CN113262781A - Metal platinum catalyst and preparation method and application thereof - Google Patents
Metal platinum catalyst and preparation method and application thereof Download PDFInfo
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- CN113262781A CN113262781A CN202110615945.4A CN202110615945A CN113262781A CN 113262781 A CN113262781 A CN 113262781A CN 202110615945 A CN202110615945 A CN 202110615945A CN 113262781 A CN113262781 A CN 113262781A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 76
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- -1 polyethylene Polymers 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 150000001299 aldehydes Chemical class 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 150000007522 mineralic acids Chemical class 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 229920000428 triblock copolymer Polymers 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 239000011148 porous material Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 11
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 10
- 229940117916 cinnamic aldehyde Drugs 0.000 description 10
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 10
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 7
- 230000004075 alteration Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of catalysts, and relates to a metal platinum catalyst, and a preparation method and application thereof. The invention provides a metal platinum catalyst, wherein a carrier of the catalyst is mesoporous alumina, an active component is metal platinum, the mesoporous alumina is prepared by a sol-gel method, and the metal platinum is loaded on the mesoporous alumina carrier in a form of nano-cluster or single atom. The metal platinum catalyst provided by the invention has excellent catalytic activity, selectivity and stability, and has the advantages of high unsaturated alcohol selectivity, high hydrogenation activity, high stability and high metal utilization rate when being applied to the reaction of synthesizing unsaturated alcohol by selective hydrogenation of unsaturated aldehyde.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a metal platinum catalyst, and a preparation method and application thereof.
Background
Unsaturated alcohol is an important fine chemical intermediate, and is widely applied to the production of high value-added products such as flavors, fragrances, medicines and the like. At present, industrially unsaturated alcohol is mainly prepared by selective hydrogenation of unsaturated aldehyde, a homogeneous system is mostly adopted in the technical process, metal hydrides such as lithium aluminum hydride, aluminum isopropoxide and the like are used as reducing agents, the production process can obtain higher unsaturated alcohol selectivity, but the metal hydrides have high danger and high cost, and a large amount of waste liquid which is difficult to treat is generated in the production process, so that the requirements of green chemical industry are not met. Compared with homogeneous catalysts, heterogeneous catalysts have the advantages of easy separation, reusability, environmental protection and the like, and researchers at home and abroad are dedicated to developing heterogeneous supported catalysts to replace reducing agents in the original homogeneous system. However, the design difficulty of the heterogeneous catalyst is that the bond energy and enthalpy change of the C ═ C bond energy and hydrogenation free energy in the unsaturated aldehyde molecule are both lower than that of C ═ O, and when the traditional supported catalyst is adopted, the C ═ C can be preferentially hydrogenated to form saturated aldehyde or completely hydrogenated to form saturated alcohol due to more active sites, so that the target product unsaturated alcohol is difficult to obtain. In addition, the traditional supported catalyst has the problems of low metal utilization rate and poor stability.
In conclusion, the high-dispersion supported platinum catalyst is developed, the catalytic activity and the unsaturated alcohol selectivity of the catalyst in the unsaturated aldehyde hydrogenation reaction are improved, and the improvement of the metal utilization rate has important research significance in the fields of heterogeneous catalysis and fine chemical engineering.
Disclosure of Invention
The invention aims to overcome the defects of low selectivity and metal utilization rate of unsaturated alcohol, low catalyst activity and poor stability of a heterogeneous catalyst in the reaction of synthesizing the unsaturated alcohol by selectively hydrogenating unsaturated aldehyde in the prior art, and provides a metal platinum catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the metal platinum catalyst is characterized in that a carrier of the catalyst is mesoporous alumina, an active component of the catalyst is metal platinum, and the mesoporous alumina is prepared by a sol-gel method.
Preferably, the loading of the metal platinum is 0.01 wt% to 0.02 wt%. Calculation of the load amount in the present invention: the supported amount is (mass of platinum/mass of carrier) × 100%.
Preferably, the preparation method of the mesoporous alumina comprises the following steps:
1) dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an organic alcohol solvent to prepare a solution A;
2) dissolving inorganic acid and aluminum alkoxide in an organic alcohol solvent to prepare a solution B;
3) and adding the solution A into the solution B, stirring, drying and roasting to obtain the mesoporous alumina.
Preferably, the first and second liquid crystal materials are,
in the step 1), the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the organic alcohol solvent is 1: (8-10), the ratio is g/mL;
in the step 2), the ratio of the inorganic acid to the aluminum alkoxide to the organic alcohol solvent is (3-4): (4-5): 20, the proportion relation is mL/g/mL;
in the step 3), the stirring temperature is 20-30 ℃, the stirring time is 48-60h, the drying temperature is 40-60 ℃, the drying time is 48-72h, the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h.
Preferably, the organic alcohol solvent is ethanol; the inorganic acid is nitric acid, and the mass fraction of the nitric acid is 60-70%; the aluminum alkoxide is aluminum isopropoxide.
Preferably, the metal platinum is loaded on the mesoporous alumina support in the form of nanoclusters or single atoms.
The invention also provides a preparation method of the metal platinum catalyst, which comprises the following steps:
s1, preparing mesoporous alumina;
s2, mixing the metal platinum precursor with an organic alcohol solvent to prepare a metal platinum-containing solution;
s3, mixing and soaking the solution containing the metal platinum and the mesoporous alumina by adopting a soaking method so as to load the metal platinum on the mesoporous alumina, and then roasting and reducing to obtain the metal platinum catalyst.
Preferably, the preparation method of the mesoporous alumina in the step S1 comprises the following steps:
1) dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an organic alcohol solvent to prepare a solution A;
2) dissolving inorganic acid and aluminum alkoxide in an organic alcohol solvent to prepare a solution B;
3) and adding the solution A into the solution B, stirring, drying and roasting to obtain the mesoporous alumina.
Preferably, in step 1), the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the organic alcohol solvent is 1: (8-10), the ratio is g/mL;
in the step 2), the ratio of the inorganic acid to the aluminum alkoxide to the organic alcohol solvent is (3-4): (4-5): 20, the proportion relation is mL/g/mL;
in the step 3), the stirring temperature is 20-30 ℃, the stirring time is 48-60h, the drying temperature is 40-60 ℃, the drying time is 48-72h, the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h.
Preferably, the organic alcohol solvent is ethanol; the inorganic acid is nitric acid, and the mass fraction of the nitric acid is 60-70%; the aluminum alkoxide is aluminum isopropoxide.
Preferably, in the step S2, the metal platinum concentration of the metal platinum-containing solution is 18 to 20mmol/L, and the metal platinum precursor is chloroplatinic acid;
the impregnation method in step S3 is an isometric impregnation method.
Preferably, in step S3, the metal-containing platinum solution is diluted with water to be equal volume to the mesoporous alumina (where the equal volume is relative to the pore volume of the mesoporous alumina), and then the diluted metal-containing platinum solution is mixed with the mesoporous alumina and stirred, and the mixture is subjected to ultrasound, aging, drying and roasting to obtain the metal platinum catalyst.
Preferably, in the step S3, the ultrasonic power is 100-250W, and the ultrasonic time is 2-3 h; aging at 20-30 deg.C for 8-12 h; the drying temperature is 80-100 ℃, and the drying time is 8-12 h; the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h; the reduction temperature is 350 ℃ and 450 ℃, and the reduction time is 3-5 h.
The invention also provides the application of the metal platinum catalyst or the metal platinum catalyst prepared by the preparation method in unsaturated aldehyde hydrogenation reaction.
Preferably, the metal platinum catalyst is applied to the reaction of preparing unsaturated alcohol by hydrogenating unsaturated aldehyde.
