CN107570171B - Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof - Google Patents
Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof Download PDFInfo
- Publication number
- CN107570171B CN107570171B CN201710612634.6A CN201710612634A CN107570171B CN 107570171 B CN107570171 B CN 107570171B CN 201710612634 A CN201710612634 A CN 201710612634A CN 107570171 B CN107570171 B CN 107570171B
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- cobaltosic oxide
- stirring
- high speed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a cobaltosic oxide supported nano gold catalyst, a preparation method and application thereof, wherein a cyclohexane solution of oleylamine is dripped into Co (NO)3)2Obtaining a solution A from the aqueous solution; adding cetyl trimethyl ammonium bromide and n-butyl alcohol into water, adding a chloroauric acid solution to form a solution B, and dropwise adding the solution A into the solution B to obtain a dispersion liquid; reacting NaBH4And dropwise adding the aqueous solution into the dispersion liquid, and simultaneously introducing high-purity oxygen to wash, dry and roast the obtained precipitate to obtain the required catalyst. The invention utilizes the method of complexation-oxidation to synthesize the novel cobaltosic oxide supported nano gold catalyst in one step, realizes the uniform dispersion of gold nano particles, greatly reduces the cost of the catalyst on the basis of ensuring the activity, and has wider market application prospect.
Description
Technical Field
The invention relates to a cobaltosic oxide supported nano gold catalyst, a preparation method and application thereof, in particular to a preparation method and application of a supported gold catalyst for catalytic elimination of volatile organic compounds.
Background
With the higher control requirement of the national environmental protection laws and regulations on the discharge of the VOCs atmospheric pollutants, in recent years, great attention is paid to the treatment of waste gas containing volatile organic compounds. Various technologies have been developed for the exhaust emission of VOCs, including thermal destruction, adsorption, and catalytic oxidation. Thermal destruction requires high operating temperatures and high equipment investment, energy consumption and costs, and therefore may not be the most effective. In some cases, the removal of VOCs from exhaust emissions by adsorption with an adsorbent such as activated carbon is an alternative method. However, this method does not destroy the contaminants but merely enriches them, easily causing secondary pollution. In addition, the adsorption efficiency can be affected by the type and concentration of volatile organic compounds in the exhaust emissions. Catalytic oxidation is an efficient and economical way to destroy volatile organic compounds in exhaust emissions. The d electron orbit of the noble metal is not filled, reactants are easily adsorbed on the surface, an intermediate active compound is favorably formed, and the catalyst has high catalytic activity, comprehensive excellent characteristics of oxidation resistance, corrosion resistance and the like and good application effect. Transition metal oxides are often used as catalysts for catalytic combustion due to their low cost and relatively stable structure.
In microemulsion systems, the dispersed phases are present in sizes smaller than 100 nm, separated from each other to form microreactors. The nano particle catalyst prepared by the microemulsion method has the advantages of small particle size, large specific surface area, narrow distribution, easy control, high catalytic activity, good selectivity, good thermal stability and the like. Although the cobaltosic oxide has good catalytic activity as a catalytic combustion catalyst for hydrocarbon pollutants, the cobaltosic oxide still has the problem of poor thermal stability in the use process. It is easily sintered at high temperature and even converted into inert CoO, thus greatly reducing its catalytic activity. Patent (CN 105817229 a) reports that the anti-sintering performance of cobaltosic oxide can be improved by using a cerium-zirconium solid solution to support cobalt oxide, however, when the catalyst is baked at 500 ℃, the conversion rates of the cobalt oxide can reach 10%, 50% and 90% at 210 ℃, 266 ℃ and 350 ℃, respectively, and the conversion rates of the cobaltosic oxide-supported nano-gold catalyst can reach 10%, 50% and 90% at 200 ℃, 220 ℃ and 260 ℃, respectively, so that the performance of the catalyst can be further improved, which indicates that the method plays a certain role in the high-temperature stability of cobaltosic oxide, and has a very important significance in developing and applying the catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to: provides a preparation method of cobaltosic oxide supported nano gold catalyst.
