CN107537479B - Catalyst for degrading volatile organic pollutants and preparation method thereof - Google Patents
Catalyst for degrading volatile organic pollutants and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for degrading volatile organic pollutants and a preparation method thereof. The catalyst comprises a substrate and gold loaded on the surface of the substrate, wherein the gold exists in an ion form, the substrate is semiconductor oxide, the mass ratio of the gold to the semiconductor oxide is 0.0001-0.0003: 100, and the catalyst is a thermal catalyst. The preparation method of the catalyst comprises the following steps: 1) preparing a chloroauric acid aqueous solution with the pH value of 6-8; 2) adding semiconductor oxide powder into a chloroauric acid aqueous solution; 3) stirring and centrifuging the mixture obtained in the step 2), removing supernatant, and drying the obtained precipitate; 4) calcining the precipitate obtained in the step 3) in a muffle furnace at the temperature of 300-350 ℃ for 3-5 hours, then cooling the precipitate to room temperature along with the furnace, taking out the precipitate and grinding the precipitate to obtain the doped modified catalyst for degrading the volatile organic pollutants. The catalyst prepared by the method has higher thermal catalytic activity than other methods, has low manufacturing cost and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of inorganic material environmental purification, and particularly relates to a catalyst for degrading volatile organic pollutants and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are organic compounds existing in the air in the form of vapor at normal temperature, and include alkanes, aromatic hydrocarbons, aldehydes, ketones, and the like. The harm of VOCs is obvious, and when the concentration of VOCs in a room exceeds a certain concentration, people can feel headache, nausea, vomiting and limb weakness in a short time; in severe cases, convulsions, coma and hypomnesis will occur. VOCs pollution in the room has attracted attention.
The problem of VOCs in indoor air in China is serious. Poor-quality building materials and decoration materials are introduced into the market, and excessive synthetic materials and coatings are used for indoor decoration, so that the problem of overproof caused by the poor-quality building materials and decoration materials is paid attention to. Too tight fresh air volume of doors and windows or even no fresh air is an important factor for causing the concentration of VOCs to rise in order to prevent dust and sound or save energy in air-conditioning heating. In this regard, the following proposals have been made by researchers:
① pollution source control, environment protection type decoration material selection, pollution reduction as the primary condition for pollution control, application of photocatalysis technology in the development of new type building decoration material, coating TiO on wallpaper, furniture panel, fluorescent lamp, and window glass in Japan and America2Film, removing VOCs and bacteria by photocatalytic oxidation. But the cost is high, and the commercial popularization cannot be realized.
② the adsorption technology controls the VOCs in the room. The adsorption technology is the most common control technology for removing indoor VOCs at present, and common adsorbents comprise: granular activated carbon, activated carbon fibers, zeolite, sub-sieves, porous clay minerals, activated alumina, silica gel and the like, wherein granular activated carbon, activated alumina containing potassium permanganate and modified granular carbon are most commonly used. However, the adsorption material has a short service cycle, and due to the reactivity and thermal instability of some compounds (such as formaldehyde and the like), the adsorption material is not easy to recover from the adsorbent, and VOCs cannot be thoroughly removed;
③ photocatalytic oxidation technology for controlling indoor VOCs, the photocatalytic oxidation technology mainly utilizes TiO2When the photocatalytic performance of the semiconductor material is equal, VOCs adsorbed on the surface of the catalyst are oxidized to generate CO2And H2And O. Current research indicates that most VOCs in indoor air are oxidized photocatalytically, however there is constant controversy regarding the products of their vapor phase photocatalytic degradation. Theoretically, photocatalysis can completely oxidize VOCs, but in practical application, the photocatalysis of VOCs may generate intermediate products such as aldehyde ketone, vinegar, acid and the like.
Disclosure of Invention
The invention aims to provide a thermal catalyst which has small Au loading capacity and can efficiently degrade volatile organic pollutants and a preparation method of the thermal catalyst.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the catalyst comprises a substrate and gold loaded on the surface of the substrate, wherein the gold exists in an ion form, the substrate is semiconductor oxide, and the mass ratio of the gold to the semiconductor oxide is 0.0001-0.0003: 100.
In the above embodiment, the semiconductor oxide may be ZnO or CeO2Or may be TiO2If it is TiO2，TiO2Is a mixed crystal form of anatase and rutile.
