CN108855104A - A kind of ormolu support type grade porous aluminum oxide catalyst and preparation method thereof - Google Patents
A kind of ormolu support type grade porous aluminum oxide catalyst and preparation method thereof Download PDFInfo
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- CN108855104A CN108855104A CN201810767492.5A CN201810767492A CN108855104A CN 108855104 A CN108855104 A CN 108855104A CN 201810767492 A CN201810767492 A CN 201810767492A CN 108855104 A CN108855104 A CN 108855104A
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
Abstract
The invention discloses a kind of ormolu support type grade porous aluminum oxide catalyst and preparation method thereof.This approach includes the following steps：1) aluminium secondary butylate solution is instilled in acetonitrile and the mixed solution of deionized water and reaction is hydrolyzed, obtain solid carrier grade hole γ-Al2O3；2) by step 1) resulting solid carrier grade hole γ-Al2O3, nitrate trihydrate copper, zinc nitrate hexahydrate, water be added flask in, then be added urea stirring, obtain mixed solution；3) mixed solution of step 2) is reacted in oil bath pan；4) mixed solution after step 3) reaction is filtered into drying, obtains solid product；5) step 4) obtained solid product is placed in Muffle furnace and is calcined；6) the calcined solid product of step 5) is placed in tube furnace under atmosphere of hydrogen and is restored to get the catalyst.Gained specific surface area of catalyst of the invention is larger, has more active sites, and metal active constituent is uniformly distributed in carrier surface, has good prospect in terms of catalytic hydrogenation.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of CuZn alloy support type grade hole γ-Al2O3Catalyst and
Preparation method.
Background technique
Aromatic amine compound is widely used in the synthesis of drug, pesticide, polymer, has in the industrial production important
Value.Aromatic amine compound generally can be by restoring corresponding fragrant nitro compound preparation.In general, in fragrant nitro
In the catalytic hydrogenation of compound, the noble metal catalysts such as Pd, Pt have high catalytic activity nearest, but still there are many not
Foot.For example, the reserves of noble metal are low, at high price, toxicity is higher, these all limit the application of noble metal catalyst.And it is honest and clean
It is the rich reserves of valence metal (such as Cu, Fe, Co), cheap, there is very big application potential in catalytic hydrogenation field.Wherein
Cu series catalysts all show excellent catalytic performance in terms of carbon dioxide reduction, synthesis gas ethyl alcohol and esters add,
Especially also there is good hydrogenation activity to 4- nitrophenol.
Solid catalyst generally requires certain carrier, and carrier not only plays dispersion and carried metal, while carrier
Effects on Microstructure reactants and products catalyst surface be enriched with, influence the performance of catalyst.Resist since aluminium oxide has
The characteristics of breaking strength is high, and specific surface is moderate, aperture and the adjustable section of porosity, good water absorption, therefore aluminium oxide can support foot
The active component enough measured not only can provide acid centre, but also can provide basic center and the inertia of carrier can prevent carrier and work
Property the acid function that generates of ingredient synergistic effect, inhibit oligomerisation reaction and many advantages, such as double bond transfer reaction, so it can make
For excellent carrier.
Summary of the invention
The present invention provides a kind of CuZn alloy support type grade hole γ-Al to solve above-mentioned technical problem2O3Catalyst and its
Preparation method is improved the load capacity and dispersibility of CuZn alloy using the high-specific surface area of carrier, prevented to a certain extent
The agglomeration of CuZn alloy, while acid centre and basic center being provided, promote the progress of catalysis reaction.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of CuZn alloy support type grade hole γ-Al2O3The preparation method of catalyst, it includes the following steps：
1) aluminium secondary butylate solution is instilled in acetonitrile and the mixed solution of deionized water and reaction is hydrolyzed, obtain solid load
Body grade hole γ-Al2O3；
2) by step 1) resulting solid carrier grade hole γ-Al2O3, nitrate trihydrate copper, zinc nitrate hexahydrate, deionized water
It is added in flask, urea is then added, is uniformly mixed, obtains mixed solution；
3) mixed solution obtained by step 2) is reacted in oil bath pan；
4) mixed solution after step 3) reaction is filtered into drying, obtains solid product；
5) step 4) obtained solid product is placed in Muffle furnace and is calcined；
6) the calcined solid product of step 5) is placed in tube furnace under atmosphere of hydrogen and is restored to get the CuZn alloy
Support type grade hole γ-Al2O3Catalyst.
