CN108906039A - A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene - Google Patents
A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene Download PDFInfo
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Abstract
A kind of low-load amount gold of the present invention and golden platinum catalyst with core-casing structure preparation method and its application in catalysis oxidation toluene.Two kinds of intermetallic synergistic effects of golden platinum are utilized in catalyst preparation of the invention, and organic solvent is used to make nano metal particles fine dispersion as surfactant.The catalyst Au@Pt/Al2O3With noble metal Au for the first active component, with Pt for the second active component, the Al high with specific surface, thermal stability is good2O3For carrier, the load capacity 0.12wt% of total metal.The simple synthetic method of the catalyst, cost is relatively low, and operating condition is mild, embodies the objective of Green Chemistry.Compared with other noble metal catalysts in the prior art, Catalyst Design coreshell type structure, experiments have shown that having apparent advantage, 1000ppm toluene can be completely oxidized to carbon dioxide and water at 210 DEG C, and it is generated without other products, show good low-temperature catalytic activity, practical value with higher.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of low-load amount Au catalyst, especially Au/Al2O3With
Au@Pt/Al2O3Type nucleocapsid catalyst and preparation method thereof and its application in catalysis oxidation toluene.
Background technique
Volatile organic matter (volatile organic compounds) VOCs refers to that saturated vapor pressure is greater than under room temperature
Boiling point is in 50-260 DEG C of organic compounds below under 133.32Pa, normal pressure, or it is any at normal temperatures and pressures can volatilization it is organic
Solid or liquid.VOCs is mainly derived from industrial production and social life, for example comes from petrochemical industry, vehicle exhaust, paint
Coating, textile manufacturing, medical pesticide, fuel combustion etc..It is containing toluene in these emissions, therefore toluene becomes interior
One of with the main goods and materials of outdoor pollution.Know that toluene has very big harm to health by report, short term contact toluene can be to skin
The irritating effect of mucous membrane, Central nervous have paralysis effect；Neurasthenia can be made one by being under toluene environment for a long time.Therefore,
Seek one kind effectively and the toluene in the method for strong operability elimination air is of great significance.
Currently, having following method for the processing of VOCs：Absorption process, absorption method, condensation method, membrane separation process, photocatalytic-oxidation
Change method, biological degradation method, impulse electric corona method, catalytic oxidation etc..VOCS higher for some concentration and that component is single is suitable
Condensation is preferably used, the methods of liquid absorption and activated carbon adsorption recycle organic compound effectively.However for
For most of industry actual discharge VOC, concentration is often lower, and composition is also complex, recycles value less, therefore adopt
It is more feasible method with destruction technology, is compared to biological degradation method, photocatalysis and thermal incineration technology, catalytic combustion technology
Highly efficient energy saving and environmental-friendly, it is that organic compounds is made to carry out nonflame combustion under lower initiation temperature by catalyst
Burn, resolve into carbon dioxide and vapor, and release amount of heat realize reaction from heat supply.Catalytic oxidation, which has, is applicable in model
Enclose wide, eliminate high-efficient, energy saving, and it is without secondary pollution the advantages that, be acknowledged as eliminating the best means of VOCs.
At present there are mainly three types of catalysis oxidation VOCs：First is that noble metal catalyst, is with noble metals such as Au, Pt, Pd, Ru
It represents；Second is that catalyst of transition metal oxide, common are V2O5、MnOx、Co3O4、CeO、CuO、Fe2O3Deng：Third is that compound
Oxide catalyst, mainly perovskite composite oxide and spinelle composite oxides.Composite oxide catalysts it
Between since it is there are the interaction of structure and electronics modulation, catalytic activity is higher than corresponding single oxide, but can
It can some slightly below noble metals.Three kinds of catalyst respectively have advantage and disadvantage, and noble metal catalyst catalytic activity is high, thermal stability is strong, anti-
Answer that temperature is low, good selective, but since its resource is not that very abundant, price is more expensive, while in processing sulfur-bearing
Catalyst poisoning can be made to inactivate with the VOcs containing chlorine.Substitute of the catalyst of transition metal oxide as noble metal catalyst,
Although relative low price, resource is relatively abundant, it is compared to catalytic activity of noble metal or poor.
