CN114870849A - Composite oxide aerogel catalytic material and preparation method and application thereof - Google Patents

Composite oxide aerogel catalytic material and preparation method and application thereof Download PDF

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CN114870849A
CN114870849A CN202210343464.7A CN202210343464A CN114870849A CN 114870849 A CN114870849 A CN 114870849A CN 202210343464 A CN202210343464 A CN 202210343464A CN 114870849 A CN114870849 A CN 114870849A
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aerogel
tio
composite oxide
zro
catalytic material
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陈英文
范梦婕
李梦翔
刘济宁
沈岳松
王雪峰
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Jiangsu Aikedao Environmental Protection Engineering Technology Co ltd
Nanjing Langke Environmental Protection Technology Co ltd
Nanjing Tech University
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Nanjing Langke Environmental Protection Technology Co ltd
Nanjing Tech University
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Abstract

Composite oxide aerogel catalytic material and preparation method and application thereof, and ZrO prepared from composite oxide aerogel catalytic material 2 ‑TiO 2 The aerogel is used as a carrier and is loaded with transition metal oxide, and the loading amount is 5-20 wt.%. The invention utilizes ZrO 2 ‑TiO 2 The high porosity and abundant acid sites of the aerogel can promote the rapid adsorption and decomposition of substrate molecules and play a role in promoting catalysis. The prepared catalyst is used for evaluating the performance of the catalytic oxidation reaction of low-concentration dichloromethane, and the dichloromethane entering and exiting the reactor is analyzed by gas chromatography. The catalyst has a gas volume space velocity of 5000-40000 h under the condition that the concentration of dichloromethane is 1000-10000 ppm ‑1 When the reaction temperature is 300-420 ℃, the dichloromethane can be catalytically oxidized into CO 2 、H 2 O and HCl.