The invention further aims to provide a cobaltosic oxide-supported nanogold catalyst product obtained by the preparation method.
Yet another object of the present invention is to: provides the application of the cobaltosic oxide supported nano gold catalyst.
The purpose of the invention is realized by the following scheme: a preparation method of cobaltosic oxide supported nano gold catalyst comprises the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form a uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And dropwise adding the aqueous solution into the dispersion liquid, simultaneously introducing 20ml/min of high-purity oxygen to ensure an oxygen-enriched environment, wherein the reaction temperature is 40 ℃, washing the obtained precipitate, drying in a drying oven at 100 ℃ for 12h, and placing in a muffle furnace, wherein the roasting temperature is 300-500 ℃, and the roasting time is 2h, so as to obtain the required catalyst.
The invention utilizes a complexing-oxidizing method to synthesize a novel cobaltosic oxide supported nano gold catalyst in one step, realizes the uniform dispersion of gold nanoparticles, supports noble metal nanoparticles by a transition metal oxide, improves the atom utilization rate of noble metal and effectively reduces the dosage of the noble metal through the interaction of the noble metal and a carrier, and improves the high-temperature stability of the catalyst. The method greatly reduces the cost of the catalyst on the basis of ensuring the activity, so that the method has wider market application prospect.
The invention provides a cobaltosic oxide supported nano gold catalyst obtained by the preparation method. The Au/CoOx supported catalyst effectively reduces the ignition temperature of propane combustion, propane can be completely combusted at 270 ℃, and the working temperature of the Au/CoOx supported catalyst is suitable for heat accumulating type catalytic combustion equipment.
The invention also provides application of the cobaltosic oxide supported nano gold catalyst in catalytic elimination of volatile organic compounds.
The invention has the advantages that: the novel cobaltosic oxide supported nano-gold catalyst is synthesized in one step by using a microemulsion method, the uniform dispersion of gold nanoparticles is realized, and the catalyst has the characteristics of good activity and high-temperature stability and simple preparation method. The cobaltosic oxide supported nano gold catalyst product obtained by the method effectively reduces the ignition temperature of propane combustion, and is suitable for heat accumulating type catalytic combustion equipment.
Drawings
FIG. 1 is a high resolution scanning electron micrograph of the Au/CoOx supported catalyst of example 1.
Detailed Description
The following examples are given to illustrate the invention in more detail with reference to the accompanying drawings, but the invention is not limited thereto. All catalyst activity evaluations for the catalytic combustion of propane were carried out in a fixed-bed microreactor (8 mm internal diameter quartz, 250mm long), with a catalyst dosage of 100mg and a temperature automatically controlled using a K-type thermocouple. The standard steel cylinder gas is mixed with air through a gas distribution system and enters a reactor for combustion. The flow rate was controlled by a mass flow meter, the concentration of propane was 0.1vol%, and the amount of exhaust gas treated per gram of catalyst per hour was 30L. The main reaction products are carbon dioxide and water.
Example 1
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 300 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-300. A high resolution scanning electron micrograph of the Au/CoOx supported catalyst is shown in FIG. 1.
T in Table 1 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
example 2
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 400 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-400.
T in Table 2 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
example 3
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 500 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-500.
T in Table 3 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
the calcination temperature is increased, and the reaction temperature required for the conversion to 10%, 50% or 90% is also increased.
Claims (3)
1. A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) dissolving 100ml oleylamine in cyclohexane300ml of 0.1mol/L Co (NO) is dropwise added3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And dropwise adding the aqueous solution into the dispersion liquid, introducing pure oxygen of 20ml/min to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a drying oven at 100 ℃ for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at the temperature of 300 ℃ and 500 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst.