The preparation method of the catalyst for degrading the volatile organic pollutants comprises the following steps:
1) preparing a chloroauric acid aqueous solution with the pH value of 6-8;
2) adding semiconductor oxide powder into a chloroauric acid aqueous solution, wherein the mass ratio of Au to metal elements in the semiconductor oxide is 0.01-0.05: 100;
3) stirring and centrifuging the mixture obtained in the step 2), removing supernatant, and drying the obtained precipitate;
4) calcining the precipitate obtained in the step 3) in a muffle furnace at the temperature of 300-350 ℃ for 3-5 hours, then cooling the precipitate to room temperature along with the furnace, taking out the precipitate and grinding the precipitate to obtain the doped modified thermal catalyst for efficiently eliminating the volatile organic compounds.
In the scheme, the drying temperature in the step 3) is 80 ℃.
In the scheme, the centrifugal rotating speed in the step 3) is 1500-2000 r/min, and the centrifugal time is 5-10 min.
In the scheme, the stirring in the step 3) is continuously stirred for 2-3 hours at the temperature of 30 ℃.
In the above scheme, the calcination temperature in step 4) is 300 ℃.
In the above scheme, the volatile organic pollutant is formaldehyde or formic acid.
The catalyst prepared by the method can effectively eliminate volatile organic pollutants formaldehyde or formic acid.
The invention has the beneficial effects that: the method has the advantages of simple and easily obtained raw materials, simple process by taking the semiconductor oxide as the raw material. The creativity of the invention is mainly represented by organically combining the load modification process of the semiconductor oxide with the deposition precipitation method process which is easy to realize large-scale production, greatly simplifying the doping modification process, and simultaneously, the obtained thermal catalyst can achieve higher degradation efficiency under the condition of small Au load and greatly reduce the production cost.
Drawings
FIG. 1 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 12And XRD pattern of commercial P25.
FIG. 2 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 32Ultraviolet diffuse reflectance pattern of (a).
FIG. 3 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 22Thermally catalyzed CO in formic acid degradation process2Generating the graph.
FIG. 4 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 22Thermal catalytic formic acid degradation profile.
FIG. 5 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 12Thermally catalyzing CO in formaldehyde degradation process2Generating the graph.
FIG. 6 shows the thermal catalyst Au/TiO for degrading volatile organic pollutants prepared in example 12Thermal catalytic formaldehyde degradation diagram.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings and examples.
The semiconductor oxide in the following examples is selected from TiO2It is understood that ZnO and CeO2The present invention can be implemented as well, and will not be described herein again.
Example 1
The preparation method of the catalyst for degrading the volatile organic pollutants comprises the following steps:
1) with chloroauric acid (AuCl)3·HCl·4H2O) crystal is a source of Au element, and 0.002mol/L chloroauric acid solution is prepared by a volumetric flask;
2) adding 1mol/L NaOH solution into the chloroauric acid solution obtained in the step 1), adjusting the pH value of the chloroauric acid solution to about 7, and standing for later use;
3) weighing 1g of commercial P25 powder, adding the powder into a chloroauric acid aqueous solution, and mixing the powder according to a mass ratio of Au: determining the volume of the chloroauric acid solution to be added to be 152 mu L when the Ti is 0.01 percent;
4) continuously stirring the mixture obtained in the step 3) for 3 hours at the temperature of 30 ℃, then centrifuging the mixture for 10 minutes at the rotating speed of 2000r/min, and drying the precipitate obtained after removing the supernatant in an oven at the temperature of 80 ℃;
5) calcining the precipitate obtained in the step 4) in a muffle furnace at 300 ℃ for 5 hours, then cooling to room temperature along with the furnace, and grinding to obtain the doping modified high-efficiency Au/TiO2A thermal catalyst.
6) The mass content of the supported Au element in the prepared sample is 0.00011 percent measured by an atomic absorption spectrometer.
Example 2
The preparation method of the catalyst for degrading the volatile organic pollutants comprises the following steps:
1) preparing a 0.002mol/L chloroauric acid aqueous solution with a pH value of 7 as shown in example 1;
2) weighing 1g of commercial P25 powder, adding the powder into a chloroauric acid aqueous solution, and mixing the powder according to a mass ratio of Au: determining the volume of the chloroauric acid solution to be added to be 456 mu L when the Ti is 0.03%;
3) continuously stirring the mixture obtained in the step 2) for 3 hours at 30 ℃, then centrifuging the mixture for 10 minutes at the rotating speed of 2000r/min, and drying the precipitate obtained after removing the supernatant in an oven at 80 ℃;
4) calcining the precipitate obtained in the step 3) in a muffle furnace at 300 ℃ for 5 hours, then cooling to room temperature along with the furnace, and grinding to obtain the doping modified high-efficiency Au/TiO2A thermal catalyst.
5) The mass content of the supported Au element in the prepared sample is 0.00023 percent according to the measurement of an atomic absorption spectrometer.