Description

Composite oxide aerogel catalytic material and preparation method and application thereof
Technical Field
The invention belongs to the field of waste gas treatment, and particularly relates to a composite oxide aerogel catalytic material, and a preparation method and application thereof.
Background
chlorine-Containing Volatile Organic Compounds (CVOCs) are widely derived from industries such as medicines and chemical engineering, and in recent years, with rapid development of the industries, the emission of the CVOCs is increasing, so that the CVOCs have continuous harm to human health and environment, and the treatment of the CVOCs is also receiving increasing attention.
Currently, in the methods for treating CVOCs generated in industrial production, catalytic combustion technology is widely studied and applied due to its advantages of high efficiency, low energy consumption, and the like. However, in the practical application process, the existing catalyst has the defects of low mineralization rate, easy chlorine poisoning and the like, and CVOCs can not be completely decomposed into harmless CO in the catalytic degradation process 2 ，H 2 O and HCl, and is easy to generate Cl poisoning to cause inactivation, and the deep catalytic capability and chlorine resistance of the catalystFurther improvements are needed.
Aerogel is a highly dispersed solid material which is a network porous structure formed by linking colloidal particles or high polymer molecules with each other and is filled with a gaseous dispersion medium. The catalyst carrier has the characteristics of high porosity, uniform pores, high specific surface area, high mechanical strength and the like through modification, and is an ideal material as a catalyst carrier. For example, the publication No. CN106328947B adopts three-dimensional graphene aerogel supported transition metal sulfides, and the two transition metal sulfides have nanoscale crystal grain sizes, are uniformly dispersed, and have good electrochemical properties. With the research on the field of the aerogel in recent years, the preparation of the metal oxide aerogel can avoid supercritical drying at present, simplify the preparation process, reduce the production cost and further promote the industrialization process.
Relevant studies have shown that the catalytic degradation mechanism of methylene chloride is divided into two steps. Firstly, substrate molecules are adsorbed on the surface of a catalyst, and the C-Cl bond is broken under the action of an acid site to form an intermediate product. Then, the intermediate product is oxidized and decomposed into harmless small molecules under the action of the active component so as to realize degradation. ZrO (ZrO) 2 -TiO 2 The oxide has rich acid sites, and the ratio of B acid to L acid is balanced, so that the oxide is a high-quality solid acid carrier in the process of catalytic oxidation of CVOCs. Cu has better deep oxidation capability, the bonding property with Cl is higher than that of most transition metals, the chlorine resistance is better, other active components can be protected in the composite catalyst, and the stability of the catalyst can be improved. Ce oxide has high oxygen storage capacity, and Ce 3+ And Ce 4+ The interconversion between the two can form flowing oxygen vacancy, so that the oxygen vacancy has better oxidation reduction capability. In addition, Ce has highly localized 4f orbitals, can effectively store reduction electrons and is transferred to adsorbate small molecule O 2 And the activation of the catalyst on the surface of the catalyst is enhanced, so that the catalytic performance is further improved. At present, the research on deep oxidation of CVOCs is less, noble metal palladium is mostly added in related research to improve the deep oxidation capability of the catalyst, the cost is higher, the chlorine poisoning resistance is poor, and the catalyst is not industrialized due to the defects of high cost and the like.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a composite oxide aerogel catalytic material, a preparation method and application thereof, wherein ZrO is synthesized 2 -TiO 2 The aerogel carrier provides rich porosity, specific surface area and acid sites, the nano-scale copper cerium oxide is anchored and supported, the deep catalytic capability and chlorine toxicity resistance are enhanced, and CuO-CeO with high specific surface area, high dispersibility, high chlorine resistance and high deep catalytic oxidation capability is developed 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
The technical scheme is as follows: a composite oxide aerogel catalytic material prepared from ZrO 2 -TiO 2 The aerogel is used as a carrier and is loaded with transition metal oxide, and the loading amount is 5-20 wt.%.
ZrO of the above 2 -TiO 2 The mol ratio of Zr to Ti in the aerogel is 1 (2-8).
ZrO of the above 2 -TiO 2 The molar ratio of Zr to Ti in the aerogel is 1:2, 1:4 or 1: 8.
The doped transition metal oxide is copper oxide and cerium oxide.
The molar ratio of the doped transition metal Cu to Ce is 1 (5-10).
The molar ratio of the doped transition metal Cu to Ce is 1:5 or 1: 10.
The preparation method of the composite oxide aerogel catalytic material comprises the following synthetic steps: dissolving zirconium oxychloride in 30mL of ethanol-water mixed solution to obtain zirconium oxychloride alcohol aqueous solution, wherein the volume ratio of ethanol to water is 1:1, dissolving tetrabutyl titanate in 30mL of ethanol to obtain tetrabutyl titanate alcohol solution, adding the zirconium oxychloride alcohol aqueous solution into the tetrabutyl titanate alcohol solution, fully stirring, adding 10g of 1,2 epoxypropane, standing for gelation in a 50 ℃ water bath, adding ethanol after gelation, ageing in a 50 ℃ water bath for 24h, drying in a 120 ℃ drying oven, and roasting in an air atmosphere of 450- 2 -TiO 2 A carrier powder; dissolving active component precursor nitrate in water, adding the active component precursor nitrate which is copper nitrate and cerium nitrateProduced ZrO 2 -TiO 2 The carrier powder is stirred for 12 hours, dried in an oven at 120 ℃, and then roasted for 4 hours in the air atmosphere at 550 ℃ and 450 ℃ to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide catalyst.
The oxides of the above active components are present in the form of nanoparticles in the framework of the support.
The composite oxide aerogel catalytic material is applied to the preparation of industrial waste gas products in petrochemical industry, pharmaceutical industry and electronic industry.
Has the advantages that: the invention is based on the synthesis of ZrO 2 -TiO 2 The aerogel carrier loads copper cerium oxide and utilizes ZrO 2 -TiO 2 The high porosity and abundant acid sites of the aerogel can promote the rapid adsorption and decomposition of substrate molecules and play a role in promoting catalysis. ZrO (ZrO) 2 -TiO 2 The special structure of the aerogel can provide rich anchoring sites for active components, so that the copper cerium oxide is completely dispersed in the form of nanoparticles to form the high-degree composite oxide catalyst. Wherein, the active component is CuO-CeO 2 And ZrO 2 -TiO 2 The aerogel carriers are highly compounded to form a substrate-intermediate-mineralized closed degradation path, so that the deep catalytic oxidation capability and chlorine toxicity resistance of the catalyst to CVOCs are promoted. The prepared catalyst is used for evaluating the performance of the catalytic oxidation reaction of low-concentration dichloromethane, and the dichloromethane entering and exiting the reactor is analyzed by gas chromatography. The catalyst has a gas volume space velocity of 5000-40000 h under the condition that the concentration of dichloromethane is 1000-10000 ppm -1 When the reaction temperature is 300-420 ℃, the dichloromethane can be catalytically oxidized into CO 2 、H 2 O and HCl.