2. A tricobalt tetraoxide-supported nanogold catalyst obtained by the production method according to claim 1.
3. The use of the cobaltosic oxide-supported nanogold catalyst according to claim 2 for catalytic elimination of volatile organic compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710612634.6A CN107570171B (en) | 2017-07-25 | 2017-07-25 | Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710612634.6A CN107570171B (en) | 2017-07-25 | 2017-07-25 | Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107570171A CN107570171A (en) | 2018-01-12 |
| CN107570171B true CN107570171B (en) | 2020-04-28 |
Family
ID=61033681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710612634.6A Active CN107570171B (en) | 2017-07-25 | 2017-07-25 | Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107570171B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990461A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Propane full-catalytic oxidation agent of cobaltosic oxide as well as preparation method and application of oxidation agent |
| CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
| CN106552630A (en) * | 2016-10-26 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of spherical CoOXBase catalyst and preparation method and application |
-
2017
- 2017-07-25 CN CN201710612634.6A patent/CN107570171B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990461A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Propane full-catalytic oxidation agent of cobaltosic oxide as well as preparation method and application of oxidation agent |
| CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
| CN106552630A (en) * | 2016-10-26 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of spherical CoOXBase catalyst and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Fe/Au核壳复合纳米粒子的制备及表征;端木云 等;《东南大学学报（自然科学版）》;20040531;第34卷(第3期);前言部分、第1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107570171A (en) | 2018-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109201048B (en) | Monoatomic catalyst and its preparing process | |
| CN102824909B (en) | Catalyst for low-temperature catalytic combustion of volatile organic compounds and preparation method thereof | |
| CN107442106A (en) | The preparation method of VOCs catalytic decomposition O composite metallic oxide catalysts | |
| CN108671917A (en) | A kind of catalyst and preparation method thereof of efficient cryogenic catalysis VOCs exhaust gas decompositions | |
| CN107159202B (en) | Manganese-doped palladium supported catalyst and preparation method and application thereof | |
| CN108246312A (en) | Catalyst and preparation method with low temperature active purification of volatile organic pollutant | |
| CN105833901B (en) | A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN107855123B (en) | Pd/SiO2@Al2O3Nanocrystalline material and preparation method and application thereof | |
| CN102101051B (en) | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides | |
| WO2022089668A1 (en) | Platinum-loaded flower-like iron-cerium composite material and preparation method therefor and application thereof in low-temperature thermal catalytic treatment of toluene | |
| CN115672319A (en) | Preparation method of catalyst for reducing catalytic combustion temperature of volatile organic compounds | |
| WO2024146222A1 (en) | Method for preparing highly-dispersed pt/ceo2 by using atomically dispersed platinum as precursor and use | |
| CN109745995B (en) | Wide-temperature-window SCR flue gas denitration catalyst and preparation method and application thereof | |
| CN114160104A (en) | Kiln flue gas CO2Trapping and utilizing coupling material and application thereof | |
| CN111111656A (en) | High-temperature-resistant catalytic combustion catalyst for normal-temperature catalytic ignition of VOCs self-sustaining combustion and preparation method and application thereof | |
| CN113663671A (en) | Ternary metal catalyst and preparation method and application thereof | |
| CN107570171B (en) | Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof | |
| CN106984318B (en) | Bimetal cobalt-based catalyst, preparation method and application | |
| CN113210010A (en) | VOC catalyst coated in different areas and preparation method thereof | |
| CN106552630A (en) | A kind of spherical CoOXBase catalyst and preparation method and application | |
| CN110433800B (en) | Preparation and application of supported ruthenium catalyst with crystal face effect | |
| CN113731445B (en) | Photocatalyst taking barium stannate as carrier to load cadmium sulfide quantum dots, and preparation method and application thereof | |
| CN108176349B (en) | Al (aluminum)2O3@TiO2Preparation method of core-shell structure simultaneous desulfurization and denitrification adsorbent | |
| CN114832848B (en) | Catalyst and preparation method and application thereof | |
| CN108448123B (en) | Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |