CN107537479A - A kind of degrading volatile organic pollutant catalyst and preparation method thereof - Google Patents
A kind of degrading volatile organic pollutant catalyst and preparation method thereof Download PDFInfo
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- CN107537479A CN107537479A CN201710695997.0A CN201710695997A CN107537479A CN 107537479 A CN107537479 A CN 107537479A CN 201710695997 A CN201710695997 A CN 201710695997A CN 107537479 A CN107537479 A CN 107537479A
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Abstract
The present invention relates to a kind of degrading volatile organic pollutant catalyst and preparation method thereof.The catalyst includes matrix and is carried on the gold of matrix surface, and gold exists in the form of an ion, and matrix is conductor oxidate, and the mass ratio of gold and conductor oxidate is 0.0001~0.0003:100, the catalyst is thermocatalyst.The preparation method of the catalyst is：1) secure ph is 6~8 aqueous solution of chloraurate；2) semiconductor oxide powder is added in aqueous solution of chloraurate；3) precipitation of gained is dried after mixture stirring, centrifugation, removal supernatant obtained by step 2)；4) step 3) gained sediment is calcined 3~5 hours in 300 350 DEG C of muffle furnaces, then cools to room temperature with the furnace, and the degrading volatile organic pollutant catalyst of doping vario-property is obtained after taking out grinding.Have the thermocatalytic higher than other method active by catalyst made from this method, manufacturing cost is low, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to inorganic material technical field of environmental purification, and in particular to a kind of degrading volatile organic pollution
Catalyst and preparation method thereof.
Background technology
Volatile organic matter (VOCs) refers to a kind of organic compound being present in vapour form at normal temperatures in air
Thing, including alkanes, aromatic hydrocarbons, aldehydes, ketone etc..VOCs harm exceedes finite concentration it is obvious that working as VOCs concentration in room
When, people can feel headache, Nausea and vomiting, limbs fatigue in a short time；It can twitch, go into a coma when serious, failure of memory.
Occupying indoor VOCs pollution has attracted people's attention.
VOCs problems in China's room air are than more serious.Construction material and finishing material inferior come into the market and
Interior decoration employs excessive synthetic material, coating, and excessive problem must cause our concern caused by.In order to anti-
Dirt sound insulation or air-conditioning heating energy-saving and make the excessively tight resh air requirement of door and window small even without fresh air be also cause VOCs concentration rise
A critically important factor.On the other hand, there is researcher to propose following suggestion and measure：
1. controlling pollution sources, from environmental type finishing material, the primary bar that pollution generating capacity is control pollution is reduced
Part.Japan, U.S. etc. country photocatalysis technology is applied in the exploitation of new decorative material for building, wallpaper, furniture panel,
TiO is applied on fluorescent lamp, glass pane2Film, VOCs and bacterium are removed by photochemical catalytic oxidation.But its cost is higher, nothing
Method is carried out commercialization and promoted.
2. adsorption technology controls indoor VOCs.Adsorption technology is the most frequently used control technology of current removal indoor VOCs, often
Adsorbent has：Granular activated carbon, NACF, zeolite, sub- sieve, adobe ore, activated alumina and silica gel etc.,
It is wherein again the most frequently used with granular activated carbon, the activated alumina containing potassium permanganate and modified particles charcoal.But sorbing material makes
It is short with the cycle, and due to some compounds (such as formaldehyde) reactivity and to heat it is unstable, be not easy to reclaim from adsorbent,
VOCs can not thoroughly be removed；
3. photocatalysis oxidation technique controls indoor VOCs.Photocatalysis oxidation technique mainly utilizes TiO2Deng semi-conducting material
Photocatalysis performance, oxidation-adsorption catalyst surface VOCs, generate CO2And H2O.Current research shows, in room air
Most of VOCs can by photochemical catalytic oxidation, but on its gas-phase photocatalysis degraded product but always exist dispute.Reason
By upper photocatalysis can complete oxidation VOCs, but in practical application VOCs light-catalyzed reaction may produce as aldehyde ketone, vinegar and
The intermediate products such as acid.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of Au load capacity it is small and can efficient degradation volatile it is organic
The preparation method of the thermocatalyst of pollutant and the catalyst.
In order to solve the above technical problems, technical scheme is as follows：
Catalyst of the present invention includes matrix and is carried on the gold on described matrix surface, and gold is deposited in the form of an ion
Matrix is conductor oxidate, and the gold is 0.0001~0.0003 with the mass ratio of conductor oxidate:100.
In such scheme, the conductor oxidate can be ZnO or CeO2, or TiO2, if TiO2, TiO2
For anatase and the mixing crystal formation of rutile.