Preferably, the reaction temperature is 70-90 ℃ and the hydrogen pressure is 3.0-4.0 MPa.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention provides a metal platinum catalyst, wherein a carrier of the catalyst is mesoporous alumina, an active component is metal platinum, the mesoporous alumina is prepared by a sol-gel method, and mesoporous Al2O3Middle Al3+Has three coordination modes of four coordination, five coordination and eight coordination, wherein, five coordination Al3+In a coordination unsaturated state, can be used for fixing nano-clusters or single atoms, and the mesoporous alumina contains Lewis acid sites, and can also be used in unsaturated aldehyde hydrogenation reactionThe mesoporous alumina prepared by the sol-gel method is used as a carrier and has a large amount of penta-coordinated Al3The catalyst has excellent catalytic activity and stability by unsaturated coordination environment and uniform active sites and simultaneously matched with loaded metal platinum, and the metal-carrier interaction, and has high unsaturated alcohol selectivity and high metal utilization rate when being applied to the reaction of synthesizing unsaturated alcohol by selective hydrogenation of unsaturated aldehyde.
Compared with the existing nano catalyst, the high-dispersion metal platinum catalyst provided by the invention can improve the metal utilization rate and reduce the preparation cost of the catalyst, and the geometric and electronic structure of the high-dispersion metal catalyst is also obviously changed, so that the catalyst has a series of properties different from those of the nano catalyst.
2) The invention provides a metal platinum catalyst, and further a preparation method of the mesoporous alumina comprises the following steps: dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an organic alcohol solvent to prepare a solution A; dissolving inorganic acid and aluminum alkoxide in an organic alcohol solvent to prepare a solution B; and adding the solution A into the solution B, stirring, drying and roasting to obtain the mesoporous alumina.
The mesoporous alumina prepared by the method has more penta-coordinate Al in a coordination unsaturated state3+The catalyst can be used as an anchor point of high-dispersion metal to fix high-dispersion platinum atoms or platinum nanoclusters, can be used as a high-dispersion supported platinum catalyst capable of catalyzing selective hydrogenation of unsaturated aldehyde to synthesize unsaturated alcohol, and has high hydrogenation activity and unsaturated alcohol selectivity in the hydrogenation reaction of unsaturated aldehyde. The utilization rate of the high-dispersion platinum catalyst metal is close to 100%, and the catalytic sites are highly uniform.
3) The preparation method of the metal platinum catalyst provided by the invention comprises the steps of taking mesoporous alumina synthesized by a sol-gel method as a carrier, loading noble metal platinum on the mesoporous alumina by adopting an isometric impregnation method, and roasting and reducing to obtain the mesoporous alumina-loaded high-dispersion platinum catalyst. Has higher catalytic activity and cinnamyl alcohol selectivity in the reaction of synthesizing cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde. The catalyst has the advantages of simple synthesis process, convenient operation and easy large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a 0.01 wt% Pt/Al high dispersion platinum catalyst synthesized in example 12O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b);
FIG. 2 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Electron micrograph of (a): (a) an HAADF-STEM map, (b) O, Al and Pt three-element histograms in HAADF-STEM mode, (c) an Al element histogram in HAADF-STEM mode, (d) an O element histogram in HAADF-STEM mode, and (e) a Pt element histogram in HAADF-STEM mode;
FIG. 3 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Spherical aberration electron micrographs under different magnifications;
FIG. 4 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Catalytic performance in cinnamaldehyde hydrogenation reactions;
FIG. 5 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b);
FIG. 6 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3Spherical aberration electron micrographs of different parts;
FIG. 7 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3Catalytic performance in cinnamaldehyde hydrogenation reactions.
FIG. 8 is 0.1 wt% Pt/Al for the catalyst of comparative example 12O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b);
FIG. 9 is 0.1 wt% Pt/Al for the catalyst of comparative example 12O3Spherical aberration electron micrographs of;
FIG. 10 is 0.1 wt% Pt/Al for the catalyst of comparative example 12O3Catalytic performance in cinnamaldehyde hydrogenation reactions;
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a platinum metal catalyst (0.01 wt% Pt/Al)2O3) The catalyst carrier is mesoporous alumina, the active component is metal platinum, and the loading capacity of the metal platinum is 0.01 wt%;
the preparation method of the metal platinum catalyst comprises the following steps:
s1, preparing the mesoporous alumina carrier by adopting a sol-gel method: 4.2g P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, i.e., PEO-PPO-PEO) was dissolved in 40mL of ethanol to form solution A; dissolving 6.4mL of nitric acid with mass fraction of 67% and 8.16g of aluminum isopropoxide in 40mL of ethanol to form a solution B; slowly adding the solution A into the solution B under stirring, covering the mixed solution with a PE film, stirring for 48 hours at 25 ℃, and drying for 48 hours in a 60 ℃ forced air drying oven; and roasting the dried gel in a muffle furnace at the heating rate of 1 ℃/mi1 and the roasting temperature of 400 ℃ for 4h, and naturally cooling to room temperature after roasting to obtain the mesoporous alumina.