Au base catalyst once past following period of time have always been considered as be catalytically inactive noble metal, it is not excessive
It is studied by people.But discovery recent years Au also has greatly activity, also gradually attracts attention.The expensive gold of support type
Metal catalyst has many advantages, such as that catalytic activity is high, initiation temperature is low, thermal stability is good, universality is strong, leads in catalysis oxidation VOCs
Domain has obtained extensive research, but due to the scarcity of resources of noble metal, price is more expensive, so consider from the direction for reducing cost,
The load capacity for reducing noble metal is an optional method.Though single-metal reforming catalyst has its preferable catalytic performance, according to report
Road bimetallic (nucleocapsid, alloy) catalyst can more improve its reactivity, can generate a kind of synergistic effect between two kinds of metals, because
This bimetallic catalyst gradually causes the attention of vast researcher again.
Patent：CN1827213A has invented a kind of load nano-Au catalyst and preparation method thereof, and load type nano gold is urged
Agent is made of Au, Al and Ti or Si and Ag, Cu, Ce, Fe or Zn, wherein main active component of the Au as catalyst, Al are used
Make the carrier of catalyst, Ti or Si are used as the auxiliary agent of catalyst carrier, Ag, Cu, the auxiliary activity of Ce, Fe or Zn as catalyst
Component.Advantages of the present invention:Gold is uniformly dispersed, and the granularity of gained gold component particles is easy to adjust；The stabilization of catalyst
Property it is high；It is particularly suitable for the oxidation that using co-precipitation or deposition-precipitation method is difficult to gold-supported of those isoelectric pH values less than 6
Object carrier.Catalyst provided by the invention for hexamethylene can in the case where reaction condition is mild oxidation prepare cyclohexanone and
Cyclohexanol, and activity and selectivity is good, catalyst amount is small, is easy to be recycled.
Patent：CN104353459A invention be related to the load type bimetal catalyst of catalysis oxidation a kind of, preparation method and
It is applied.The catalyst with titanium dioxide admire for carrier, the first active component be titanium dioxide follow closely, the second active component be manganese oxide,
Any one in oxidation brill, copper oxide or oxidation decorations can promote pair there are concerted catalysis effect between two kinds of active components
The catalysis oxidation efficiency.Compared with commercial support type is platinum catalyst, cost is relatively low for catalyst of the invention, and universality is strong, right
For a variety of complete oxidation temperature all between 170 DEG C -250 DEG C, overall performance is better than commercialization platinum catalyst, and reacts and produce eventually
The selectivity of object is very high, before having preferable application.
Summary of the invention
To solve the above problems, the present invention provides a kind of low-load amount Au catalyst and preparation method thereof and its be catalyzed
Aoxidize the application in toluene.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of low-load amount Au catalyst provided by the invention, it is characterised in that the catalyst is with noble metal Au for first
Active constituent, with Pt for the second active component, with Al2O3For carrier, on the basis of the quality of carrier, the first, second active component
Load capacity be respectively 0.02%-0.12 (preferably 0.04%), 0-0.12% (preferably 0.08%).
The low-load amount Au catalyst is Au/Al2O3Catalyst (when the second activity component load quantity is 0) or double gold
Belong to nucleocapsid Au@Pt/Al2O3(when the second activity component load quantity is greater than 0).
Further, the present invention also provides the preparation methods of the low-load amount Au catalyst is：
When the second active component Pt load capacity is equal to 0%, the preparation method is that：(1) by HAuCl4·4H2O addition has
In solvent, at Hydrogen Vapor Pressure 1-4MPa, at 20-60 DEG C of reduction temperature, stirring carries out reduction reaction, and obtained Au nanometers molten
Liquid；(2) by carrier Al2O3Incipient impregnation is in gained Au nano-solution, stirring and adsorbing standing and drying, in 400-500 DEG C of condition
Au/Al is made in lower calcining 4-5h2O3Catalyst.
When the second active component Pt load capacity is greater than 0%, the preparation method is：(a) by HAuCl4·4H2O is added
In organic solvent, at Hydrogen Vapor Pressure 1-4MPa, at 20-60 DEG C of reduction temperature, stirring carries out reduction reaction, and obtained Au nanometers molten
Liquid；(b) by H2PtCl4·6H2O is added in Au nano-solution obtained by step (1), Hydrogen Vapor Pressure 1-4MPa, reduction temperature 20-60
At DEG C, stirring carries out reduction reaction, obtains bimetal nano particles solution；(c) by carrier Al2O3Incipient impregnation is in step (b)
In resulting bimetal nano particles solution, stirring and adsorbing, standing and drying calcines 4-5h under the conditions of 400-500 DEG C, is made double
Metal nucleocapsid Au Pt/Al2O3Catalyst.
Further, in step (1) or step (a), the HAuCl4·4H2O is in terms of the first active component A u in organic solvent
In mass concentration be generally 0.5-2.5mg/mL, particularly preferably 1.0mg/mL.