Example 3
The preparation method of the catalyst for degrading the volatile organic pollutants comprises the following steps:
1) preparing a 0.002mol/L chloroauric acid aqueous solution with a pH value of 7 as shown in example 1;
2) weighing 1g of commercial P25 powder, adding the powder into a chloroauric acid aqueous solution, and mixing the powder according to a mass ratio of Au: determining the volume of the chloroauric acid solution to be added to be 760 mu L when the Ti is 0.05 percent;
3) continuously stirring the mixture obtained in the step 2) for 3 hours at 30 ℃, then centrifuging the mixture for 10 minutes at the rotating speed of 2000r/min, and drying the precipitate obtained after removing the supernatant in an oven at 80 ℃;
4) calcining the precipitate obtained in the step 3) in a muffle furnace at 300 ℃ for 5 hours, then cooling to room temperature along with the furnace, and grinding to obtain the doping modified high-efficiency Au/TiO2A thermal catalyst.
5) The mass content of the supported Au element in the prepared sample is 0.00032 percent measured by an atomic absorption spectrometer.
Comparative example
Preparation of Au/TiO2A thermal catalyst, comprising the steps of:
1) preparing a 0.002mol/L chloroauric acid aqueous solution with a pH value of 7 as shown in example 1;
2) weighing 1g of commercial P25 powder, adding the powder into a chloroauric acid aqueous solution, and mixing the powder according to a mass ratio of Au: determining the volume of the chloroauric acid solution to be added to be 152mL when the Ti is 1 percent;
3) continuously stirring the mixture obtained in the step 2) for 3 hours at 30 ℃, then centrifuging the mixture for 10 minutes at the rotating speed of 2000r/min, and drying the precipitate obtained after removing the supernatant in an oven at 80 ℃;
4) calcining the precipitate obtained in the step 3) in a muffle furnace at 300 ℃ for 5 hours, then cooling to room temperature along with the furnace, and grinding to obtain the doping modified high-efficiency Au/TiO2A thermal catalyst.
5) The mass content of the loaded Au element in the prepared sample is measured by an atomic absorption spectrometer to be 0.15 percent.
Evaluation of the performance of the thermal catalyst obtained in the above manner:
using formaldehyde and formic acid (Chinese medicine reagent) as volatile organic compounds which are degraded by thermal catalysis, wherein the dosage of the thermal catalyst is 0.08g, the injection amount of formic acid of the volatile organic compounds is 25 mu L, and the injection amount of formaldehyde is 15 mu L, raising the temperature in a reactor to 140 ℃ by using a temperature controller to carry out thermal catalysis reaction, and carrying out the thermal catalysis reaction for 70min or 44min later on with the formaldehydeDegradation of concentration and CO2Concentrations were generated at room temperature to evaluate thermal catalyst performance. Au/TiO prepared by example2The performance of the hot catalyst is compared to a commercial P25 catalyst as shown.
FIG. 1 shows the high efficiency Au/TiO prepared in example 12XRD pattern of hot catalyst vs commercial P25. The prepared high-efficiency Au/TiO can be known from the figure2The thermal catalyst does not have obvious Au peaks, which indicates that the supported Au content in the sample is extremely trace, and simultaneously, the phase and the crystallinity of the commercial P25 are not changed, and the sample still has a mixed crystal form of anatase and rutile.
FIG. 2 shows the high efficiency Au/TiO prepared in example 32Uv diffuse reflectance pattern of hot catalyst vs commercial P25. As can be seen, the high efficiency Au/TiO prepared by this example2The highest absorption peak of the thermal catalyst at the wavelength of about 550nm does not appear, namely the plasma resonance phenomenon does not appear, which shows that the high-efficiency Au/TiO prepared by the embodiment2The thermal catalyst supported Au element was present in the sample in an ionic form.
FIGS. 3 and 4 show the high-performance Au/TiO prepared in example 22Thermal catalytic degradation of formic acid by thermal catalyst with commercial P25. As can be seen from the combination of FIGS. 3 and 4, the high efficiency Au/TiO prepared by the present invention is injected with formic acid for 15min2The formic acid concentration in the hot catalyst begins to drop substantially, while a large amount of CO is produced2. As can be seen from fig. 4, after 44min, the degradation rate of the thermally catalyzed formic acid of the sample of the invention reaches 73.33%, and the degradation rates of the formic acid of the samples of example 1 and example 3 are 80.21% and 74.56%, respectively; whereas the formic acid degradation rate of the commercial P25 and the high-loading Au samples in the comparative examples was about 8.89%.
