114054020 A CN114054020 A CN 114054020A
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formaldehyde
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麻春艳
宋茂勇
潘菊霜
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The invention discloses a perovskite structure material and application thereof in preparing a moisture-proof catalyst for removing formaldehyde at room temperature. The perovskite structure material has the following chemical general formula: MMnO3Wherein, M metal is one or two of copper, zinc, iron and nickel. The perovskite structure material can be used as a moisture-proof catalyst for removing formaldehyde at room temperature, and compared with a noble metal catalyst, the moisture-proof perovskite crystal form catalyst for removing formaldehyde has low cost and simple preparation method; the use condition is simple, and the operation and implementation are convenient; can be used for effectively removing formaldehyde pollution at room temperature and can quickly and stably completely oxidize formaldehyde into CO at room temperature and ambient humidity2And H2O, no productionSecondary pollution is generated; the formaldehyde is removed at room temperature, and the product has excellent moisture resistance and stability. The moisture-proof catalyst for removing formaldehyde at room temperature is suitable for removing formaldehyde pollution in households, vehicles, offices and the like with environmental humidity in a closed or semi-closed manner.

Description

Perovskite structure material and application thereof in removing formaldehyde at room temperature
Technical Field
The invention belongs to the field of environmental catalysis, and particularly relates to a perovskite structure material and application thereof in removing formaldehyde at room temperature.
Background
Formaldehyde is an irritant odor gas released from furniture, textiles, decorative materials, etc., and is one of the major pollutants in a local space. The world health organization international agency for research on cancer ranks formaldehyde as the first carcinogen, and long term exposure to low concentrations of formaldehyde can cause health problems.
The existing formaldehyde removal technology comprises an adsorption method, a plasma technology, a photocatalysis method and a thermal catalysis method, but has the defects of adsorbent saturation, byproduct generation, low efficiency, energy requirement and the like. The room temperature catalytic oxidation technology is an effective method for removing formaldehyde by catalytically oxidizing and decomposing the formaldehyde into carbon dioxide and water at room temperature.
According to literature reports, the catalysts capable of effectively removing formaldehyde at room temperature mainly include supported noble metal Pt catalysts (Applied Surface Science,2017,411,105-&Technology,2014,48(16): 9702-; applied Catalysis B Environmental,2020,268: 118461-118466) and Ag catalysts (Catalysis Today,2016,277, 257-265). CN 102240549A discloses a high-efficiency moisture-resistant room-temperature formaldehyde removal catalysis technology, which takes honeycomb ceramics as a carrier and loads MnO with pore channels doped with Ag2And then noble metal Pt is loaded as an active component. However, the total amount of noble metal is limited, and the price is high, so that the application of the noble metal catalyst in practice is severely restricted.
The transition metal is widely studied because of its low cost, but the water vapor contained in the air affects the activity and stability of the catalyst, and the conversion rate of formaldehyde decreases with the increase of humidity. Such as spinel MnCo at room temperature2O4The conversion of formaldehyde on the catalyst decreased with increasing humidity and was completely deactivated within 2 hours (Applied Catalysis B: Environmental,2019,254, 76-85.). At 99 ℃ in epsilon-MnO2Above that, the addition of water (46% relative humidity) reduced the conversion of formaldehyde from about 60% to 49% (Chemical Engineering Journal 2020,388.124146-124157). MnO at room temperature2On the catalyst, the addition of water (38% relative humidity) reduced the initial conversion of formaldehyde from 45% to 12% and was completely deactivated in 50 minutes (Journal of Hazardous Materials,2021,414, 125542-125552). In MnOx–CeO2A decrease in formaldehyde conversion with increasing humidity was also observed on the mixed oxide catalyst (Applied Catalysis B: Environmental 2006,62(3-4), 265-273.). And MnO2The catalyst can not realize the complete conversion of 200ppm of formaldehyde into CO within 11 hours2And H2O(Environmental Science&Technology,2015,49(20):12372-12379)。
Thus, the rapid and stable conversion of formaldehyde to CO is achieved at room temperature in the presence of ambient humidity2And H2O remains a challenge.
