CN115739073A - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
A catalyst, a preparation method and application thereof, wherein the catalyst comprises the following chemical formula: AMn 2+2x O 5+3x (ii) a A is at least one of Sm, la, Y, gd, sr, ce, ba and Ca, and x is larger than 0. The catalyst can catalyze pollutants such as ozone, volatile organic compounds and the like to be efficiently decomposed at low temperature.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a catalyst and a preparation method and application thereof.
Background
With the rapid development of industry, a large amount of Volatile Organic Compounds (VOCs) are produced and applied to industries such as petrochemicals, automobiles, electronics, chemical engineering, biomedicines, industrial coating, furniture, packaging and printing, and the like, and since VOCs have strong volatility and are generally toxic, VOCs can form PM2.5 and ozone (O) through photochemical reaction 3 ) Can form haze and alsoCan harm human health; o having both strong oxidizing property 3 The ozone generator is widely applied to industries of sterilization, disinfection, water treatment, packaging, printing and the like, and can generate a large amount of ozone when devices such as UV photolysis, plasma, high-voltage static electricity, an ozone generator and the like are used. International environmental Air Quality Standards (NAAQS) states that the limiting concentration of acceptable ozone for humans in one hour is 260. Mu.g/m 3 . At 320. Mu.g/m 3 1h activity in ozone environment will cause cough, dyspnea and lung function decline. Ozone can also participate in the reaction of unsaturated fatty acid, amino and other proteins in organisms, so that people who directly contact high-concentration ozone for a long time have symptoms of fatigue, cough, chest distress, chest pain, skin wrinkling, nausea, headache, accelerated pulse, memory deterioration, visual deterioration and the like. Ozone can also cause plant leaves to turn yellow and even wither, damage to plants, even reduction in yield of agricultural and forestry plants, reduction in economic benefit and the like. Ozone can react relatively quickly with organic compounds containing unsaturated carbon-carbon bonds (including rubber, styrene, unsaturated fatty acids and esters thereof) in manufactured products of indoor building materials (such as surface coatings of latex paints and the like), household goods (such as cork appliances, carpets and the like), silk, cotton, cellulose acetate, nylon and polyester, thereby causing dye fading, discoloration of photo image layers, aging of tires and the like. VOC and O not effectively treated 3 The air quality and the human health are damaged when the air is discharged into the atmosphere; in order to improve the air quality, the emphasis on VOC and O in important industries is urgently needed to be strengthened 3 The treatment of (1). The main technologies for treating VOC at present are a direct combustion method, a catalytic combustion method, a plasma combined ozone method, a vacuum ultraviolet combined ozone method and the like. The catalytic combustion method uses a catalyst containing noble metal active components such as platinum, palladium or ruthenium, and decomposes VOC at 250-500 ℃. However, the conventional catalyst needs to decompose volatile organic compounds at high temperature (for example, 200 ℃ or higher), and thus is expensive.
Disclosure of Invention
According to a first aspect, in an embodiment, there is provided a catalyst comprising the formula:
AMn 2+2x O 5+3x ；
a is at least one of Sm, la, Y, gd, sr, ce, ba and Ca, and x is larger than 0.
According to a second aspect, in an embodiment, there is provided a method of preparing the catalyst of the first aspect, comprising:
a first solution preparation step including mixing a salt containing a, a salt containing manganese, and a solvent to obtain a first solution;
a second solution preparation step, which comprises mixing the first solution with a complexing agent according to the formula amount to obtain a second solution;
a gel preparation step, which comprises heating the second solution to prepare sol, and continuously heating to prepare gel;
and a calcination step, including calcination of the gel to produce the catalyst.
According to a third aspect, in an embodiment, there is provided the use of the catalyst of the first aspect in catalysing the decomposition of a pollutant.
According to the catalyst, the preparation method and the application of the catalyst, the catalyst can catalyze the synergistic efficient decomposition of ozone and volatile organic compounds under the low-temperature condition without being carried out at high temperature, so that the treatment cost of pollutants such as the volatile organic compounds is effectively reduced.
Drawings
FIG. 1 is a schematic view of a purification apparatus according to example 1;
FIG. 2 is a schematic view of an exploded apparatus according to embodiment 2.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted in different instances or may be replaced by other materials, methods. In some instances, certain operations related to the present application have not been shown or described in detail in order to avoid obscuring the core of the present application from excessive description, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification and drawings are for the purpose of clearly describing certain embodiments only and are not intended to imply a required sequence unless otherwise indicated where a certain sequence must be followed.
The numbering of the components as such, e.g., "first", "second", etc., is used herein only to distinguish the objects as described, and does not have any sequential or technical meaning.
