CN106693987B - A kind of palladium gallium oxide bimetal nano catalyst of efficient catalytic methyl hydride combustion and preparation - Google Patents
A kind of palladium gallium oxide bimetal nano catalyst of efficient catalytic methyl hydride combustion and preparation Download PDFInfo
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- CN106693987B CN106693987B CN201611139648.2A CN201611139648A CN106693987B CN 106693987 B CN106693987 B CN 106693987B CN 201611139648 A CN201611139648 A CN 201611139648A CN 106693987 B CN106693987 B CN 106693987B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
A kind of palladium gallium oxide bimetal nano catalyst of efficient catalytic methyl hydride combustion and preparation, belong to technical field of function materials.PdGa bimetal nano particles are loaded into γ-Al2O3On carrier, then passes through calcination and form Pd-GaOx/Al2O3Catalyst.The load capacity of Metal Palladium is 1.0wt%.The preparation method comprises the following steps:, using the method for liquid phase coreduction, palladium acetylacetonate is restored simultaneously with gallium chloride in oleyl amine system, the PdGa bimetallic particle of size uniformity is formed, then metallic is loaded to by Al using infusion process2O3On carrier, Pd load capacity is 1.0wt%.Loaded catalyst is formed into Pd-GaO by 450 DEG C of calcinationsx/Al2O3Nanocatalyst.Pd-GaO prepared by the present inventionx/Al2O3Nanocatalyst preparation process is simple, and nanoparticle size is uniform, has a good application prospect in catalytic field.
Description
Technical field
The present invention relates to a kind of Pd-GaOx/Al2O3Nanocatalyst and preparation method thereof, and in particular to gone back altogether using liquid phase
Former method prepares PdGa alloy particle of uniform size, is loaded to Al using infusion process2O3Surface forms Pd- after subsequent calcination
GaOx/Al2O3Structure.There is the Pd-GaO of high catalytic activity to methane oxidationx/Al2O3Nanocatalyst belongs to functional material skill
Art field.
Background technique
With the continuous improvement of people's living standards, natural gas, because rich reserves, it is cheap, transport and it is easy to use,
The advantages that thermal efficiency is high, pollution is small, is widely used.But the main component of natural gas is that (content is about for most stable of hydro carbons-methane
It is 80%~90%), it is generally difficult to it activates, need to be burnt at a high temperature of 1500 DEG C or more using traditional combustion system.
But at these elevated temperatures, the O in air2And N2It is easy the NO that reaction generates serious pollution environmentx, while methane imperfect combustion
It will form atmosphere pollution CO.And methane itself is used as greenhouse gases, greenhouse effects will be much higher than CO2Isothermal chamber gas.Therefore
A kind of method for finding efficient cryogenic oxidation methane is just particularly important.And natural gas combustion can be greatly reduced in methane catalytic combustion
Temperature needed for burning, to be greatly reduced or even avoid NOxWith the formation of CO.And the exploitation of new catalyst is to realize this mistake
The key of journey.
Currently, domestic and international researcher has done a large amount of research to methyl hydride combustion catalyst, more achievement is achieved.Naturally
Gas catalyst for catalytic combustion is roughly divided into: (1) carried noble metal (Pt, Rh and Pd) catalyst；(2) transition metal (Ni, Co,
Mn, Cu and Fe etc.) oxide；(3) RE perovskite type O composite metallic oxide catalyst；(4) hexa-aluminate catalyzer etc..Its
Middle loaded noble metal catalyst is with its excellent CH4Catalytic combustion activity, low initiation temperature and preferable anti-toxicity energy
Paid much attention to.The basic research in the field has the history of decades, and obtains a large amount of significant research achievements.Mesh
Before, research of the loaded noble metal catalyst in terms of natural gas catalytic combustion is still natural gas catalytic combustion catalyst research
Emphasis.In precious metal element, for natural gas catalytic combustion again using Pd as most promising combustion of natural gas catalysis
Agent receives significant attention.Pd radicel duplex metal is because of strong interaction existing between two kinds of metals, modulation Metal Palladium that can be controllable
Geometry and electronic structure.
Existing document report, which is crossed, prepares bimetallic alloy using liquid phase co-reducing process.Such as: Liu Yuxi etc. use oleyl amine for
Solvent, using nickel acetylacetonate and acetylacetone,2,4-pentanedione gallium as source metal, using borine tert-butylamine as reducing agent, by metal precursor in oleyl amine
NiGa Nanoalloy (Yuxi Liu, Yadong Li, the et al.Advanced of size narrow ditribution has been made in coreduction in system
Materials,2016,23(28):4747-4754).Bastian J.M.Etzold etc. uses liquid phase co-reducing process, with metal
Acetylacetonate is presoma, and using benzyl alcohol as solvent, using aniline as reducing agent, the bimetal nano that size narrow ditribution is made is brilliant
Body.(M.Munoz et al.Applied Catalysis B:Environmental,2016,192,1–7).Existing document report
Road, Pd radicel duplex metal catalyst, which is compared, has certain rush for the absorption of methane and oxygen molecule and activation with pure palladium catalyst
Into effect, so that such material shows good catalytic activity in the catalytic oxidation of methane, such as: thank to the report such as few China
Road is 40000h when air speed-1When being lower than 480 DEG C with reaction temperature, methane is in 0.26wt%Co3.5Pd/3DOM CeO2On catalyst
Conversion ratio can achieve 90% (Shaohua Xie, et al.Journal of Catalysis, 2016,342:17-26).
As far as we know, there is presently no document reports to cross Pd-GaOx/Al2O3The preparation method of catalyst nano crystalline substance and its catalysis oxygen
Change the research on methane.
Summary of the invention
The object of the present invention is to provide a kind of Pd-GaO of efficient catalytic methane oxidationx/Al2O3Nanocatalyst and its system
Preparation Method, and in particular to it is nanocrystalline using liquid phase co-reducing process preparation PdGa, quotient is loaded to for PdGa is nanocrystalline using infusion process
Use Al2O3On carrier, then passes through calcination and form Pd-GaOx/Al2O3。
A kind of palladium gallium oxide bimetal nano catalyst of efficient catalytic methyl hydride combustion, which is characterized in that palladium gallium oxide is double
Metal nanoparticle is supported on γ-Al2O3Pd-GaO is denoted as on carrierx/Al2O3The molar ratio of nanocatalyst, palladium and gallium is 1:
4。
The preparation method of above-mentioned catalyst, which is characterized in that the PdGa bimetal nano crystalline substance of size uniformity uses infusion process
Load to carrier Al2O3On, calcination process is then passed through, the i.e. Pd-GaO of palladium gallium oxide bimetal nano catalyst is obtainedx/Al2O3
Nanocatalyst.Pd-GaOxLoad capacity can be loaded as needed, the load capacity of Metal Palladium is preferably 1.0wt%.
The preparation method of the PdGa bimetal nano crystalline substance of above-mentioned size uniformity, comprising the following steps:
It feeds intake according to the molar ratio of Metal Palladium and gallium for 1:4, weighs palladium acetylacetonate and GaCl3Butanol solution, be added
Into oleyl amine, 70 DEG C of stirring 30min, are denoted as solution A under protection of argon gas；It weighs borine tert-butylamine to be added in oleyl amine, stir
Dissolution, is denoted as solution B, the borine tert-butylamine of every 0.04mol corresponds to 2.5ml oleyl amine in solution B；By solution A in argon atmosphere
180 DEG C of holding 10min are warming up to, solution B is added dropwise in solution A at this time, mixed solution are then warming up to 250 DEG C, heat preservation
1h, then it is down to room temperature, it is centrifugated, the PdGa bimetal nano for obtaining size uniformity is brilliant.The nanoparticle that finally centrifugation is obtained
Son is distributed in hexamethylene and saves.
Wherein palladium acetylacetonate and GaCl3Butanol solution be palladium acetylacetonate and GaCl3It is molten using butanol as few as possible
It solves, the dosage relation of palladium acetylacetonate and oleyl amine is 0.05mmol:10ml in solution A；The dosage relation of solution A and solution B is
So that palladium acetylacetonate: the molar ratio of borine tert-butylamine is 5:4.
Obtained PdGa bimetal nano crystalline substance is loaded on carrier using infusion process, calcination process is then passed through, obtains
Pd-GaOx/Al2O3Nanocatalyst.Specific step is as follows:
The amount that the cyclohexane solution of PdGa bimetal nano crystalline substance must be contained required for calculating according to required load capacity, by γ-
Al2O3Carrier is added to the cyclohexane solution of bimetal nano crystalline substance, stirring dipping 8h, and centrifugation obtains loaded catalyst；It will obtain
Loaded catalyst be fitted into porcelain boat and be placed in Muffle furnace, rise to 450 DEG C from room temperature with the rate of 5 DEG C/min, and in the temperature
Lower holding 5h, cooling obtain Pd-GaOx/Al2O3Catalyst.
Gained palladium gallium oxide bimetal nano catalyst of the invention is used for methane oxidization catalyzing.
Methane concentration is 2%, methane/oxygen molar ratio is 1/8 and air speed is the reaction condition of 80000mL/ (gh)
Under, catalyst T50%(methane conversion reaches required reaction temperature when 50%) and T90%(methane conversion reaches 90% when institute
Need reaction temperature) it is respectively 363 DEG C and 397 DEG C.
The features such as the present invention has nano particle diameter uniform, and size is controllable, and preparation process is simple.
Pd-GaO prepared by the present inventionx/Al2O3Catalyst has the uniform and preferable crystallinity of bimetallic particle diameter
Feature, and be in highly dispersed state in carrier surface, it has a good application prospect in catalytic field.
Utilize D8ADVANCE type X-ray diffractometer (XRD), JEOL-2010 type transmission electron microscope (TEM) and Shimadzu
Crystal structure, particle morphology and the catalysis oxygen to methane of catalyst obtained by the Instrument measurings such as GC-2010 gas-chromatography (GC)
Change activity.The result shows that all having preferable crystallinity, Pd-GaO using each sample obtained by method of the inventionxNanometer
Particle is in highly dispersed state in carrier surface, and bimetal supported catalyst compares purer palladium chtalyst to the catalytic oxidation activity of methane
Agent significantly improves.
Detailed description of the invention
Fig. 1 is obtained Pd-GaOx/Al2O3And Pd/Al2O3The XRD spectra of sample, wherein curve (a) and (b) are respectively
Embodiment 1 and contrast sample Pd/Al2O3XRD spectra (Fig. 1 cannot with colour, be directly changed to black and white)；
Fig. 2 is obtained Pd-GaOx/Al2O3And Pd/Al2O3The TEM photo of sample, wherein figure (a), (b) and (c) with
It and (d) is respectively PdGa particle, embodiment 1 and Pd/Al2O3TEM photo；
Fig. 3 is obtained Pd-GaOx/Al2O3And Pd/Al2O3The activity curve of methane oxidization catalyzing on sample.
Specific embodiment
It is elaborated below with embodiment.In order to the present invention is explained further, it is described in conjunction with the accompanying the present invention and obtains pair
Methane oxidation has the Pd-GaO of excellent catalytic activityx/Al2O3Catalyst.
Embodiment 1
It feeds intake according to the molar ratio of Metal Palladium and gallium for 1:4: taking 0.05mmol palladium acetylacetonate and 0.2mmolGaCl3's
Butanol solution is added in 10ml oleyl amine, under protection of argon gas 70 DEG C of stirring 30min, is formed solution, is denoted as solution A.It weighs
The borine tert-butylamine of 0.04mol is added in 2.5ml oleyl amine, and stirring and dissolving is denoted as solution B.Solution A is risen in argon atmosphere
Solution B is slowly dropped into solution A by temperature at this time to 180 DEG C of holding 10min.Then mixed solution is warming up to 250 DEG C, protected
Warm 1h, then it is down to room temperature, it is centrifugated, washing, the PdGa bimetal nano for obtaining size uniformity is brilliant.Finally centrifugation is obtained
Nanoparticle is distributed in a certain amount of hexamethylene and saves.
Obtained PdGa bimetal nano crystalline substance is loaded on carrier using infusion process, calcination process is then passed through, obtains
Pd-GaOx/Al2O3Nanocatalyst.Specific step is as follows:
It is bis- containing PdGa required for being calculated according to load capacity (load capacity of the Metal Palladium of the present embodiment is 1.0wt%)
The amount of metal cyclohexane solution, by γ-Al2O3Carrier is added to the weighed cyclohexane solution containing bimetal nano crystalline substance.Stirring
8h is impregnated, centrifugation, drying obtain loaded catalyst.Obtained catalyst is fitted into porcelain boat to be placed in Muffle furnace, with 5 DEG C/min
Rate rise to 450 DEG C from room temperature, and keep 5h at such a temperature, cooling obtains Pd-GaOx/Al2O3Catalyst.
Methane concentration is 2%, methane/oxygen molar ratio is 1/8 and air speed is the reaction condition of 80000mL/ (gh)
Under, catalyst T50%(methane conversion reaches required reaction temperature when 50%) and T90%(methane conversion reaches 90% when institute
Need reaction temperature) it is respectively 363 DEG C and 397 DEG C.
Pd-GaO obtained by above-described embodimentx/Al2O3The XRD spectra of sample is shown in Fig. 1, and wherein curve (a) and (b) are respectively
Embodiment 1 and Pd/Al2O3XRD spectra；Obtained Pd-GaOx/Al2O3The TEM photo of sample is shown in Fig. 2, wherein figure (a),
It (b) is PdGa metallic, (c) and (d) distinguishes embodiment 1 and Pd/Al2O3TEM photo；Obtained Pd-GaOx/Al2O3Sample
Product and Pd/Al2O3Sample is shown in Fig. 3 to the catalytic activity curve of methane oxidation.