S2, preparing a metal-containing platinum solution: h is to be2PtCl6·6H2Dissolving O in ethanol to obtain a solution containing metal platinum, wherein the concentration is 19.3 mmol/L;
s3, preparing the mesoporous alumina supported high-dispersion platinum catalyst by adopting an isometric impregnation method: diluting 0.05mL of the metal-containing platinum solution prepared in step S2 to 1.5mL with water to obtain a diluted metal-containing platinum solution (with a metal platinum concentration of 0.643 mmol/L); dripping the 1.5mL of diluted metal-containing platinum solution into 2.0g (with the pore volume of 1.5mL) of the mesoporous alumina carrier obtained in the step S1, fully and uniformly stirring by using a glass rod, and carrying out ultrasonic treatment on the obtained mixture, wherein the ultrasonic power is 200W, and the ultrasonic time is 2h, so that the metal precursor is uniformly distributed in a carrier pore channel; after the ultrasonic treatment is finished, the mixture is placed at 25 ℃ for aging for 12h, and then is placed in a forced air drying oven at 80 ℃ for drying for 12 h; transferring the dried mixture to a muffle furnace for roasting, wherein the heating rate is 1 ℃/mi1, the roasting temperature is 400 ℃, the roasting time is 4h, and naturally cooling to room temperature after roasting; finally, reducing gas with the flow rate of 50mL/mi1 is used (the reducing gas is H2And N2The volume ratio of hydrogen is 20 percent), the reduction is carried out at 400 ℃ for 3h to obtain the metal platinum catalyst (0.01wt percent Pt/Al)2O3)。
Performance verification
FIG. 1 is a 0.01 wt% Pt/Al high dispersion platinum catalyst synthesized in example 12O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b);
as can be seen from FIG. 1, the catalyst has a type IV isotherm, H2The type hysteresis loop indicates that the catalyst is a mesoporous material; the specific surface area 371m of the catalyst was calculated by the method Bru1auer-Emmett-Teller (BET)2(ii)/g; the pore diameter and pore volume of the catalyst were calculated by the Barrett-Joy1er-Hale1da (BJH) methodAre 7.01 m and 0.68cm3/g。
FIG. 2 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Electron micrograph of (a): (a) an HAADF-STEM map, (b) O, Al and Pt three-element histograms in HAADF-STEM mode, (c) an Al element histogram in HAADF-STEM mode, (d) an O element histogram in HAADF-STEM mode, and (e) a Pt element histogram in HAADF-STEM mode; it can be seen from FIG. 2 that the metal Pt is uniformly distributed in Al2O3On a carrier.
FIG. 3 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Spherical aberration electron micrographs under different magnifications; some isolated bright spots appear in fig. 3, illustrating that the platinum metal is present as a single atom.
FIG. 4 is 0.01 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 12O3Catalytic performance in cinnamaldehyde hydrogenation reactions; the reaction conditions were 0.3g of the reactant cinnamaldehyde, 30mL of solvent ethanol, 0.3g of catalyst 0.01 wt% Pt/Al2O3The reaction temperature is 80 ℃, and the hydrogen pressure is 3.0 MPa; as can be seen from the reaction results of fig. 4, when the conversion of cinnamaldehyde was 98%, the selectivity of cinnamyl alcohol was as high as 97.6%.