Further, in step (b), the H2PtCl4·6H2O is in terms of the second active component Pt in the quality of Au nano-solution
Concentration is generally 0.5-2.5mg/mL, particularly preferred 2.0mg/mL.
Further, organic solvent described in step (1) or step (a) is propene carbonate, ethyl alcohol etc..
In the present invention, when the second active component Pt load capacity is equal to 0%, in Au nano-solution the quality of active component A u with
Carrier Al2O3Relationship between quality is determined by required Au load capacity.
Likewise, when the second active component Pt load capacity is greater than 0%, active component Pt in bimetal nano particles solution
Quality, the quality of Au and carrier Al2O3Between relationship determined by required Pt load capacity, Au load capacity.
Further, Hydrogen Vapor Pressure is 1-4MPa, particularly preferably 4MPa in step (1) or step (a).
Further, the time of reduction reaction described in step (1) or step (a) is generally 0.5-5h, particularly preferably 2h.
Further, reduction temperature is 20-60 DEG C, particularly preferably 40 DEG C in step (1) or step (a).
Further, when the second active component Pt load capacity is greater than 0%, Hydrogen Vapor Pressure is generally 1-4MPa in step (b),
Particularly preferably 4MPa.
Further, when the second active component Pt load capacity is greater than 0%, the time one of reduction reaction described in step (b)
As be 0.5-5h, particularly preferably 3h.
Further, when the second active component Pt load capacity is greater than 0%, step (b) reduction temperature is 20-60 DEG C, especially
Preferably 40 DEG C.
In preparation method of the present invention, the preparation of Au nano-solution is not required to that stabilizer is added, only in organic solvent
Au nano-solution can directly be prepared.In obtained Au nano-solution, the size of Au nanoparticle is in 5-30nm or so.
The present invention also provides application of the low-load amount Au catalyst in toluene catalytic oxidation reaction.
By the gas chromatograph equipped with fid detector come the reactant and production of on-line checking and quantitative analysis toluene oxidation
Object, the results showed that, there is the performance of efficiently catalyzing and oxidizing toluene, monometallic using the catalyst of the method for the invention synthesis
Au/Al2O3It can be 0.04% at 260 DEG C, toluene concentration 1000ppm, reaction velocity 18000mLg in Au load capacity-1·
h-1Under the conditions of, it can be by toluene complete oxidation.Bimetallic nucleocapsid Au@Pt/Al2O3It is 0.04%, Pt load capacity in Au load capacity
It is 0.08%, 210 DEG C, toluene concentration 1000ppm, reaction velocity 18000mLg-1·h-1Under the conditions of, it can be by toluene
Complete oxidation.The preparation method is easy, and extensively and recoverable, bimetal Au/Pt core-shell structure is than monometallic Au for raw material sources
Catalytic activity is high, has more obvious advantage.
Compared with prior art, the beneficial effects of the present invention are：Low-load amount Au catalyst preparation provided by the invention
The high supported nano-Au catalyst of the available dispersion degree of method, the catalyst is in the lower situation of noble-metal-supported amount
It is still able to maintain greater activity and stability, and organic solvent is reusable, exhaust gas waste water, preparation method letter will not be generated
Single, carrier is cheap and easy to get, and the cost of catalyst is greatly reduced, convenient for industrialization.
Detailed description of the invention
Fig. 1：Embodiment 15 prepares Au/Al2O3The TEM figure of catalyst (noble metal Au load capacity is 0.04%)；
Fig. 2：Au@PtAl prepared by embodiment 182O3Au/Al prepared by catalyst and example 22O3Catalytic performance figure.
Specific embodiment
Below by specific embodiment, invention is further explained, but protection scope of the present invention is not limited in
This.
Embodiment 1
By 0.104g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 0.5mg/mL, by 1g Al2O3Carrier is added to the Au of isometric (about 0.4ml)
In nano-particle solution, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, repeat above-mentioned
Absorption calcining is primary, obtains the Au/Al that load capacity is 0.04%2O3Catalyst.
Embodiment 2
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 3
By 0.312g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.5mg/mL, a small amount of above-mentioned Au nano-particle solution is taken to be diluted to 1.0mg/mL
Au nano-particle solution, by 1g Al2O3Carrier is added in isometric Au nano-solution, and dipping absorption is primary, stands 20
It is dry after minute, 4h then is calcined under the conditions of 400 DEG C, obtains the Au/Al that load capacity is 0.04%2O3Catalyst.
