CN103191737A - Load-type nano Au-CeO2 catalyst for degradation of volatile organic compounds and preparation method thereof - Google Patents

Load-type nano Au-CeO2 catalyst for degradation of volatile organic compounds and preparation method thereof Download PDF

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CN103191737A
CN103191737A CN2013100761370A CN201310076137A CN103191737A CN 103191737 A CN103191737 A CN 103191737A CN 2013100761370 A CN2013100761370 A CN 2013100761370A CN 201310076137 A CN201310076137 A CN 201310076137A CN 103191737 A CN103191737 A CN 103191737A
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catalyst
reaction
ceo
ethanolic solution
volatile organic
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CN103191737B (en
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蒋新
华杰锋
吴忠标
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a load-type nano Au-CeO2 catalyst for degradation of volatile organic compounds and a preparation method thereof. The catalyst is characterized in that Au is a main active component, CeO2 is a co-catalyst component, and nano-SiO2 is used as a carrier. The catalyst has excellent activity and good stability for degradation of volatile organic compounds.

Description

Supported nano-Au-the CeO of degraded volatile organic matter 2Catalysts and its preparation method
Technical field
The present invention relates to a kind of supported nano-Au-CeO of the volatile organic matter of degrading 2Catalysts and its preparation method, this catalyst are used for the degraded volatile organic matter.
Technical background
In recent years, serious day by day by the caused problem of environmental pollution of volatile organic matter (VOCs)." room air pollution " is that the continue third generation of " bituminous coal ", " photochemical fog " pollutes.Characteristics such as in many environmental improvement technology, catalytic oxidation (burning) has that operation energy consumption is low, efficient is high, non-secondary pollution, equipment are simple, clearance height become a kind of environmental improvement technology of desirable removal organic pollution and receive much concern.The research Production by Catalytic Combustion Process is carried out deep oxidation to VOCs and is removed and have great importance the catalyst that focuses on preparing low light-off temperature, high selectivity of research.Nanometer Au has been subjected to scholars' extensive concern after being found to have the performance of higher catalyzing acetylene hydrochlorinate and low temperature CO oxidation.Nano-Au catalyst can be applicable to numerous areas such as environmental improvement, Green Chemistry.Aspect elimination VOCs, to local atmosphere pollutants such as methyl alcohol and derivative formaldehyde, formic acid, catalyst A u/ α-Fe 2O 3Be lower than 100 ℃ just can be with its complete oxidation, and possess certain water-resistance; To catalysis benzene complete oxidation, nanometer Au loads on the CeO of high-ratio surface 2On, also can be in the time of 250 ℃ the benzene of catalyzed conversion 90%.
Studies show that it is the nanoscale Au particle for preparing high dispersive that the Au catalyst has highly active important prerequisite, adds the oxidability that other suitable components can be improved catalyst, thereby improve the catalytic activity of degraded volatile organic matter.General Au catalyst has two kinds of non-loading type and support types, and wherein non-loading type Au catalyst is reunited easily in catalytic process and grown up and then inactivation, and the catalyst recycling rate of waterused is low.Support type Au Preparation of catalysts method is numerous, and as coprecipitation, deposition-precipitation method, sol-gel process etc., but these methods often can not obtain polymolecularity, the catalyst of homogeneous grain diameter.Therefore, developing a kind of good dispersion, size distribution homogeneous, Au and other components has better interaction, and the loaded catalyst that has greater activity simultaneously seems very necessary.
The loaded catalyst of this method preparation, epigranular, good dispersion, carrier can be modified, and its load particle properties has controllability.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of support type Au-CeO for the degraded volatile organic matter 2Catalysts and its preparation method.
A kind of supported nano-Au-CeO for the degraded volatile organic matter 2Catalyst is main active component with Au, CeO 2Be co-catalyst component, with nanoscale SiO 2Be carrier.
By the described SiO of quality percentage composition 2: 64 ~ 91%, Au:0.2 ~ 4.5%, CeO 2: 4.6 ~ 33%, Au: CeO 2: 0.02 ~ 0.95.
A kind of described supported nano-Au-CeO for the degraded volatile organic matter 2The Preparation of catalysts method, step is as follows:
1) volume fraction of preparation deionized water is the ethanolic solution of 0.5-2%, adds the NaOH of 0.015 ~ 0.2 g, adds 0.5g nano carrier SiO under the stirring condition 2, to fully mixing;
2) preparation 50ml contains Ce (NO 3) 36H 2O is the ethanolic solution of 0.06-0.7g, drops in the system that mixes that step 1) obtains reaction 1-5h under the stirring condition;
3) will be through step 2) system that obtains is transferred to temperature in-20-25 ℃ the environment, adds the 50ml ethanolic solution that is dissolved with 0-0.04g NaOH under the stirring condition, fully mix;
4) in the system that obtains through step 3), will be dissolved with 0.002-0.05g HAuCl under the stirring condition 46H 2The 50ml ethanolic solution of O drops in the system; Behind reaction 1 ~ 5h, will be dissolved with 0.0002 ~ 0.006g NaBH 4The 50ml ethanolic solution drop in the above-mentioned system, continue reaction 0.5 ~ 3h, through repeatedly centrifugal, disperse again, wash, dry and 200 ~ 600 ℃ of conditions under obtain catalyst after the roasting.