In above scheme, the introduction volume volume ratio of step 1) acetonitrile, water and aluminium secondary butylate solution is (20-30):(5-
15):(3-7)。
In above scheme, the hole of solid carrier grade described in step 2) γ-Al2O3It is with deionized water introduction volume mass ratio
1:100, with solid carrier grade hole γ-Al2O3The amount of mass ratio 9.44% introduces nitrate trihydrate copper, with solid carrier grade hole
γ-Al2O3The amount of mass ratio (11.44~57.2) % introduces zinc nitrate hexahydrate, with the molar ratio of urea and metal ion for 1:
100 introduce urea.
In above scheme, reaction temperature described in step 3) is 80 DEG C, reaction time 10-20h.
In above scheme, calcination temperature described in step 4) is 400 DEG C~450 DEG C, calcination time 1-3h.
In above scheme, the step 5) reduction temperature is 350 DEG C~450 DEG C, recovery time 2h, heating rate 2
℃/min。
The CuZn alloy support type grade hole γ-Al of the preparation method preparation2O3Catalyst, specific surface area 291
~386m2/ g, CuZn alloy are uniformly distributed in grade hole γ-Al2O3Surface.
The principle of the present invention is：
For the present invention first using aluminium secondary butylate as silicon source, acetonitrile and water prepare carrier grade hole γ-Al2O3, then with precipitating
Method, is zinc source by copper source and zinc nitrate hexahydrate of nitrate trihydrate copper, is deposited into carrier surface, is prepared into this using reduction
Catalyst.It is 2.5~15.0% that wherein metal active constituent, which accounts for the mass percent of carrier,.
Beneficial effects of the present invention are：
1) present invention gained CuZn alloy support type grade hole γ-Al2O3Catalyst has high specific surface area, and exists
Macropore duct and meso-hole structure, CuZn alloy are uniformly distributed in grade hole γ-Al2O3The presence on surface, Zn can effectively improve Cu
The stability and dispersibility of particle.
2) preparation method of the present invention is simple, reaction condition is mild, and repetitive rate is high, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is CuZn alloy support type grade obtained hole γ-Al in the embodiment of the present invention 12O3The wide-angle diffraction of catalyst
XRD diagram.
Fig. 2 is CuZn alloy support type grade obtained hole γ-Al in the embodiment of the present invention 12O3(a) nitrogen of catalyst
Adsorption curve, (b) mesoporous pore size distribution map.
Fig. 3 is CuZn alloy support type grade obtained hole γ-Al in the embodiment of the present invention 22O3The scanning electron microscope of catalyst
Figure.
Fig. 4 is CuZn alloy support type grade obtained hole γ-Al in the embodiment of the present invention 22O3(a) nitrogen of catalyst
Adsorption curve, (b) mesoporous pore size distribution map.
Fig. 5 is CuZn alloy support type grade obtained hole γ-Al in the embodiment of the present invention 32O3The UV-Vis of catalyst schemes
Spectrum.
Specific embodiment
Further the present invention will be described with reference to the accompanying drawings and examples, but the contents of the present invention are not limited solely to
The following examples.
In following embodiment, unless specific instructions, the reagent is commercially available chemical reagent.
Embodiment 1
A kind of CuZn alloy support type grade hole γ-Al2O3Catalyst, preparation method includes the following steps：
1) it measures 20mL acetonitrile solution to be added in the beaker of 50ml, the deionized water of 5mL is added, after mixing evenly, be added dropwise
3g aluminium secondary butylate solution stirs 10 minutes, obtains solid product I；
2) it weighs 1g solid product I to be added in 200ml round-bottomed flask, 100ml deionized water is added, stirs evenly, then claim
Taking 0.0944g nitrate trihydrate copper, (metallic copper accounts for the grade hole γ-Al2O3The 2.5% of quality of materials ratio) flask is added, then claim
Taking 0.1144g zinc nitrate hexahydrate, (metallic zinc accounts for the grade hole γ-Al2O3The 2.5% of quality of materials ratio) it is added in flask, it stirs
Mix uniformly, then weigh 4.6514g urea (molar ratio of metal ion and urea be 1:100) it is added in flask, stirs evenly, obtain
Mixed solution II；
3) mixed solution I I is reacted in oil bath pan, reaction temperature is 80 DEG C, and reaction time 10h obtains mixed solution III；
4) it uses aperture to filter for 0.45 μm of organic filter membrane mixed solution III, is transferred in 60 DEG C of baking ovens, dry water
Point, obtain solid product；
5) above-mentioned solid product is placed in Muffle furnace and is calcined, calcination temperature is 400 DEG C, calcination time 1h；
6) by calcined solid product be placed in tube furnace reductase 12 h under 350 DEG C of atmosphere of hydrogen (2 DEG C of heating rate/
Min) to get CuZn alloy support type grade hole γ-Al2O3Catalyst.