Embodiment 4
By 0.416g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 2.0mg/mL, a small amount of above-mentioned Au nano-particle solution is taken to be diluted to 1.0mg/mL
Au nano-particle solution, by 1g Al2O3Carrier is added in isometric Au nano-solution, and dipping absorption is primary, stands 20
It is dry after minute, 4h then is calcined under the conditions of 400 DEG C, obtains the Au/Al that load capacity is 0.04%2O3Catalyst.
Embodiment 5
By 0.520g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 2.5mg/mL, a small amount of above-mentioned Au nano-particle solution is taken to be diluted to 1.0mg/mL
Au nano-particle solution, by 1g Al2O3Carrier is added in isometric Au nano-solution, and dipping absorption is primary, stands 20
It is dry after minute, 4h then is calcined under the conditions of 400 DEG C, obtains the Au/Al that load capacity is 0.04%2O3Catalyst.
According to Au/Al made from the preparation method of embodiment 1-52O3It is real to carry out catalysis oxidation to toluene respectively for catalyst
It tests, catalytic performance result such as the following table 1 (wherein T50Indicate temperature of the toluene conversion at 50%, T98Indicate toluene in conversion ratio
Temperature when being 98%, similarly hereinafter)：
Table 1
From upper table 1 as can be seen that in H2Under the conditions of pressure is 4MPa, reaction temperature is 40 DEG C, the recovery time is 3h, Au
When the concentration of nano-solution is 1mg/mL, Au/Al2O3Catalytic effect it is best.
After the concentration for determining Au nano-solution, continue the influence for probing into pressure to nanoparticle.
Embodiment 6
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 3MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 7
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 2MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 8
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 1MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Au/Al is made according to embodiment 2 and embodiment 6-8 preparation method2O3Catalyst carries out catalysis oxygen to toluene respectively
Change experiment, catalytic performance result such as the following table 2：
Table 2
| Embodiment | T50 | T98 |
| 2 | 195 | 260 |
| 6 | 195 | 270 |
| 7 | 200 | 280 |
| 8 | 203 | 285 |
From upper table 2 as can be seen that the concentration of Au nano-solution is 1mg/mL, reaction temperature is 40 DEG C, recovery time
Under the conditions of 3h, H2When pressure is 4MPa, Au/Al2O3Catalytic effect it is best.
Determine concentration, the H of nano-solution2After pressure, continue the influence for probing into temperature to nanoparticle.
Embodiment 9
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 20 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 10
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 30 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 11
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 50 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 12
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 60 DEG C,
It is stirred to react 3h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Au/Al is made according to embodiment 2 and embodiment 9-12 preparation method2O3Catalyst carries out catalysis oxygen to toluene respectively
Change experiment, catalytic performance result such as the following table 3：
Table 3
| Embodiment | T50 | T98 |
| 2 | 195 | 260 |
| 9 | 200 | 290 |
| 10 | 198 | 290 |
| 11 | 200 | 280 |
| 12 | 200 | 285 |
As can be seen that the concentration in Au nano-solution is 1mg/mL, H from upper table 42Pressure is 4MPa, the recovery time is
Under the conditions of 3h, when reaction temperature is 40 DEG C, Au/Al2O3Catalytic effect it is best.
Determine concentration, the H of nano-solution2After pressure and reaction temperature, continue the exploratory response time to the shadow of nanoparticle
It rings.
Embodiment 13
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 0.5h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3It is molten that carrier is added to isometric Au nanoparticle
In liquid, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, and obtaining load capacity is 0.04%
Au/Al2O3Catalyst.
Embodiment 14
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 1h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 15
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 2h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 16
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 4h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Embodiment 17
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 5h, obtains the Au nano-solution of 1.0mg/mL, by 1g Al2O3Carrier is added to isometric Au nano-particle solution
In, dipping absorption, standing is dried after twenty minutes, then calcines 4h under the conditions of 400 DEG C, obtains the Au/ that load capacity is 0.04%
Al2O3Catalyst.
Au/Al is made according to embodiment 2 and embodiment 13-17 preparation method2O3Catalyst is respectively catalyzed toluene
Oxidation experiment, catalytic performance result such as the following table 4：
Table 4
| Embodiment | T50 | T98 |
| 2 | 195 | 260 |
| 13 | 200 | 295 |
| 14 | 197 | 290 |
| 15 | 195 | 260 |
| 16 | 195 | 295 |
| 17 | 200 | 300 |
As can be seen that the concentration in Au nano-solution is 1mg/mL, H from upper table 42Pressure is 4MPa, reaction temperature is
Under the conditions of 40 DEG C, when the recovery time is 2h, Au/Al2O3Catalytic effect it is best.
Determine one-component Au/Al2O3Optimum preparating condition after, continue to prepare bimetal Au@Pt/Al2O3Type nucleocapsid.