Disclosure of Invention
The invention aims to provide a perovskite structure material and application thereof in removing formaldehyde at room temperature, wherein the perovskite structure material is MMnO with a perovskite structure3The catalyst, M metal is one or two of copper, zinc, iron and nickel, can quickly and stably oxidize the formaldehyde into CO completely under the environment humidity2And H2O, wide applicable humidity range, simple preparation method, lower cost than noble metal catalyst, no need of external energy input during catalytic reaction, and suitability for removing closed and semi-closed formaldehyde pollution in households, vehicles, offices and the like with environmental humidity.
In a first aspect, the present invention provides a perovskite structure material having the following general chemical formula: MMnO3Wherein, M metal is one or two of copper, zinc, iron and nickel. Exemplary combinations include combinations of copper and zinc, copper and iron, copper and nickel, zinc and iron, zinc and nickel, iron and nickel, and the like.
In the perovskite structure material, the M metal may be a combination of copper and zinc, and preferably, the molar ratio of copper and zinc is x (1-x), where x is 0.01 to 0.99, for example, 0.01: 0.99, 0.10: 0.90, 0.30: 0.70, 0.45: 0.55, 0.50: 0.50, 0.65: 0.35, 0.80: 0.20, etc.
In the perovskite structure material, the M metal may be a combination of copper and iron, and preferably, the molar ratio of copper and iron is x (1-x), where x is 0.02 to 0.98, for example, 0.02: 0.98, 0.20: 0.80, 0.30: 0.70, 0.45: 0.55, 0.50: 0.50, 0.70: 0.30, 0.85: 0.15, etc.
In the perovskite structure material, the M metal is a combination of copper and nickel, and preferably, the molar ratio of copper to nickel is x (1-x), where x is 0.1 to 0.9, for example, 0.10: 0.90, 0.20: 0.80, 0.30: 0.70, 0.50: 0.50, 0.80: 0.20, 0.90: 0.10, etc.
In the perovskite structure material, the M metal is a combination of zinc and iron, and preferably, the molar ratio of zinc to iron is x (1-x), where x is 0.05 to 0.95, for example, 0.05: 0.95, 0.10: 0.90, 0.35: 0.65, 0.45: 0.55, 0.50: 0.50, 0.80: 0.20, 0.95: 0.05, etc.
In the perovskite structure material, the M metal is a combination of zinc and nickel, and preferably, the molar ratio of zinc to nickel is x (1-x), where x is 0.2 to 0.8, for example, 0.20: 0.80, 0.30: 0.70, 0.45: 0.55, 0.50: 0.50, 0.6: 0.4, 0.80: 0.20, etc.
In the perovskite structure material, the M metal is a combination of iron and nickel, and preferably, the molar ratio of iron to nickel is x (1-x), where x is 0.15 to 0.85, for example, 0.15: 0.85, 0.20: 0.80, 0.30: 0.70, 0.45: 0.55, 0.50: 0.50, 0.80: 0.20, 0.85: 0.15, etc.
The preparation method of the perovskite structure material comprises the following steps:
(1) mixing an aqueous solution of manganese salt with an aqueous solution of metal salt of the M metal to obtain a metal salt solution;
(2) mixing the aqueous solution of bicarbonate with the metal salt solution for coprecipitation to obtain a precipitate;
(3) and drying the precipitate and then roasting to obtain the perovskite structure material.
In the step (1), the manganese salt can be any water-soluble manganese salt, such as manganese nitrate;
the metal salt of M metal can be any water-soluble metal salt of M metal, such as M nitrate;
the ratio of the aqueous solution of manganese salt to the aqueous solution of metal salt of M metal is controlled in such a way that the molar ratio of manganese to M metal is 1: 5-5: 1, specifically 1: 1;
for example, the concentration of the aqueous solution of the manganese salt may be 0.1mmol/L to 200mmol/L, specifically 50 mmol/L;
the concentration of the aqueous solution of the metal salt of the M metal can be 0.1 mmol/L-200 mmol/L, and specifically can be 50 mmol/L;
the volume ratio of the aqueous solution of manganese salt to the aqueous solution of metal salt of M metal may be 1: 9-9: 1, specifically 1: 1.
in the step (2), the concentration of the bicarbonate can be 0.1 mmol/L-500 mmol/L, and specifically can be 36 mmol/L;
the bicarbonate may be NH4HCO3、KHCO3、NaHCO3Any one of (a);
the volume ratio of the aqueous solution of bicarbonate to the metal salt solution may be 1: 9-9: 1, specifically 1: 1.
in the step (2), the temperature of the coprecipitation can be room temperature (15-30 ℃), and the time can be 12 hours;
the coprecipitation is carried out under the condition of stirring;
the method further comprises a step of washing the precipitate after the coprecipitation, such as washing the precipitate with ultrapure water and absolute ethanol multiple times.
In the step (3), the drying temperature can be 60-100 ℃, and specifically can be 60 ℃; the time can be 1-12 h, specifically 6 h;
the roasting is carried out in the air;
the roasting temperature can be 120-550 ℃, and specifically can be 350 ℃;
the roasting time can be 1-10 hours, and specifically can be 4 hours.
In a second aspect, the present invention provides the use of the perovskite structure material described above in the presence of ambient humidity at room temperature to remove formaldehyde or in the preparation of a moisture-resistant catalyst for removing formaldehyde at room temperature.
The M metal and the Mn metal in the perovskite structure material are connected through an oxygen atom to generate a synergistic effect, so that the catalyst has H2Affinity of O.
The humidity in the formaldehyde removal environment can be 0% to 90%, preferably 40% to 65%.
The concentration of formaldehyde in the environment for removing formaldehyde can be 2-200 ppm.
In a third aspect, the invention provides a moisture-resistant catalyst for removing formaldehyde at room temperature, which is made of the perovskite structure material.
The catalyst can be prepared and formed into different structures according to actual application, for example, the catalyst can be prepared into honeycomb shapes when used in an air purification device, and can be prepared into particles when used for placing in a closed space.
In a fourth aspect, the present invention provides a method for removing formaldehyde, comprising the steps of: removing formaldehyde at room temperature by using the moisture-resistant catalyst.
The moisture-proof catalyst can remove formaldehyde at room temperature and ambient humidity, and completely oxidize the formaldehyde into carbon dioxide and water.
The humidity of the formaldehyde-removing environment of the moisture-proof catalyst is 0-90%, preferably 40-65%.
The concentration of formaldehyde in the formaldehyde-removing environment of the moisture-proof catalyst is 2-200 ppm.
In a fifth aspect, the present invention provides a formaldehyde removal device comprising a catalyst assembly, wherein the catalyst in the catalyst assembly is the moisture-resistant catalyst described in any one of the above.
The assembly process of the formaldehyde removing device is as follows: the catalyst unit is prepared by molding a powder type catalyst, assembling the catalyst unit to form a formaldehyde-removed catalyst assembly, and then placing the assembly in an air purification apparatus.
When the device is used, flowing air passes through the device, formaldehyde contained in the air is contacted with a catalyst component in the device and is oxidized and decomposed into carbon dioxide and water by the catalyst, and thus the formaldehyde is removed.
Compared with the prior art, the invention has the advantages that:
(1) compared with the noble metal catalyst, the moisture-proof perovskite crystal form catalyst for removing formaldehyde has low cost and simple preparation method.
(2) The catalyst for removing formaldehyde has simple use conditions and convenient operation and implementation, can be used for effectively removing formaldehyde pollution at room temperature, and can quickly and stably completely oxidize formaldehyde into CO at room temperature under ambient humidity2And H2O, does not produce secondary pollution, CO2The selectivity can reach 100 percent, and the formaldehyde conversion rate can reach 100 percent.