Beneficial effect of the present invention is:
1) carrier is nano level silica gel particle, eliminated in the course of reaction in extend influence.
2) Au and CeO 2Epigranular, good dispersion, its particle diameter of regulation and control that can be more convenient, wherein changing preparation parameter can be easy and effective regulation and control Au particle diameter in the 6-20nm scope.
3) catalyst has good effect for the degraded volatile organic matter, is oxidized to example with catalysis benzene, and the conversion ratio of benzene can reach about 97% in the time of 300 ℃.
Description of drawings
The degrade supported nano-Au-CeO of volatile organic matter of Fig. 1 2The catalyst transmission electron microscope photo.
The degrade supported nano-Au-CeO2 catalyst XRD result schematic diagram of volatile organic matter of Fig. 2.
The degrade supported nano-Au-CeO2 catalyst benzene oxidation results schematic diagram of volatile organic matter of Fig. 3.
The specific embodiment
Specify the present invention below in conjunction with drawings and Examples.
Embodiment 1
Get 0.5g SiO 2(specific surface is about 200 m 2/ g) be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.04g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.147g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to-20 ℃, and adding is dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst A.Wherein catalyst transmission electron microscope (TEM) photo is seen Fig. 1, and XRD the results are shown in Figure 2.
Take benzene as the characteristic of model reaction thing examination catalyst.Take by weighing the 0.05g catalyst A, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 27.2%; In the time of 300 ℃, the benzene conversion ratio is 97%, and catalytic result is seen Fig. 3.
Embodiment 2
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.18g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.65g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 0 ℃, and adding is dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst B.
Take by weighing the 0.1g catalyst B, mix with 3.0g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 23.8%; In the time of 300 ℃, the benzene conversion ratio is 29.6%.
Embodiment 3
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.04g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.147g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 0 ℃, drips the 50ml ethanolic solution that is dissolved with 0.04g NaOH, absorption 3h; Add and be dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst C.
Take by weighing 0.05g catalyst C, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 5.3%; In the time of 320 ℃, the benzene conversion ratio is 11.2%.
Embodiment 4
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.04g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.147g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 25 ℃, and adding is dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst D.
Take benzene as the characteristic of model reaction thing examination catalyst.Take by weighing 0.05g catalyst D, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 19.7%; In the time of 320 ℃, the benzene conversion ratio is 73.2%.
Embodiment 5
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.018g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.066g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 0 ℃, and adding is dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst E.
Take by weighing 0.05g catalyst E, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 12.2%; In the time of 300 ℃, the benzene conversion ratio is 40.5%.
Embodiment 6
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 1ml deionized water, 0.04g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.147g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 0 ℃, and adding is dissolved with 0.002g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0002g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst F.
Take by weighing 0.05g catalyst F, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 17.4%; In the time of 300 ℃, the benzene conversion ratio is 33.5%.
Embodiment 7
Get 0.5g SiO 2Be dispersed in the 200ml ethanol, add the 4ml deionized water, 0.04g NaOH, stirring and adsorbing, reaction under 25 ℃ of temperature, behind the absorption 3h, other gets 50ml ethanol and adds the 0.147g cerous nitrate, is added dropwise to reaction system, continues reaction 3h.Above-mentioned system is transferred to 0 ℃, and adding is dissolved with 0.05g HAuCl 46H 2The 50ml ethanolic solution of O adsorbs; Behind the absorption 3h, drip and be dissolved with 0.0052g NaBH 4The 50ml ethanolic solution, the reaction 1h after, through repeatedly centrifugal, disperse again, wash, dry and under 400 ℃ of conditions roasting 2h obtain catalyst G.
Take by weighing 0.05g catalyst G, mix with 1.5g quartz sand, fill in the stainless steel reaction pipe of 4mm.Reaction tube is placed in the tubular heater.Catalyst at first through behind the uniform temperature activation 2h, feeds the air that contains benzene and reacts.The concentration of benzene is taken a sample gas chromatographic analysis before and after the reaction by six-way valve.Determine the conversion ratio of benzene by the variation of concentration before and after the reaction tube.Analyze as can be known, in the time of 260 ℃, the benzene conversion ratio is 26.8%; In the time of 300 ℃, the benzene conversion ratio is 69%.