The preparation method of degrading volatile organic pollutant catalyst of the present invention, comprises the following steps：
1) secure ph is 6~8 aqueous solution of chloraurate；
2) semiconductor oxide powder is added in aqueous solution of chloraurate, the Au and metallic element in conductor oxidate
Mass ratio be 0.01~0.05:100；
3) mixture stirring, centrifugation, the precipitation drying for removing gained after supernatant obtained by step 2)；
4) step 3) gained sediment is calcined 3~5 hours in 300-350 DEG C of muffle furnace, then cools to room temperature with the furnace,
The efficient elimination volatile organic matter thermocatalyst of doping vario-property is obtained after taking out grinding.
In such scheme, the drying temperature in step 3) is 80 DEG C.
In such scheme, the centrifugal rotational speed in step 3) is 1500~2000r/min, and centrifugation time is 5~10min.
In such scheme, the stirring in step 3) is to be continuously stirred at 30 DEG C 2~3 hours.
In such scheme, the calcining heat in step 4) is 300 DEG C.
In such scheme, the volatile organic pollution is formaldehyde or formic acid.
Catalyst prepared by methods described can efficiently eliminate volatile organic contaminant formaldehyde or formic acid.
Beneficial effects of the present invention are：The raw material of the inventive method is simple and easy to get, using conductor oxidate as raw material, technique
Process is simple.The creativeness of invention is mainly manifested in the loaded modified process conductor oxidate with being easily achieved scale metaplasia
The deposition-precipitation method process of production combines, and greatly simplifies doping vario-property process, meanwhile, obtained thermocatalyst is born in Au
Higher degradation efficiency can be reached in the case of carrying capacity very little, production cost is greatly lowered.
Brief description of the drawings
Fig. 1 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 12And commercial P25
XRD.
Fig. 2 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 32Uv drses
Figure.
Fig. 3 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 22Thermocatalytic formic acid drops
CO in solution preocess2Generation figure.
Fig. 4 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 22Thermocatalytic formic acid drops
Xie Tu.
Fig. 5 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 12Thermocatalytic formaldehyde drops
CO in solution preocess2Generation figure.
Fig. 6 is the degrading volatile organic pollution thermocatalyst Au/TiO prepared by embodiment 12Thermocatalytic formaldehyde drops
Xie Tu.
Embodiment
To make those skilled in the art more fully understand technical scheme, with reference to the accompanying drawings and examples to this
Invention is described in further detail.
That the conductor oxidate in following examples is selected is TiO2, it is to be understood that ZnO and CeO2Equally can be real
The existing present invention, will not be repeated here.
Embodiment 1
Degrading volatile organic pollutant catalyst is prepared, step is as follows：
1) with gold chloride (AuCl3·HCl·4H2O) crystal is the source of Au elements, and 0.002mol/L is prepared with volumetric flask
Chlorauric acid solution；
2) 1mol/L NaOH solution is added into chlorauric acid solution obtained by step 1), the pH value of chlorauric acid solution is transferred to
About 7, stand for standby use；
3) weigh 1g commercialization P25 powders to add in aqueous solution of chloraurate, according to mass ratio Au：Ti=0.01% determines to add
The μ L of chlorauric acid solution volume 152 entered；
4) mixture obtained by step 3) continuously stirs 3 hours at 30 DEG C, then with rotating speed 2000r/min centrifugation
10min, being deposited in 80 DEG C of baking ovens for gained is dried after removing supernatant；
5) step 4) gained sediment is calcined 5 hours in 300 DEG C of muffle furnaces, room temperature is then cooled to the furnace, after grinding
Obtain the efficient Au/TiO of doping vario-property2Thermocatalyst.
6) it is 0.00011% to measure the Au elements mass content loaded in obtained sample by Atomic Absorption Spectrometer.
Embodiment 2
Degrading volatile organic pollutant catalyst is prepared, step is as follows：
1) as described in Example 1, secure ph is 7 0.002mol/L aqueous solution of chloraurate；
2) weigh 1g commercialization P25 powders to add in aqueous solution of chloraurate, according to mass ratio Au：Ti=0.03% determines to add
The μ L of chlorauric acid solution volume 456 entered；
3) mixture obtained by step 2) continuously stirs 3 hours at 30 DEG C, then with rotating speed 2000r/min centrifugation
10min, being deposited in 80 DEG C of baking ovens for gained is dried after removing supernatant；
4) step 3) gained sediment is calcined 5 hours in 300 DEG C of muffle furnaces, room temperature is then cooled to the furnace, after grinding
Obtain the efficient Au/TiO of doping vario-property2Thermocatalyst.
5) it is 0.00023% to measure the Au elements mass content loaded in obtained sample by Atomic Absorption Spectrometer.