FIGS. 5 and 6 show the high-performance Au/TiO prepared in example 12Thermal catalytic degradation of formaldehyde by thermal catalyst versus commercial P25. As can be seen from the combination of FIGS. 5 and 6, the formaldehyde concentration started to decrease greatly and a large amount of CO was produced 10min after the injection of formaldehyde2. As can be seen from FIG. 6, after 70min, the concentration of the thermocatalytic formaldehyde of the sample of the present invention has been reduced to 500ppm, the degradation rate reaches 90.48%, and the formaldehyde degradation rates of the samples of example 2 and example 3 are 91.45% and 90.31%, respectively;while the formaldehyde concentrations of commercial P25 and Au-containing samples with large loading are 3500ppm and 3000ppm respectively, and the degradation rate is lower than 42%.
Performance evaluation Table of thermal catalyst
| Initial Au: ti | Amount of Au supported | 44min, formic acid degradation rate | 70min, formaldehyde degradation rate | |
| |
0 | 0 | 8.89％ | 42％ |
| Comparative example | 1:100 | 0.15％ | 8.89％ | 42％ |
| Example 1 | 0.01：100 | 0.00011％ | 80.21％ | 90.48％ |
| Example 2 | 0.03:100 | 0.00023％ | 73.33％ | 91.45％ |
| Example 3 | 0.05:100 | 0.00032％ | 74.56％ | 90.31％ |
The catalyst has a good volatile organic matter degradation effect under the loading of trace Au.
In addition, it is understood that other semiconductors oxidize ZnO and CeO2The same degradation effect of volatile organic compounds can be achieved under the loading of a trace amount of Au.
Claims (7)
1. The catalyst for degrading the volatile organic pollutants comprises a substrate and gold loaded on the surface of the substrate, wherein the gold exists in an ion form, the substrate is a semiconductor oxide, the mass ratio of the gold to the semiconductor oxide is 0.0001-0.0003: 100, the catalyst is a thermal catalyst, and the semiconductor oxide is titanium dioxide P25.
2. The method of claim 1, wherein the method comprises the steps of:
1) preparing a chloroauric acid aqueous solution with the pH value of 6-8;
2) adding semiconductor oxide powder into a chloroauric acid aqueous solution, wherein the mass ratio of Au to metal elements in the semiconductor oxide is 0.01-0.05: 100;
3) stirring and centrifuging the mixture obtained in the step 2), removing supernatant, and drying the obtained precipitate;
4) calcining the precipitate obtained in the step 3) in a muffle furnace at the temperature of 300-350 ℃ for 3-5 hours, then cooling the precipitate to room temperature along with the furnace, taking out the precipitate and grinding the precipitate to obtain the doped modified catalyst for degrading the volatile organic pollutants.
3. The method of claim 2, wherein the drying temperature in step 3) is 80 ℃.
4. The method according to claim 2, wherein the centrifugation speed in step 3) is 1500-2000 r/min, and the centrifugation time is 5-10 min.
5. The method of claim 2, wherein the stirring in step 3) is performed at 30 ℃ for 2-3 hours.
6. The method of claim 2, wherein the calcination temperature in step 4) is 300 ℃.
7. The method of claim 2, wherein the volatile organic contaminant is formaldehyde or formic acid.
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| CN101612578A (en) * | 2008-06-24 | 2009-12-30 | 中国人民解放军63971部队 | Nano catalyst of a kind of eliminating formaldehyde at room temperature and preparation method thereof |
| CN102389795A (en) * | 2011-09-29 | 2012-03-28 | 复旦大学 | Nano gold catalyst for use in hydrogen production by decomposition of formic acid and preparation method thereof |
| CN103736484A (en) * | 2014-01-13 | 2014-04-23 | 中山大学 | Supported integrated catalyst for formaldehyde purification and preparation method thereof |
| CN107029705A (en) * | 2017-05-18 | 2017-08-11 | 厦门大学 | The preparation and its application of a kind of load type metal catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612578A (en) * | 2008-06-24 | 2009-12-30 | 中国人民解放军63971部队 | Nano catalyst of a kind of eliminating formaldehyde at room temperature and preparation method thereof |
| CN102389795A (en) * | 2011-09-29 | 2012-03-28 | 复旦大学 | Nano gold catalyst for use in hydrogen production by decomposition of formic acid and preparation method thereof |
| CN103736484A (en) * | 2014-01-13 | 2014-04-23 | 中山大学 | Supported integrated catalyst for formaldehyde purification and preparation method thereof |
| CN107029705A (en) * | 2017-05-18 | 2017-08-11 | 厦门大学 | The preparation and its application of a kind of load type metal catalyst |
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