Drawings
FIG. 1 is a graph showing the conversion efficiency of examples 1-10 for DCM;
FIG. 2 is a graph showing the conversion efficiency of examples 11-13 for DCM;
FIG. 3 is a schematic view of the tail gas distribution in example 3;
FIG. 4 is a schematic view of the tail gas distribution in example 12.
Detailed Description
Example 1:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 3.4g of tetrabutyl titanate are dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 2; 0.24g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 2:
3.22g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 6.8g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 2; 0.24g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 3:
1.61g of zirconium oxychloride were dissolved in30g of ethanol and water are fully stirred until dissolved in a mixed solution with the volume ratio of 1: 1. 6.8g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 4; 0.24g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 4:
3.22g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 13.6g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 4; 0.24g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 5:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 13.6g of tetrabutyl titanate are dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding aqueous solution of zirconium oxychloride to titanic acidStirring in tetrabutyl alcohol solution for 10min, adding 10g of 1,2 propylene oxide to gel, and standing in water bath at 50 deg.C to gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 8; 0.24g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 6:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 3.4g of tetrabutyl titanate are dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 2; 0.48g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 7:
3.22g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 6.8g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol after gelation, continuing aging in 50 deg.C water bath for 24 hr, and finishing agingThen the gel is put into a 120 ℃ oven for drying and then is roasted for 4 hours in 500 ℃ air atmosphere to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 2; 0.48g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 8:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 6.8g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 4; 0.48g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 9:
3.22g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 13.6g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 4;0.48g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 10:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 13.6g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 Grinding an aerogel carrier for later use, wherein the molar ratio of Zr to Ti is =1: 8; 0.48g of copper nitrate and 4.34g of cerium nitrate were dissolved in 20g of water, followed by addition of the resulting ZrO 2 -TiO 2 Stirring aerogel carrier powder for 12h, drying in a 120 ℃ oven, and roasting in 500 ℃ air atmosphere for 4h to obtain CuO-CeO 2 /ZrO 2 -TiO 2 A composite oxide aerogel catalyst.
Example 11:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 3.4g of tetrabutyl titanate are dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 An aerogel carrier, wherein the Zr to Ti molar ratio =1: 2.
Example 12:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 6.8g of titaniumTetrabutyl sulfate is dissolved in 10g of ethanol and stirred well until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 An aerogel carrier, wherein the Zr to Ti molar ratio =1: 4.
Example 13:
1.61g of zirconium oxychloride was dissolved in 30g of a mixed solution of ethanol and water in a volume ratio of 1:1, and sufficiently stirred until dissolved. 13.6g of tetrabutyl titanate is dissolved in 10g of ethanol and stirred thoroughly until homogeneous. Adding zirconium oxychloride alcohol aqueous solution into tetrabutyl titanate alcohol solution, stirring for 10min, adding 10g of 1, 2-epoxypropane to make it gel, and standing in water bath at 50 deg.C to make gel. Adding ethanol into the gel, continuing aging in a water bath at 50 ℃ for 24h, drying the gel in an oven at 120 ℃ after aging is finished, and roasting in an air atmosphere at 500 ℃ for 4h to obtain ZrO 2 -TiO 2 An aerogel carrier, wherein the Zr to Ti molar ratio =1: 8.
CuO-CeO obtained in the invention 2 /ZrO 2 -TiO 2 The composite oxide aerogel catalyst has excellent catalytic performance on DCM, and provides a direction for the research of other catalytic oxidation catalysts. The catalyst prepared by the method has the characteristics of large specific surface area, high active substance dispersion, high catalytic activity, strong chlorine poisoning resistance, excellent deep oxidation capability and the like.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A composite oxide aerogel catalytic material, characterized in that: with ZrO 2 -TiO 2 The aerogel is used as a carrier and is loaded with transition metal oxide, and the loading amount is 5-20 wt.%.
2. The composite oxide aerogel catalytic material of claim 1, wherein the ZrO 2 is selected from the group consisting of 2 -TiO 2 The mol ratio of Zr to Ti in the aerogel is 1 (2-8).
3. The composite oxide aerogel catalytic material of claim 2, wherein the ZrO-O-Si-O-s 2 -TiO 2 The molar ratio of Zr to Ti in the aerogel is 1:2, 1:4 or 1: 8.
4. The composite oxide aerogel catalytic material of claim 1, wherein the doped transition metal oxide is copper oxide and cerium oxide.
5. The composite oxide aerogel catalytic material of claim 1, wherein the molar ratio of doped transition metal Cu to Ce is 1 (5-10).
6. The composite oxide aerogel catalytic material of claim 5, wherein the doped transition metal Cu to Ce molar ratio is 1:5 or 1: 10.
7. The method for preparing the composite oxide aerogel catalytic material of any of claims 1 to 6, wherein the synthesis steps are as follows: dissolving zirconium oxychloride in 30mL of ethanol-water mixed solution to obtain zirconium oxychloride alcohol aqueous solution, wherein the volume ratio of ethanol to water is 1:1, dissolving tetrabutyl titanate in 30mL of ethanol to obtain tetrabutyl titanate alcohol solution, adding the zirconium oxychloride alcohol aqueous solution into the tetrabutyl titanate alcohol solution, fully stirring, adding 10g of 1,2 epoxypropane, standing for gelation in a 50 ℃ water bath, adding ethanol after gelation, ageing in a 50 ℃ water bath for 24h, drying in a 120 ℃ drying oven, and roasting in an air atmosphere of 450- 2 -TiO 2 A carrier powder; dissolving active component precursor nitrate in water, wherein the active component precursor nitrate is copper nitrate and cerium nitrate, and adding the prepared ZrO 2 -TiO 2 CarrierStirring the powder for 12h, drying the powder in a drying oven at 120 ℃, and roasting the powder for 4h in an air atmosphere at 550 ℃ and 450- 2 /ZrO 2 -TiO 2 A composite oxide catalyst.
8. The method for preparing a composite oxide aerogel catalytic material as claimed in claim 7, wherein the oxide of the active component exists in the form of nanoparticles in the framework of the carrier.
9. The use of the composite oxide aerogel catalytic material of claim 8 in the preparation of industrial waste gas products for petrochemical, pharmaceutical and electronic industries.
CN202210343464.7A 2022-03-31 2022-03-31 Composite oxide aerogel catalytic material and preparation method and application thereof Pending CN114870849A (en)

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Application publication date: 20220809