Claims (3)

1. supported nano-Au-CeO who is used for the degraded volatile organic matter 2Catalyst is characterized in that, is main active component with Au, CeO 2Be co-catalyst component, with nanoscale SiO 2Be carrier.
According to claim 1 a kind of for the degraded volatile organic matter supported nano-Au-CeO 2Catalyst is characterized in that, by the described SiO of quality percentage composition 2: 64 ~ 91%, Au:0.2 ~ 4.5%, CeO 2: 4.6 ~ 33%, Au: CeO 2: 0.02 ~ 0.95.
One kind according to claim 1 for the degraded volatile organic matter supported nano-Au-CeO 2The Preparation of catalysts method is characterized in that, step is as follows:
1) volume fraction of preparation deionized water is the ethanolic solution of 0.5-2%, adds the NaOH of 0.015 ~ 0.2 g, adds 0.5g nano carrier SiO under the stirring condition 2, to fully mixing;
2) preparation 50ml contains Ce (NO 3) 36H 2O is the ethanolic solution of 0.06-0.7g, drops in the system that mixes that step 1) obtains reaction 1-5h under the stirring condition;
3) will be through step 2) system that obtains is transferred to temperature in-20-25 ℃ the environment, adds the 50ml ethanolic solution that is dissolved with 0-0.04g NaOH under the stirring condition, fully mix;
4) in the system that obtains through step 3), will be dissolved with 0.002-0.05g HAuCl under the stirring condition 46H 2The 50ml ethanolic solution of O drops in the system; Behind reaction 1 ~ 5h, will be dissolved with 0.0002 ~ 0.006g NaBH 4The 50ml ethanolic solution drop in the above-mentioned system, continue reaction 0.5 ~ 3h, through repeatedly centrifugal, disperse again, wash, dry and 200 ~ 600 ℃ of conditions under obtain catalyst after the roasting.
CN201310076137.0A 2013-03-11 2013-03-11 Load-type nano Au-CeO2 catalyst for degradation of volatile organic compounds and preparation method thereof Expired - Fee Related CN103191737B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111330606A (en) * 2020-04-14 2020-06-26 浙江大学 Catalyst for efficiently degrading chlorine-containing organic waste gas at low temperature and preparation method and application thereof

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CN101992105A (en) * 2010-11-12 2011-03-30 大连理工大学 Sliver-based bimetallic catalyst for catalyzing oxidation of volatile organic contaminant, preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111330606A (en) * 2020-04-14 2020-06-26 浙江大学 Catalyst for efficiently degrading chlorine-containing organic waste gas at low temperature and preparation method and application thereof

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