Example 2
This example provides a platinum metal catalyst (0.02 wt% Pt/Al)2O3) The catalyst carrier is mesoporous alumina, the active component is metal platinum, and the loading capacity of the metal platinum is 0.02 wt%;
the preparation method of the metal platinum catalyst comprises the following steps:
s1, preparing the mesoporous alumina carrier by adopting a sol-gel method: 4.2g P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, i.e., PEO-PPO-PEO) was dissolved in 40mL of ethanol to form solution A; dissolving 6.4mL of nitric acid with mass fraction of 67% and 8.16g of aluminum isopropoxide in 40mL of ethanol to form a solution B; slowly adding the solution A into the solution B under stirring, covering the mixed solution with a PE film, stirring for 48 hours at 25 ℃, and drying the mixed solution in a forced air drying oven at 40 ℃ for 72 hours; and roasting the dried gel in a muffle furnace at the heating rate of 3 ℃/mi1 and the roasting temperature of 350 ℃ for 5h, and naturally cooling to room temperature after roasting to obtain the mesoporous alumina.
S2, preparing a noble metal platinum-containing solution: h is to be2PtCl6·6H2Dissolving O in ethanol to obtain a solution containing metal platinum, wherein the concentration is 19.3 mmol/L;
s3, preparing the mesoporous alumina supported high-dispersion platinum catalyst by adopting an isometric impregnation method: diluting 0.10mL of the metal-containing platinum solution prepared in step S2 to 1.5mL with water to obtain a diluted metal-containing platinum solution (with a metal platinum concentration of 1.287 mmol/L); dripping the 1.5mL of diluted metal-containing platinum solution into 2.0g (with the pore volume of 1.5mL) of the mesoporous alumina carrier obtained in the step S1, fully and uniformly stirring by using a glass rod, and carrying out ultrasonic treatment on the obtained mixture, wherein the ultrasonic power is 200W, and the ultrasonic time is 2h, so that the metal precursor is uniformly distributed in a carrier pore channel; after the ultrasonic treatment is finished, the mixture is placed at 25 ℃ for aging for 12h, and then is placed in a forced air drying oven at 100 ℃ for drying for 8 h; transferring the dried mixture to a muffle furnace for roasting, wherein the heating rate is 3 ℃/mi1, the roasting temperature is 350 ℃, the roasting time is 5h, and naturally cooling to room temperature after roasting; finally, reducing gas with the flow rate of 50mL/mi1 is used (the reducing gas is H2And N2The volume ratio of hydrogen is 20 percent), the reduction is carried out at the temperature of 450 ℃ for 4h, and the metal platinum catalyst (0.02wt percent Pt/Al) is obtained2O3)。
FIG. 5 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b); as can be seen in FIG. 5, the catalyst has a type IV isotherm, H2The type hysteresis loop indicates that the catalyst is a mesoporous material; the specific surface area of the catalyst was calculated to be 362m by the BET method2(ii)/g; the catalyst has a pore diameter and a pore volume of 6.61m and 0.61cm respectively calculated by the BJH method3/g。
FIG. 6 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3Spherical aberration electron micrographs of different parts; some isolated bright spots appear in FIG. 6, illustrating the presence of platinum metal as a single atom。
FIG. 7 is 0.02 wt% Pt/Al for the highly dispersed platinum catalyst synthesized in example 22O3The catalytic performance in the hydrogenation reaction of the cinnamaldehyde is that the reaction conditions are 0.3g of reactant cinnamaldehyde, 30mL of solvent ethanol, 0.15g of catalyst and 0.02 wt% of Pt/Al2O3The reaction temperature is 90 ℃, and the hydrogen pressure is 4.0 MPa; as can be seen from the reaction results of fig. 7, when the conversion of cinnamaldehyde was 71%, the selectivity of cinnamyl alcohol was as high as 89.7%.
Comparative example 1
This comparative example provides a platinum catalyst 0.1 wt% Pt/Al2O3Which differs from example 1 only in that the catalyst support was selected from commercially available mesoporous alumina (available from Alfa Aesar, with a particle size of 40-80 mesh) and Pt loading of 0.1 wt%; other preparation conditions were the same as in example 1.