In view of the shortcomings of the prior art, there is a need to develop a VOC and O with low cost, high efficiency and wider application range 3 A catalyst for the treatment of exhaust gases.
In one embodiment, the present invention specifically provides a preparation method and application of a catalyst for ozone and Volatile Organic Compounds (VOCs) synergistic purification or ozonolysis at room temperature
According to a first aspect, in an embodiment, there is provided a catalyst comprising the formula:
AMn 2+2x O 5+3x ；
a is at least one of Sm, la, Y, gd, sr, ce, ba and Ca, and x is larger than 0.
In one embodiment, a is any one of Sm, la, Y, gd, sr, ce, ba, ca.
In one embodiment, x is 0.001 to 0.3, preferably 0.01 to 0.2.
In one embodiment, the catalyst is used to catalyze the decomposition of ozone and/or volatile organics at low temperatures.
In one embodiment, the catalyst is used to catalyze ozonolysis alone at low temperatures.
In one embodiment, the catalyst is used to catalyze the decomposition of a mixture containing ozone and volatile organic compounds at low temperatures.
In an embodiment, the low temperature is 10 to 40 ℃, preferably 20 to 40 ℃, more preferably 20 to 30 ℃, more preferably 21 to 25 ℃, more preferably 25 ℃.
According to a second aspect, in an embodiment, there is provided a method of preparing the catalyst of the first aspect, comprising:
a first solution preparation step including mixing a salt containing a, a salt containing manganese, and a solvent to obtain a first solution;
a second solution preparation step, which comprises mixing the first solution with a complexing agent according to the formula amount to obtain a second solution;
a gel preparation step, which comprises heating the second solution to prepare sol, and continuously heating to prepare gel;
and a calcination step, including calcination of the gel to produce the catalyst.
In one embodiment, the solvent includes, but is not limited to, water.
In one embodiment, the complexing agent includes, but is not limited to, at least one of citric acid, oxalic acid, and maleic acid.
In one embodiment, the a-containing salt includes, but is not limited to, at least one of a nitrate, acetate, chloride, containing a.
In one embodiment, the manganese-containing salt includes, but is not limited to, a divalent manganese salt.
In one embodiment, in the gel preparation step, the second solution is heated to 60 to 90 ℃ to prepare the gel. The heating temperature of the second solution is preferably 70 to 80 ℃.
In one embodiment, the calcination temperature in the calcination step is 600 to 900 ℃.
In one embodiment, the calcination time in the calcination step is 6 to 8 hours.
According to a third aspect, in an embodiment, there is provided the use of the catalyst of the first aspect in catalysing the decomposition of a pollutant.
In one embodiment, the decomposition is performed at low temperature.
In one embodiment, the low temperature is 10 to 40 ℃, preferably 20 to 40 ℃, more preferably 20 to 30 ℃, more preferably 21 to 25 ℃, more preferably 25 ℃.
In one embodiment, low temperatures include, but are not limited to, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, and the like.
In one embodiment, the contaminant is ozone.
In one embodiment, the contaminant is a mixture of ozone and volatile organic compounds.
In one embodiment, the concentration of ozone in the mixture of ozone and volatile organic compounds is 2000ppm.
In one embodiment, the gas flow rate of the contaminant is 1L/min when the amount of the catalyst is 100 mg.
In one embodiment, the space velocity of the contaminants is 100000h -1 。
In one embodiment, the invention provides a catalyst for purifying ozone and volatile organic compounds at room temperature or purifying ozone and a preparation method thereof, so as to solve the problems of high cost and low treatment efficiency of the conventional VOC treatment technology.
In one embodiment, the mechanism of catalytic oxidation and decomposition of ozone in the present invention is:
O 3 +*→O*+O 2
O*+O 3 →O 2 *+O 2
O 2 *→O 2 +*
wherein represents the active sites on the surface of the catalyst.
O 3 Occupying active sites on the surface of the catalyst, and decomposing by the catalyst to generate strong oxidizing O and O 2 * VOC is catalytically oxidized at normal temperature to form CO 2 And H 2 O。
In one embodiment, the present invention provides a composite oxide catalyst comprising the formula: (x) Mn 2 O 3 /AMn 2 O 5 Also, AMn can be used 2+2x O 5+3x Wherein A is one of Sm, la, Y, gd, sr, ce, ba, ca and the like, and x>0。
In one embodiment, x is between 0.001 and 0.3, preferably between 0.01 and 0.2.
In one embodiment, the weight ratio of the catalyst: 100mg, particle size: 40-60 mesh, concentration of benzene: 130ppm, O 3 The concentration of (c): 2000ppm, gas flow: 1L/min, space velocity 100000h -1 Under the condition of (3), the conversion rate of VOC is more than 99 percent and O is less than 25 ℃ of the composite oxide catalyst 3 The conversion of (D) is more than 99%, and no obvious reduction is caused in 10 hours.