Embodiment 18
By 0.208g HAuCl4·4H2O is added in 100mL propene carbonate, in 4MPa H2Environment, under the conditions of 40 DEG C,
It is stirred to react 2h, obtains the Au nano-solution of 1.0mg/mL.0.530gH is added in the above solution2PtCl4·6H2O, in 4MPa
H2Environment under the conditions of 40 DEG C, is stirred to react 3h, obtains bimetal Au@Pt/Al2O3Type nuclear shell type nano meter particle solution.By 1g
Al2O3Carrier is added in isometric Au@Pt nano-particle solution, and dipping absorption, standing is dried after twenty minutes, then 400
4h is calcined under the conditions of DEG C, obtains Au@Pt/Al2O3Catalyst.
Au/Al is made according to embodiment 15 and 18 preparation method of embodiment2O3With Au@Pt/Al2O3Catalyst, respectively to first
Benzene carries out catalytic, catalytic performance result such as the following table 5：
Table 5
After it can be seen that addition precious metals pt in upper table 5, the supported Au catalysts relative to one pack system have ignition
The clear superiority that temperature is low, catalytic activity is high.
Result above is compared, we have invented the Au@Pt/Al that a kind of total content of metal is 0.12wt%2O3Type nucleocapsid knot
Structure catalyst.The catalyst is in experiment condition：Toluene concentration is 1000ppm, reaction velocity 18000mLg-1·h-1When, it can
To realize the complete oxidation to toluene at 210 DEG C.At low cost, active high and simple process, has and realizes industrialized prospect.
Claims (9)
1. a kind of low-load amount Au catalyst, it is characterised in that the catalyst with noble metal Au be the first active constituent, with Pt
For the second active component, with Al2O3For carrier, on the basis of the quality of carrier, the load capacity of the first, second active component is distinguished
For 0.02%-0.12,0-0.12%, when the second activity component load quantity is 0, the low-load amount Au catalyst is Au/
Al2O3Catalyst, when the second activity component load quantity is greater than 0, the low-load amount Au catalyst is bimetallic nucleocapsid Au@Pt/
Al2O3。
2. the preparation method of low-load amount Au catalyst as described in claim 1, it is characterised in that：
When the second active component Pt load capacity is equal to 0%, the preparation method is that：
(1) by HAuCl4·4H2O is added in organic solvent, at Hydrogen Vapor Pressure 1-4MPa, at 20-60 DEG C of reduction temperature, and stirring
Reduction reaction is carried out, Au nano-solution is made；
(2) by carrier Al2O3Incipient impregnation is in gained Au nano-solution, stirring and adsorbing standing and drying, in 400-500 DEG C of item
4-5h is calcined under part, Au/Al is made2O3Catalyst.
3. preparation method as described in claim 1, it is characterised in that：When the second active component Pt load capacity is greater than 0%, institute
Stating preparation method is：
(a) by HAuCl4·4H2O is added in organic solvent, at Hydrogen Vapor Pressure 1-4MPa, at 20-60 DEG C of reduction temperature, and stirring
Reduction reaction is carried out, Au nano-solution is made；
(b) by H2PtCl4·6H2O is added in Au nano-solution obtained by step (a), Hydrogen Vapor Pressure 1-4MPa, reduction temperature 20-60
At DEG C, stirring carries out reduction reaction, obtains bimetal nano particles solution；
(c) by carrier Al2O3Incipient impregnation is in the resulting bimetal nano particles solution of step (b), stirring and adsorbing, stands
It is dry, 4-5h is calcined under the conditions of 400-500 DEG C, and bimetallic nucleocapsid Au@Pt/Al is made2O3Catalyst.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that：In step (1) or step (a), the HAuCl4·
4H2Mass concentration of the O in terms of the first active component A u in organic solvent is 0.5-2.5mg/mL.
5. preparation method as claimed in claim 2 or claim 3, it is characterised in that：It is organic molten described in step (1) or step (a)
Agent is propene carbonate or ethyl alcohol.
6. preparation method as claimed in claim 3, it is characterised in that：H described in step (b)2PtCl4·6H2O is living with second
Property component Pt meter Au nano-solution mass concentration be 0.5-2.5mg/mL.
7. preparation method as claimed in claim 2 or claim 3, it is characterised in that：Reduction reaction described in step (1) or step (a)
Time be 0.5-5h.
8. preparation method as claimed in claim 3, it is characterised in that：The time of reduction reaction described in step (b) is 0.5-
5h。
9. application of the low-load amount Au catalyst as described in claim 1 in toluene catalytic oxidation reaction.
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