Embodiment 3
Degrading volatile organic pollutant catalyst is prepared, step is as follows：
1) as described in Example 1, secure ph is 7 0.002mol/L aqueous solution of chloraurate；
2) weigh 1g commercialization P25 powders to add in aqueous solution of chloraurate, according to mass ratio Au：Ti=0.05% determines to add
The μ L of chlorauric acid solution volume 760 entered；
3) mixture obtained by step 2) continuously stirs 3 hours at 30 DEG C, then with rotating speed 2000r/min centrifugation
10min, being deposited in 80 DEG C of baking ovens for gained is dried after removing supernatant；
4) step 3) gained sediment is calcined 5 hours in 300 DEG C of muffle furnaces, room temperature is then cooled to the furnace, after grinding
Obtain the efficient Au/TiO of doping vario-property2Thermocatalyst.
5) it is 0.00032% to measure the Au elements mass content loaded in obtained sample by Atomic Absorption Spectrometer.
Comparative example
Prepare Au/TiO2Thermocatalyst, step are as follows：
1) as described in Example 1, secure ph is 7 0.002mol/L aqueous solution of chloraurate；
2) weigh 1g commercialization P25 powders to add in aqueous solution of chloraurate, according to mass ratio Au：Ti=1% determines to add
Chlorauric acid solution volume 152mL；
3) mixture obtained by step 2) continuously stirs 3 hours at 30 DEG C, then with rotating speed 2000r/min centrifugation
10min, being deposited in 80 DEG C of baking ovens for gained is dried after removing supernatant；
4) step 3) gained sediment is calcined 5 hours in 300 DEG C of muffle furnaces, room temperature is then cooled to the furnace, after grinding
Obtain the efficient Au/TiO of doping vario-property2Thermocatalyst.
5) it is 0.15% to measure the Au elements mass content loaded in obtained sample by Atomic Absorption Spectrometer.
The performance evaluation of the thermocatalyst obtained to the above method：
It is the volatile organic matter that thermocatalytic is degraded with formaldehyde and formic acid (traditional Chinese medicines reagent), thermocatalyst of the invention is used
It is 25 μ L to measure as 0.08g, volatile organic matter formic acid injection rate, and formaldehyde injection rate is 15 μ L, with temperature controller by reactor
Temperature rises to 140 DEG C of progress heat catalysises, with the degraded varied concentration and CO of formaldehyde after heat catalysis 70min or 44min2
Room temperature produces concentration to evaluate thermocatalyst performance.The Au/TiO prepared with embodiment2Thermocatalyst and commercial P25 catalyst
Performance comparision is as shown in the figure.
Fig. 1 is the efficient Au/TiO prepared by embodiment 12The XRD of thermocatalyst and commercial P25.It is made as seen from the figure
Standby efficient Au/TiO2There are not obvious Au peaks in thermocatalyst, and the Au contents loaded in this explanation sample are extremely micro, together
When also without the thing phase and crystallinity for changing commercial P25, remain as the mixing crystal formation of anatase and rutile.
Fig. 2 is the efficient Au/TiO prepared by embodiment 32The uv drses figure of thermocatalyst and commercial P25.Can by figure
Know, the efficient Au/TiO prepared by the present embodiment2Thermocatalyst is that 550nm or so place highest absorption does not occur in wavelength
Peak, i.e., there is not plasma resonance, illustrate the efficient Au/TiO prepared by the present embodiment2The Au of thermocatalyst load
Element is present in sample in the form of ionic state.
Fig. 3 and Fig. 4 is the efficient Au/TiO prepared by embodiment 22The thermocatalytic degraded formic acid of thermocatalyst and commercial P25
Figure.Integrated from Fig. 3 and Fig. 4, after formic acid 15min is injected, the efficient Au/TiO prepared by the present invention2First in thermocatalyst
Acid concentration starts significantly to decline, while produces a large amount of CO2.As shown in Figure 4, after 44min, inventive samples thermocatalytic formic acid
Degradation rate reaches 73.33%, and embodiment 1 and the formic acid degradation rate of the sample of embodiment 3 are respectively 80.21%, 74.56%；And
The formic acid degradation rate of commercial P25 and the high capacity amount Au samples in comparative example is 8.89% or so.
Fig. 5 and Fig. 6 is the efficient Au/TiO prepared by embodiment 12The thermocatalytic degradation of formaldehyde of thermocatalyst and commercial P25
Figure.Integrated from Fig. 5 and Fig. 6, after formaldehyde 10min is injected, concentration of formaldehyde starts significantly to decline, while produces a large amount of
CO2.By Fig. 6, it can be seen that, after 70min, inventive samples thermocatalytic concentration of formaldehyde has dropped down to 500ppm, and degradation rate reaches
90.48%, and embodiment 2 and the Degradation Formaldehyde rate of the sample of embodiment 3 are respectively 91.45%, 90.31%；And commercial P25 and
Concentration of formaldehyde is respectively 3500ppm, 3000ppm in the larger sample containing Au of load capacity, and degradation rate is less than 42%.
The performance evaluation table of thermocatalyst
| Initial Au：Ti | Au load capacity | 44min, formic acid degradation rate | 70min, Degradation Formaldehyde rate | |
| Commercial P25 | 0 | 0 | 8.89% | 42% |
| Comparative example | 1:100 | 0.15% | 8.89% | 42% |
| Embodiment 1 | 0.01：100 | 0.00011% | 80.21% | 90.48% |
| Embodiment 2 | 0.03:100 | 0.00023% | 73.33% | 91.45% |
| Embodiment 3 | 0.05:100 | 0.00032% | 74.56% | 90.31% |
Catalyst of the present invention has preferable volatile organic matter degradation effect under the Au of denier load capacity.
Further it will be understood that other semiconductor oxides ZnO and CeO2, also may be used under the Au of denier load capacity
To reach identical volatile organic matter degradation effect.
Claims (9)
1. a kind of degrading volatile organic pollutant catalyst, it is characterised in that the catalyst includes matrix and load
Gold in described matrix surface, the gold exist in the form of an ion, and described matrix is conductor oxidate, the gold and semiconductor
The mass ratio of oxide is 0.0001~0.0003:100, the catalyst is thermocatalyst.
2. degrading volatile organic pollutant catalyst as claimed in claim 1, it is characterised in that the semiconductor oxide
Thing is ZnO or CeO2。
3. degrading volatile organic pollutant catalyst as claimed in claim 1, it is characterised in that the semiconductor oxide
Thing is TiO2, the TiO2For anatase and the mixing crystal formation of rutile.
4. the preparation method of the degrading volatile organic pollutant catalyst as described in any one of claims 1 to 3, its feature
It is, comprises the following steps：
1) secure ph is 6~8 aqueous solution of chloraurate；
2) semiconductor oxide powder is added in aqueous solution of chloraurate, the Au and metallic element in conductor oxidate matter
Amount is than being 0.01~0.05:100；
3) precipitation of gained is dried after mixture stirring, centrifugation, removal supernatant obtained by step 2)；
4) step 3) gained sediment is calcined 3~5 hours in 300-350 DEG C of muffle furnace, then cools to room temperature with the furnace, is taken out
The degrading volatile organic pollutant catalyst of doping vario-property is obtained after grinding.
5. the preparation method of degrading volatile organic pollutant catalyst as claimed in claim 4, it is characterised in that step
3) drying temperature in is 80 DEG C.
6. the preparation method of degrading volatile organic pollutant catalyst as claimed in claim 4, it is characterised in that step
3) centrifugal rotational speed in is 1500~2000r/min, and centrifugation time is 5~10min.
7. the preparation method of degrading volatile organic pollutant catalyst as claimed in claim 4, it is characterised in that step
3) stirring in is to be continuously stirred at 30 DEG C 2~3 hours.
8. the preparation method of degrading volatile organic pollutant catalyst as claimed in claim 4, it is characterised in that step
4) calcining heat in is 300 DEG C.
9. the preparation method of degrading volatile organic pollutant catalyst as claimed in claim 4, it is characterised in that described
Volatile organic pollution is formaldehyde or formic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894114A (en) * | 2019-03-29 | 2019-06-18 | 武汉理工大学 | A kind of modified CeO of the monatomic Au of Thermal degradation formaldehyde2The preparation method of catalyst |
| CN110967395A (en) * | 2019-12-20 | 2020-04-07 | 中国药科大学 | Gold-loaded functionalized porous TiO2Thin film and application in SALDI-MS analysis |
Citations (4)
| 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 |
-
2017
- 2017-08-15 CN CN201710695997.0A patent/CN107537479B/en active Active
Patent Citations (4)
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894114A (en) * | 2019-03-29 | 2019-06-18 | 武汉理工大学 | A kind of modified CeO of the monatomic Au of Thermal degradation formaldehyde2The preparation method of catalyst |
| CN109894114B (en) * | 2019-03-29 | 2022-06-17 | 武汉理工大学 | Monoatomic Au modified CeO for degrading formaldehyde at low temperature2Process for preparing catalyst |
| CN110967395A (en) * | 2019-12-20 | 2020-04-07 | 中国药科大学 | Gold-loaded functionalized porous TiO2Thin film and application in SALDI-MS analysis |
| CN110967395B (en) * | 2019-12-20 | 2021-03-26 | 中国药科大学 | Gold-loaded functionalized porous TiO2Thin film and application in SALDI-MS analysis |
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