In one embodiment, there is provided a method of preparing a composite oxide catalyst, comprising: the salt A and the manganese salt (namely the Mn salt) are mixed in a molar ratio n A ：n Mn =1: (2 + 2x) is added into deionized water to be mixed to obtain solution A.
In one embodiment, the method comprises the step of adding a complexing agent to the solution A to obtain a solution B, wherein the molar ratio n of the complexing agent to the (metal A + metal Mn) (complexing agent) ：n (A+Mn) ＝0.1-0.5：1。
In one embodiment, the method comprises the step of heating the solution B in a water bath at 80 ℃ for 8 hours to form the sol C.
In one embodiment, the method comprises heating sol C at 80 deg.C for 48 hours to form gel D.
In one embodiment, the method comprises taking out the gel, and calcining at 800 deg.C for 8 hr to obtain composite oxide AMn 2+2x O5+3 x 。
In one embodiment, the complexing agent is one or more of citric acid, oxalic acid, and maleic acid.
In one embodiment, the a salt is a nitrate, acetate or chloride of a and the manganese salt is a divalent manganese salt.
In one embodiment, the use of a composite oxide catalyst for ozone and volatile organic co-purification or ozone purification at room temperature is provided.
In one embodiment, the invention provides a catalyst for synergistic purification of ozone and volatile organic compounds at room temperature or ozone purification, and a preparation method and application thereof.
Example 1
In the embodiment, benzene is selected as a volatile organic compound for experiment, and the structure of the benzene is relatively stable, so as to confirm that the catalyst provided by the invention has excellent performance of catalyzing and decomposing the organic compound.
The introduced mixed gas contains 130ppm benzene, 2000ppm ozone, 1L/min gas flow and 100000h space velocity -1 The catalyst is YMn 2.2 O 5.3 Particles, YMn 2.2 O 5.3 The preparation process of the granules is as follows:
in the first step, 0.1mol of yttrium nitrate hexahydrate [ Y (NO) 3 ) 3 ·6H 2 O]And 0.22mol of manganese acetate tetrahydrate [ Mn (CH) 3 COO) 2 ·4H 2 O]Adding into 1L deionized water, stirring and mixing at 300 r/min;
secondly, adding citric acid according with a stoichiometric ratio in the stirring process;
step three, heating the mixed solution of the step one and the step two in a water bath at the temperature of 80 ℃ for 8 hours to form sol;
fourthly, continuously heating the sol for 48 hours at the temperature of 80 ℃ to form gel;
fifthly, taking out the gel, and roasting at 800 ℃ for 8 hours to obtain the composite oxide YMn 2.2 O 5.3 ；
In a sixth step, the catalyst is pelletized in order to reduce the diffusion resistance of the test gas.
100mg of particles with the particle size of 40-60 meshes are selected for the cooperative purification of ozone and volatile organic compounds, and the schematic diagram of the purification device is shown in figure 1. The results of the benzene testing at 25 ℃ are shown in Table 1.
Benzene conversion = (concentration of inlet benzene-concentration of benzene after treatment) ÷ concentration of inlet benzene × 100%.
TABLE 1
The results in table 1 show that the benzene conversion remains above 99% over 10 hours with unchanged conditions.
In the catalyst YMn 2.2 O 5.3 When the amount of the particles (the particle diameter is 40-60 meshes) is 100mg and the gas flow is 1L/min, the space velocity of the mixed gas treated by the embodiment is 1000h -1 ～200000h -1 Can efficiently catalyze and decompose medium and low concentration (1000 mg/m) 3 Below), large flux of volatile organic compounds, and significantly improved catalytic efficiency.
Example 2
In the embodiment, ozone is selected for experiments, and the catalytic effect of the catalyst on ozone alone is tested.
The introduced gas contains ozone with the concentration of 2000ppm, the gas flow is 1L/min, and the space velocity is 100000h -1 The catalyst is YMn 2.2 O 5.3 Particles, YMn 2.2 O 5.3 The preparation process of the granules is as follows:
in the first step, 0.1mol of yttrium nitrate [ Y (NO) hexahydrate 3 ) 3 ·6H 2 O]And 0.22mol of manganese acetate tetrahydrate [ Mn (CH) 3 COO) 2 ·4H 2 O]Adding into 1L deionized water, stirring and mixing at 300 r/min;
secondly, adding citric acid according with the stoichiometric ratio in the stirring process;
thirdly, heating the mixed solution of the first step and the second step in a water bath at the temperature of 80 ℃ for 8 hours to form sol;
fourthly, continuously heating the sol for 48 hours at the temperature of 80 ℃ to form gel;
fifthly, taking out the gel, and roasting at 800 ℃ for 8 hours to obtain the composite oxide YMn 2.2 O 5.3 ；
And a sixth step of granulating the catalyst in order to reduce the diffusion resistance of the test gas.
100mg of particles with a particle size of 40-60 mesh were selected for ozonolysis, and the schematic diagram of the decomposing apparatus is shown in FIG. 2. The results of the ozone conversion test at a temperature of 25 c are shown in table 2.
Ozone conversion = (concentration of inlet ozone-concentration of ozone after treatment) ÷ concentration of inlet ozone × 100%.
TABLE 2
The results in table 2 show that the ozone conversion remains above 99% over 10 hours with unchanged conditions.
In the catalyst YMn 2.2 O 5.3 When the dosage of the particles (the particle diameter is 40-60 meshes) is 100mg and the gas flow is 1L/min, the airspeed of the ozone gas treated by the embodiment is 1000h -1 ～200000h -1 The catalytic decomposition method can efficiently catalyze and decompose high-concentration (below 50000 ppm) and large-flux ozone pollutants, and remarkably improve the catalytic efficiency.
In the existing catalysts, noble metals are loaded on a base material with high specific surface area, so that the cost is high and the energy consumption is high; some plasmas are used for decomposing VOC into small molecular organic matters which are easy to oxidize and degrade, ozone molecules generate oxygen atoms and free radicals under the catalytic action of the plasmas to decompose the small molecular organic matters into carbon dioxide within 14-16 min, the decomposition efficiency is low, and the method is not suitable for scenes with medium-high concentration and large flux; some utilize ultraviolet light to crack VOC and simultaneously generate O 3 The photocatalyst and the ozone catalyst have the synergistic effect of purifying VOC and ozone, the decomposition efficiency is low, and the photocatalyst and the ozone catalyst are not suitable for scenes with medium-low concentration and large flux.
In one embodiment, catalyst YMn of the present invention 2.2 O 5.3 When the dosage of the particles (the particle diameter is 40-60 meshes) is 100mg and the gas flow is 1L/min, the space velocity of the treated mixed gas is 1000h -1 ～200000h -1 Can efficiently catalyze and decompose medium and low concentration (1000 mg/m) 3 Below), large flux of volatile organic compounds, and significantly improved catalytic efficiency.
In one embodiment, the catalyst of the invention, YMn 2.2 O 5.3 When the dosage of the particles (the particle diameter is 40-60 meshes) is 100mg and the gas flow is 1L/min, the airspeed of the treated ozone gas is 1000h -1 ～200000h -1 The catalytic decomposition method can efficiently catalyze and decompose high-concentration (below 50000 ppm) and large-flux ozone pollutants, and remarkably improve the catalytic efficiency.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. A catalyst, comprising the formula:
AMn 2+2x O 5+3x ；
a is at least one of Sm, la, Y, gd, sr, ce, ba and Ca, and x is larger than 0.
2. The catalyst according to claim 1, wherein A is any one of Sm, la, Y, gd, sr, ce, ba, ca.
3. The catalyst according to claim 1, wherein x is from 0.001 to 0.3, preferably from 0.01 to 0.2;
preferably, the catalyst has the formula YMn 2.2 O 5.3 。
4. A process for preparing a catalyst according to any one of claims 1 to 3, comprising:
a first solution preparation step including mixing a salt containing a, a salt containing manganese, and a solvent to obtain a first solution;
a second solution preparation step, which comprises mixing the first solution with a complexing agent according to the formula amount to obtain a second solution;
a gel preparation step, which comprises heating the second solution to prepare sol, and continuously heating to prepare gel;
and a roasting step, comprising roasting the gel to prepare the catalyst.
5. The method of claim 4, wherein the solvent comprises water;
preferably, the complexing agent comprises at least one of citric acid, oxalic acid, maleic acid;
preferably, the A-containing salt comprises at least one of nitrate, acetate and chloride containing A;
preferably, the manganese-containing salt comprises a divalent manganese salt.
6. The method according to claim 4, wherein in the gel preparation step, the second solution is heated to 60 to 90 ℃ to prepare a gel;
preferably, in the roasting step, the roasting temperature is 600-900 ℃;
preferably, in the roasting step, the roasting time is 6 to 8 hours.
7. Use of a catalyst according to any one of claims 1 to 3 for catalysing the decomposition of a pollutant.
8. Use according to claim 7, wherein the decomposition is carried out at low temperature;
preferably, the low temperature is 10 to 40 ℃, preferably 20 to 40 ℃.
9. The use of claim 7, wherein the contaminant comprises ozone.
10. The use of claim 7, wherein the contaminants comprise a mixture of ozone and volatile organic compounds.
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