Fig. 1 is CuZn alloy support type grade hole γ-Al obtained by the present embodiment2O3Catalyst wide-angle diffraction XRD diagram, by Fig. 1
As can be seen that material after overload shows apparent CuZn alloy phase, shows CuZn alloy compared to before unsupported
Successfully it is carried on grade hole γ-Al2O3Surface, and what CuZn alloy generated after reduction is CuZn alloy phase.
Fig. 2 is CuZn alloy support type grade hole γ-Al obtained by this example2O3Catalyst nitrogen adsorption desorption curve and hole
Diameter distribution map, the specific surface area that test result obtains material is 315m2/ g is nitrogen adsorption desorption curve by (a) figure, it can be seen that compared with
Low relative pressure, there are an apparent hysteresis loop, shows mesoporous presence between 0.4-1.0, (b) the mesoporous hole that figure obtains
Diameter distribution map can further confirm that mesoporous pore size is mainly distributed on 3.73nm.
By CuZn alloy support type grade hole γ-Al prepared by this example2O3Catalyst is big as present in its structure
The uniformity in hole and the load of meso-hole structure and surface metal, will have important application in terms of catalytic hydrogenation.
Embodiment 2
A kind of CuZn alloy support type grade hole γ-Al2O3Catalyst, preparation method includes the following steps：
1) it measures 25mL acetonitrile solution to be added in the beaker of 50ml, the deionized water of 10mL is added, after mixing evenly, be added dropwise
5g aluminium secondary butylate solution stirs 20 minutes, obtains solid product I；
2) it weighs 1g solid product I to be added in 200mL round-bottomed flask, 100mL deionized water is added, stirs evenly, then claim
Taking 0.0944g nitrate trihydrate copper, (metallic copper accounts for the grade hole γ-Al2O3The 2.5% of quality of materials ratio) flask is added, then claim
Taking 0.3433g zinc nitrate hexahydrate, (metallic zinc accounts for the grade hole γ-Al2O3The 7.5% of quality of materials ratio) it is added in flask, it stirs
Mix uniformly, then weigh 9.2668g urea (molar ratio of metal ion and urea be 1:100) it is added in flask, stirs evenly, obtain
Mixed solution II；
3) gained mixed solution I I is reacted in oil bath pan, reaction temperature is 80 DEG C, and reaction time 15h must be mixed molten
Liquid III；
4) it uses aperture to filter for 0.45 μm of organic filter membrane gained mixed solution III, is transferred in 60 DEG C of baking ovens, dry
Solid carbon dioxide point, obtains solid product；
5) above-mentioned solid product is placed in Muffle furnace and is calcined, calcination temperature is 450 DEG C, calcination time 2h；
6) above-mentioned solid product is placed in tube furnace reductase 12 h under 400 DEG C of atmosphere of hydrogen (2 DEG C/min of heating rate), i.e.,
Obtain CuZn alloy support type grade hole γ-Al2O3Catalyst.
Fig. 3 is CuZn alloy support type grade hole γ-Al obtained by the present embodiment2O3The scanning electron microscope (SEM) photograph of catalyst, in low power
As can be seen that the material surface after loaded Cu Zn alloy is coarse in scanning figure (a), but still remain part macropore hole
Road, entire grain diameter is other in the micron-scale, as can be seen that macropore hole wall is in threadiness, this fiber in high power scanning figure (b)
There is abundant mesoporous in the structure of shape.
Fig. 4 is CuZn alloy support type grade hole γ-Al obtained by this example2O3Catalyst nitrogen adsorption desorption curve and hole
Diameter distribution map, the specific surface area that test result obtains material is 291m2/ g is nitrogen adsorption desorption curve by (a) figure, it can be seen that compared with
Low relative pressure, there are an apparent hysteresis loop, shows mesoporous presence between 0.4-1.0, Jie obtained in conjunction with (b) figure
Hole graph of pore diameter distribution can further confirm that mesoporous pore size is mainly distributed on 3.55nm.
By CuZn alloy support type grade hole γ-Al prepared by this example2O3Catalyst is big as present in its structure
The uniformity in hole and the load of meso-hole structure and surface metal, will have important application in terms of catalytic hydrogenation.