Claims (4)
1. a kind of preparation method of palladium gallium oxide bimetal nano catalyst, which is characterized in that palladium gallium oxide bimetal nano is urged
Agent are as follows: palladium gallium oxide bimetal nano particles are supported on γ-Al2O3Pd-GaO is denoted as on carrierx/Al2O3Nanocatalyst, palladium
Molar ratio with gallium is 1:4；The PdGa bimetal nano crystalline substance of size uniformity is loaded into carrier Al using infusion process2O3On, then
By calcination process, the i.e. Pd-GaO of palladium gallium oxide bimetal nano catalyst is obtainedx/Al2O3Nanocatalyst, specific steps are such as
Under: the amount of the cyclohexane solution of PdGa bimetal nano crystalline substance must be contained required for calculating according to required load capacity, by γ-Al2O3It carries
Body is added to the cyclohexane solution of bimetal nano crystalline substance, stirring dipping 8h, and centrifugation obtains loaded catalyst；The load that will be obtained
Type catalyst is fitted into porcelain boat and is placed in Muffle furnace, rises to 450 DEG C from room temperature with the rate of 5 DEG C/min, and keep at such a temperature
5h, cooling obtain Pd-GaOx/Al2O3Catalyst.
2. according to the method for claim 1, which is characterized in that the preparation side of the PdGa bimetal nano crystalline substance of size uniformity
Method, comprising the following steps: feed intake according to the molar ratio of Metal Palladium and gallium for 1:4, weigh palladium acetylacetonate and GaCl3Butanol it is molten
Liquid is added in oleyl amine, and 70 DEG C of stirring 30min, are denoted as solution A under protection of argon gas；It weighs borine tert-butylamine and is added to oleyl amine
In, stirring and dissolving is denoted as solution B, and the borine tert-butylamine of every 0.04mol corresponds to 2.5ml oleyl amine in solution B；By solution A in argon gas
It is warming up to 180 DEG C of holding 10min in atmosphere, solution B is added dropwise in solution A at this time, mixed solution is then warming up to 250
DEG C, 1h is kept the temperature, then be down to room temperature, be centrifugated, the PdGa bimetal nano for obtaining size uniformity is brilliant；Finally centrifugation is obtained
Nanoparticle is distributed in hexamethylene and saves；Wherein palladium acetylacetonate and GaCl3Butanol solution be palladium acetylacetonate and GaCl3
It is dissolved using butanol as few as possible, the dosage relation of palladium acetylacetonate and oleyl amine is 0.05mmol:10ml in solution A；Solution A
Dosage relation with solution B is so that palladium acetylacetonate: the molar ratio of borine tert-butylamine is 5:4.
3. according to the method for claim 1, which is characterized in that the load capacity of Metal Palladium is 1.0wt%.
4. the palladium gallium oxide bimetal nano catalyst that method according to claim 1-3 is prepared.
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| CN107626307B (en) * | 2017-09-29 | 2021-03-26 | 北京工业大学 | Method for regulating and controlling oxidation activity of Pt-based catalyst by doping ZnO |
| CN108097247A (en) * | 2017-11-22 | 2018-06-01 | 南通斐腾新材料科技有限公司 | A kind of preparation method of high temperature resistant platinum bimetallic catalyst |
| GB201811892D0 (en) * | 2018-07-20 | 2018-09-05 | Johnson Matthey Plc | Nanoparticles and preparation method |
| CN110639548B (en) * | 2019-09-19 | 2022-06-14 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN110639549A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Universal method for preparing high-stability noble metal monatomic catalyst |
| CN110976903B (en) * | 2019-11-11 | 2021-08-17 | 中国科学院金属研究所 | Bimetal nano-particles with controllable components and sizes and uniform appearance and preparation method thereof |
| CN112108147A (en) * | 2020-09-13 | 2020-12-22 | 北京工业大学 | Platinum-manganese-based bimetallic catalyst for catalyzing ethylene oxide at low temperature |
| CN113198490A (en) * | 2021-05-26 | 2021-08-03 | 华东理工大学 | Palladium-cobalt-loaded alloy catalyst for low-temperature combustion of methane and preparation method thereof |
| CN115212878A (en) * | 2022-07-06 | 2022-10-21 | 四川大学 | Method for preparing high-performance Pd-Ga2O3 catalyst by recycling waste palladium catalyst |
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| CN103157469A (en) * | 2013-04-11 | 2013-06-19 | 北京化工大学 | Supported bimetal nanocrystal catalyst and preparation method thereof |
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