(3) The catalyst of the invention can remove formaldehyde at room temperature, and has excellent moisture resistance and stability. Under the conditions of 40% and 65% of relative humidity, the conversion rate of formaldehyde can reach 100%, and CO can reach2The selectivity also reaches 100 percent. Even under the high humidity condition with the relative humidity of 90 percent, the conversion rate of formaldehyde can be more than 90 percent, and CO can be obtained2The selectivity reaches 100%, and the formaldehyde conversion rate of the catalyst is still kept at 90% within 1000 hours.
Drawings
FIG. 1 shows ZnMnO prepared in example 1 of the present invention3XRD pattern of (a).
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of moisture resistant catalyst for removing Formaldehyde at Room temperature
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing an ammonium bicarbonate solution with the concentration of 36 mmol/L; mixing a manganese nitrate solution with the concentration of 50mmol/L and a zinc nitrate solution with the concentration of 50mmol/L according to the volume ratio of 1: 1, mixing in proportion to obtain a manganese-zinc solution of a metal mixed solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution manganese-zinc solution (the volume ratio of the precipitator solution to the metal mixed solution manganese-zinc solution is 1: 1), stirring for 12 hours at room temperature (25 ℃), and washing the generated precipitate with ultrapure water and absolute ethyl alcohol;
(3) drying the washed precipitate at 60 ℃ for 6 hours, and then roasting the precipitate in air at 350 ℃ for 4 hours to obtain the catalyst which is expressed as ZnMnO3。
ZnMnO3The XRD results of (A) are shown in FIG. 1, which shows a perovskite structure material.
Respectively adding 0.2 g of catalyst ZnMnO3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 80ppm formaldehyde, oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 1.
TABLE 1, example 1 catalytic Activity
Figure BDA0003363193890000051
Example 2 preparation of moisture resistant catalyst for Room temperature Formaldehyde removal
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing an ammonium bicarbonate solution with the concentration of 36 mmol/L; mixing a manganese nitrate solution with the concentration of 50mmol/L and an iron nitrate solution with the concentration of 50mmol/L according to the volume ratio of 1: 1 to obtain a manganese-iron solution of a metal mixed solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution ferromanganese solution (the volume ratio of the precipitator solution to the metal mixed solution is 1: 1), stirring for 12 hours at room temperature (25 ℃), and washing the generated precipitate with ultrapure water and absolute ethyl alcohol;
(3) drying the washed generated electricity at 60 ℃ for 6 hours, and then roasting the dried generated electricity in air at 350 ℃ for 4 hours to obtain the catalystThe agent is denoted as FeMnO3。
0.2 g of catalyst FeMnO respectively3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 160ppm formaldehyde, the oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 2.
TABLE 2, example 2 catalytic Activity
Figure BDA0003363193890000061
Example 3 preparation of moisture resistant catalyst for Room temperature Formaldehyde removal
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing an ammonium bicarbonate solution with the concentration of 36 mmol/L; mixing a manganese nitrate solution with the concentration of 50mmol/L and a nickel nitrate solution with the concentration of 50mmol/L according to the volume ratio of 1: 1 to obtain a nickel-manganese solution of a metal mixed solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution manganese-nickel solution (the volume ratio of the precipitator solution to the metal mixed solution is 1: 1), stirring at room temperature (25 ℃) for 12 hours, and washing the generated precipitate with ultrapure water and absolute ethyl alcohol;
(3) drying the washed precipitate at 60 deg.C for 6 hr, calcining at 350 deg.C in air for 4 hr to obtain NiMnO catalyst3。
0.2 g of catalyst NiMnO respectively3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 200ppm formaldehyde, the oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 3.
TABLE 3, example 3 catalytic Activity
Figure BDA0003363193890000062
Example 4
The procedure is as in example 1, except that the catalyst is used in an amount of 0.1 g and the initial concentration of formaldehyde is 20 ppm. The results of activity evaluation are shown in Table 4.
TABLE 4, example 4 catalytic Activity
Figure BDA0003363193890000071
Example 5
The procedure is as in example 2, except that the catalyst is used in an amount of 0.1 g and the initial concentration of formaldehyde is 8 ppm. The results of activity evaluation are shown in Table 5.
TABLE 5, example 5 catalytic Activity
Figure BDA0003363193890000072
Example 6
The procedure is as in example 3, except that the catalyst is used in an amount of 0.1 g and the initial concentration of formaldehyde is 20 ppm. The results of activity evaluation are shown in Table 6.
TABLE 6, example 6 catalytic Activity
Figure BDA0003363193890000073
Example 7 preparation of moisture resistant catalyst for Room temperature Formaldehyde removal
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing 36mmol/L ammonium bicarbonate solution with concentration; mixing a manganese nitrate solution with the concentration of 50mmol/L, ferric nitrate with the concentration of 25mmol/L and a nickel nitrate solution with the concentration of 25mmol/L according to the volume ratio of 1: 1: 1 to obtain a metal mixed solution manganese nickel iron solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution manganese nickel iron solution (the volume ratio of the precipitator solution to the metal mixed solution is 1: 1), stirring for 12 hours at room temperature (25 ℃), and washing with ultrapure water and absolute ethyl alcohol;
(3) the washed precipitate was dried at 60 ℃ for 6 hours and then calcined at 350 ℃ for 4 hours in air, and the catalyst obtained was noted as FexNi1-xMnO3(in this example, x is 0.5).
0.2 g of catalyst FexNi1-xMnO3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 2ppm formaldehyde, oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 7.
TABLE 7, example 7 catalytic Activity
Figure BDA0003363193890000081
Example 8
The rest is the same as in example 7, but the initial concentration of formaldehyde is 180 ppm. The results of activity evaluation are shown in Table 8.
TABLE 8, example 8 catalytic Activity
Figure BDA0003363193890000082
Example 9 preparation of moisture resistant catalyst for Room temperature Formaldehyde removal
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing an ammonium bicarbonate solution with the concentration of 36 mmol/L; mixing a manganese nitrate solution with the concentration of 50mmol/L, zinc nitrate with the concentration of 25mmol/L and an iron nitrate solution with the concentration of 25mmol/L according to the volume ratio of 1: 1: 1 to obtain a manganese zinc iron solution of a metal mixed solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution manganese zinc iron solution (the volume ratio of the precipitator solution to the metal mixed solution is 1: 1), stirring for 12 hours at room temperature (25 ℃), and washing with ultrapure water and absolute ethyl alcohol;
(3) the washed precipitate was dried at 60 ℃ for 6 hours and then calcined at 350 ℃ for 4 hours in air, and the catalyst obtained was noted as ZnxFe1-xMnO3(in this example, x is 0.5).
0.2 g of catalyst Zn are respectively addedxFe1-xMnO3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 60ppm formaldehyde, the oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 9.
TABLE 9, example 9 catalytic Activity
Figure BDA0003363193890000091
Example 10
The procedure is as in example 9, but the initial concentration of formaldehyde is 200 ppm. The results of activity evaluation are shown in Table 10.
TABLE 10, example 10 catalytic Activity
Figure BDA0003363193890000092
Example 11 preparation of moisture resistant catalyst for Room temperature Formaldehyde removal
The moisture-proof catalyst for removing formaldehyde at room temperature is prepared according to the following steps:
(1) preparing an ammonium bicarbonate solution with the concentration of 36 mmol/L; mixing a manganese nitrate solution with the concentration of 50mmol/L, zinc nitrate with the concentration of 25mmol/L and a nickel nitrate solution with the concentration of 25mmol/L according to the volume ratio of 1: 1: 1 to obtain a metal mixed solution manganese zinc nickel solution;
(2) quickly adding the prepared precipitator solution ammonium bicarbonate solution into the metal mixed solution manganese-zinc-nickel solution (the volume ratio of the precipitator solution to the metal mixed solution is 1: 1), stirring for 12 hours at room temperature (25 ℃), and washing with ultrapure water and absolute ethyl alcohol;
(3) the washed precipitate was dried at 60 ℃ for 6 hours and then calcined at 350 ℃ for 4 hours in air, and the catalyst obtained was noted as ZnxNi1-xMnO3(in this example, x is 0.5).
0.2 g of catalyst Zn are respectively addedxNi1-xMnO3Fixed in a quartz fixed bed reactor maintained at 25 ℃. The reaction gas composition was 20ppm formaldehyde, the oxygen concentration was 20%, nitrogen was the balance gas, and the gas flow rate was 50 mL/min. The relative humidities of the reaction gases were 20%, 40%, 65% and 90%, respectively, and the results of the activity evaluations are shown in Table 11.
TABLE 11, example 11 catalytic Activity
Figure BDA0003363193890000101
Example 12
The same procedure as in example 11 was repeated, except that the initial concentration of formaldehyde was 200 ppm. The results of activity evaluation are shown in Table 12.
TABLE 12, example 12 catalytic Activity
Figure BDA0003363193890000102
Example 13
0.2 g of the ZnMnO of the catalyst of example 1 are separately added3Placing in a sealed 10L transparent cabin containing formaldehyde, and reacting at 25 deg.C. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 10ppm, the oxygen concentration in the air is about 20%, and the relative humidity of the reaction gas is 20%, 40%, 65% and 90% respectively. After reacting for 60 minutes, the concentration of formaldehyde detected by a formaldehyde detector is reduced to 0 ppm.
Example 14
The same procedure as in example 13 was repeated, except that the initial concentration of formaldehyde was 120 ppm. The results of activity evaluation are shown in Table 13.
TABLE 13, example 14 catalytic Activity
Figure BDA0003363193890000111
Example 15
The same procedure as in example 13 was repeated, except that the initial concentration of formaldehyde was 200 ppm. The results of activity evaluation are shown in Table 14.
TABLE 14, example 15 catalytic Activity
Figure BDA0003363193890000112
Example 16
0.2 g of the catalyst of example 2, FeMnO, respectively3Placing in a sealed 10L transparent cabin containing formaldehyde, and reacting at 25 deg.C. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 80ppm, the oxygen concentration in the air is about 20%, and the relative humidity of the reaction gas is 20%, 40%, 65% and 90% respectively. After 60 minutes of reaction, the formaldehyde concentration was measured by a formaldehyde detector, and the activity evaluation results are shown in Table 15.
TABLE 15, example 16 catalytic Activity
Figure BDA0003363193890000113
Example 17
The same procedure as in example 16 was repeated, except that the initial concentration of formaldehyde was 200 ppm. The results of activity evaluation are shown in Table 16.
TABLE 16, example 17 catalytic Activity
Figure BDA0003363193890000114
Example 18
0.2 g of the catalyst NiMnO of example 3 are separately charged3Placing in a sealed 10L transparent cabin containing formaldehyde, and reacting at 25 deg.C. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 2ppm, the oxygen concentration in the air is about 20 percent, and the reaction gas is relatively wetThe degrees are 20%, 40%, 65%, 90%, respectively. After reacting for 60 minutes, the concentration of formaldehyde detected by a formaldehyde detector is reduced to 0 ppm.
Example 19
The same procedure as in example 18 was repeated, except that the formaldehyde concentration was 200 ppm. The results of activity evaluation are shown in Table 17.
TABLE 17, example 19 catalytic Activity
Figure BDA0003363193890000121
Example 20
0.1 g of the catalyst Zn of example 11 are each separately addedxNi1-xMnO3Placing in a sealed 10L transparent cabin containing formaldehyde, and reacting at 25 deg.C. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 2ppm, the oxygen concentration in the air is about 20%, and the relative humidity of the reaction gas is 20%, 40%, 65% and 90% respectively. After reacting for 60 minutes, the concentration of formaldehyde detected by a formaldehyde detector is reduced to 0 ppm.
Example 21
The same procedure as in example 20 was repeated, except that the formaldehyde concentration was 180 ppm. The results of activity evaluation are shown in Table 18.
TABLE 18, example 21 catalytic Activity
Figure BDA0003363193890000122
Example 22
0.1 g of the catalyst Fe from example 7xNi1-xMnO3Placing the mixture in a sealed 10L transparent cabin containing formaldehyde, and reacting at 25 ℃. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 5ppm, the oxygen concentration in the air is about 20%, and the relative humidity of the reaction gas is 20%, 40%, 65% and 90% respectively. After reacting for 60 minutes, the concentration of formaldehyde detected by a formaldehyde detector is reduced to 0 ppm.
Example 23
The same procedure as in example 22 was repeated, except that the initial concentration of formaldehyde was 200 ppm. The results of activity evaluation are shown in Table 19.
TABLE 19, example 23 catalytic Activity
Figure BDA0003363193890000131
Examples 24,
500 g of Fe in powder form are first mixed in each casexNi1-xMnO3Forming catalyst to obtain granular catalyst unit (cylindrical granule with particle size of 0.5-1cm and diameter of 0.1-0.5), placing the granular catalyst unit in porous box to obtain formaldehyde-removing catalyst component, placing into air-changing port of air purification device, and placing the air purification device at 20m2In the atmosphere cabin. The temperature of the large air cabin is 25 ℃. The formaldehyde gas is generated by volatilization of polyformaldehyde, the concentration is 2ppm, the oxygen concentration in the air is about 20%, and the relative humidity of the reaction gas is 20%, 40%, 65% and 90% respectively. After reacting for 60 minutes, the formaldehyde concentration is reduced to 0 ppm.
The above examples are merely illustrative of specific embodiments of the present invention and are provided to illustrate the detailed composition and use of the catalyst of the present invention, but are not intended to represent that the present invention can be practiced only by relying on the above detailed composition and use. Therefore, the protection scope of the present invention is not limited to the above examples, and all the substitution or optimization of the catalyst raw material, the addition of other auxiliary components, the optimization or substitution of the use parameters, and the like in the present invention are within the protection scope of the present invention.

Claims (8)

1. A perovskite structure material characterized in that: has the following chemical formula: MMnO3Wherein, M metal is one or two of copper, zinc, iron and nickel.
2. The perovskite structure material according to claim 1, characterized in that: the M metal is a combination of copper and zinc, the molar ratio of the copper to the zinc is x (1-x), and x is 0.01-0.99; or the like, or, alternatively,
the M metal is a combination of copper and iron, the molar ratio of the copper to the iron is x (1-x), and the x is 0.02-0.98; or the like, or, alternatively,
the M metal is a combination of copper and nickel, the molar ratio of the copper to the nickel is x (1-x), and x is 0.1-0.9; or the like, or, alternatively,
the M metal is a combination of zinc and iron, the molar ratio of the zinc to the iron is x (1-x), and x is 0.05-0.95; or the like, or, alternatively,
the M metal is a combination of zinc and nickel, the molar ratio of the zinc to the nickel is x (1-x), and x is 0.2-0.8; or the like, or, alternatively,
the M metal is a combination of iron and nickel, the molar ratio of the iron to the nickel is x (1-x), and x is 0.15-0.85.
3. Use of the perovskite structure material as claimed in claim 1 or 2 for removing formaldehyde under room temperature conditions in the presence of ambient humidity or for preparing a moisture-resistant catalyst for removing formaldehyde at room temperature.
4. A moisture-resistant catalyst for removing formaldehyde at room temperature, which is made of the perovskite-structured material according to claim 1 or 2.
5. A formaldehyde removal method comprises the following steps: formaldehyde is removed at room temperature using the moisture tolerant catalyst of claim 4.
6. The method of claim 5, wherein: the humidity of the moisture-proof catalyst in a formaldehyde removing environment is 0-90%, preferably 40-65%.
7. The method according to claim 5 or 6, characterized in that: the concentration of formaldehyde in the formaldehyde-removing environment of the moisture-proof catalyst is 2-200 ppm.
8. A remove formaldehyde device, includes catalyst components, its characterized in that: the catalyst in the catalyst assembly is a moisture tolerant catalyst as set forth in claim 4.
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