Embodiment 3
A kind of CuZn alloy support type grade hole γ-Al2O3Catalyst, preparation method includes the following steps：
1) it measures 30mL acetonitrile solution to be added in the beaker of 50mL, the deionized water of 15mL is added, after mixing evenly, be added dropwise
7g aluminium secondary butylate solution stirs 30 minutes, obtains solid product I；
2) it weighs 1g solid product I to be added in 200mL round-bottomed flask, 100mL deionized water is added, stirs evenly, then claim
Taking 0.0944g nitrate trihydrate copper, (metallic copper accounts for the grade hole γ-Al2O3The 2.5% of quality of materials ratio) flask is added, then claim
Taking 0.5720g zinc nitrate hexahydrate, (metallic zinc accounts for the grade hole γ-Al2O3The 12.5% of quality of materials ratio) it is added in flask, it stirs
Mix uniformly, then weigh 13.8822g urea (molar ratio of metal ion and urea be 1:100) it is added in flask, stirs evenly,
Obtain mixed solution II；
3) mixed solution II is reacted in oil bath pan, reaction temperature is 80 DEG C, and reaction time 20h obtains mixed solution III；
4) it uses aperture to filter for 0.45 μm of organic filter membrane mixed solution III, is transferred in 80 DEG C of baking ovens, dry water
Point, obtain solid product；
5) above-mentioned solid product is placed in Muffle furnace and is calcined, calcination temperature is 400 DEG C, calcination time 3h；
6) above-mentioned burnt solid product is placed in tube furnace reductase 12 h (heating rate 2 under 450 DEG C of atmosphere of hydrogen
DEG C/min) to get CuZn alloy support type grade hole γ-Al2O3Catalyst.
Fig. 5 is CuZn alloy support type grade hole γ-Al obtained by the present embodiment2O3The UV of catalyst reduction 4- nitrophenol
Map is tested, reaction system is measured every 5min, test result shows in the preceding 30min of reaction, absorbs at 400nm
Peak intensity constantly reduces, and illustrates that the content of p-nitrophenol in reaction system is decreased obviously, when reaction reaches 40min, at 400nm
Apparent absorption peak is not observed, has absolutely proved that the catalyst has very high catalytic activity.
CuZn alloy support type grade hole γ-Al prepared by the present invention2O3Catalyst macropore as present in its structure
The uniformity loaded with meso-hole structure and surface metal, will have important application in terms of catalytic hydrogenation.
The foregoing is merely the preferred embodiment of the present invention, it is noted that comes for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, make several modifications and variations, these belong to protection model of the invention
It encloses.
Claims (7)
1. a kind of preparation method of ormolu support type grade porous aluminum oxide catalyst, which is characterized in that it includes following step
Suddenly：
1) aluminium secondary butylate solution is instilled in acetonitrile and the mixed solution of deionized water and reaction is hydrolyzed, obtain solid carrier etc.
Grade hole γ-Al2O3；
2) by step 1) resulting solid carrier grade hole γ-Al2O3, nitrate trihydrate copper, zinc nitrate hexahydrate, deionized water be added
In flask, urea is then added, is uniformly mixed, obtains mixed solution；
3) mixed solution obtained by step 2) is reacted in oil bath pan；
4) mixed solution after step 3) reaction is filtered into drying, obtains solid product；
5) step 4) obtained solid product is placed in Muffle furnace and is calcined；
6) the calcined solid product of step 5) is placed in tube furnace under atmosphere of hydrogen and is restored to get CuZn alloy load
Type grade hole γ-Al2O3Catalyst.
2. preparation method according to claim 1, which is characterized in that step 1) acetonitrile, water and aluminium secondary butylate solution draw
Entering amount with volume ratio is 20-30:5-15:3-7.
3. preparation method according to claim 1, which is characterized in that the hole γ of solid carrier grade described in step 2)-
Al2O3It is 1 with deionized water introduction volume mass ratio:100, with solid carrier grade hole γ-Al2O3The amount of mass ratio 9.44% is drawn
Enter nitrate trihydrate copper, with solid carrier grade hole γ-Al2O3The amount of mass ratio 11.44~57.2% introduces zinc nitrate hexahydrate, with
The molar ratio of urea and metal ion is 1:100 introduce urea.
4. preparation method according to claim 1, which is characterized in that reaction temperature described in step 3) is 80 DEG C, reaction
Time is 10-20h.
5. preparation method according to claim 1, which is characterized in that calcination temperature described in step 4) is 400 DEG C~450
DEG C, calcination time 1-3h.
6. preparation method according to claim 1, which is characterized in that the step 5) reduction temperature is 350 DEG C~450
DEG C, recovery time 2h, heating rate is 2 DEG C/min.
7. the ormolu support type grade porous aluminum oxide of described in any item preparation method preparations is urged according to claim 1~6
Agent, which is characterized in that its specific surface area is 291~386m2/ g, CuZn alloy are uniformly distributed in grade hole γ-Al2O3Surface.
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Cited By (2)
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| CN110586198A (en) * | 2019-09-29 | 2019-12-20 | 武汉理工大学 | Hierarchical porous macroporous-mesoporous gamma-Al2O3Catalyst carrier material and preparation method thereof |
| WO2023125060A1 (en) * | 2021-12-29 | 2023-07-06 | 中国石油天然气股份有限公司 | Gas-phase aldehyde hydrogenation catalyst, preparation method therefor and application thereof |
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Application publication date: 20181123 |