FIG. 8 is 0.1 wt% Pt/Al for the catalyst of comparative example 12O3The nitrogen adsorption and desorption curve (a) and the pore size distribution diagram (b); as can be seen in FIG. 8, the catalyst has a type IV isotherm, H2The type hysteresis loop indicates that the catalyst is a mesoporous material; the specific surface area of the catalyst is 264m calculated by using a BET method2(ii)/g; the catalyst has a pore diameter and a pore volume of 5.71m and 0.38cm respectively calculated by the BJH method3(ii) in terms of/g. FIG. 9 is a 0.1 wt% Pt/Al ratio of the metallic platinum catalyst of comparative example 12O3The spherical aberration electron microscope image of (2) shows that the metal Pt is distributed on the alumina carrier in the form of nano particles, and the distribution range of the particle size is wide.
The test was carried out under the same reaction conditions as in example 1, this comparative example catalyst 0.1 wt% Pt/Al2O3In the unsaturated aldehyde hydrogenation reaction, the selectivity to the target product unsaturated alcohol was low, and when the conversion of cinnamaldehyde was 20.7%, the selectivity of cinnamyl alcohol was only 34.5%, and the results are shown in fig. 10.
In conclusion, the mesoporous alumina prepared by the sol-gel method is the penta-coordinated Al in the coordination unsaturated state3+The method has the advantages of simple operation and easy scale production, and can synthesize highly dispersed platinum catalyst by using the immersion method under the interaction with metal atomsAnd (4) producing.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (16)
1. The metal platinum catalyst is characterized in that a carrier of the catalyst is mesoporous alumina, an active component of the catalyst is metal platinum, and the mesoporous alumina is prepared by a sol-gel method.
2. The platinum metal catalyst according to claim 1, wherein the loading of platinum metal is 0.01 to 0.02 wt%.
3. The metallic platinum catalyst according to claim 1 or 2, wherein the preparation method of the mesoporous alumina comprises the following steps:
1) dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an organic alcohol solvent to prepare a solution A;
2) dissolving inorganic acid and aluminum alkoxide in an organic alcohol solvent to prepare a solution B;
3) and adding the solution A into the solution B, stirring, drying and roasting to obtain the mesoporous alumina.
4. The metallic platinum catalyst according to any one of claims 1 to 3,
in the step 1), the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the organic alcohol solvent is 1: (8-10), wherein the proportion relation is g/mL;
in the step 2), the ratio of the inorganic acid to the aluminum alkoxide to the organic alcohol solvent is (3-4): (4-5): 20, the proportion relation is mL/g/mL;
in the step 3), the stirring temperature is 20-30 ℃, the stirring time is 48-60h, the drying temperature is 40-60 ℃, the drying time is 48-72h, the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h.
5. The platinum metal catalyst according to any one of claims 1 to 4, wherein the organic alcohol solvent is ethanol; the inorganic acid is nitric acid, and the mass fraction of the nitric acid is 60-70%; the aluminum alkoxide is aluminum isopropoxide.
6. The metallic platinum catalyst according to any one of claims 1 to 5, wherein the metallic platinum is supported on the mesoporous alumina support in the form of nanoclusters or monoatomic atoms.
7. A method for preparing the platinum metal catalyst according to any one of claims 1 to 6, comprising the steps of:
s1, preparing mesoporous alumina;
s2, mixing the metal platinum precursor with an organic alcohol solvent to prepare a metal platinum-containing solution;
s3, mixing and soaking the solution containing the metal platinum and the mesoporous alumina by adopting a soaking method so as to load the metal platinum on the mesoporous alumina, and then roasting and reducing to obtain the metal platinum catalyst.
8. The method of preparing a platinum catalyst according to claim 7, wherein the step S1 of preparing the mesoporous alumina comprises the steps of:
1) dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an organic alcohol solvent to prepare a solution A;
2) dissolving inorganic acid and aluminum alkoxide in an organic alcohol solvent to prepare a solution B;
3) and adding the solution A into the solution B, stirring, drying and roasting to obtain the mesoporous alumina.
9. The method for preparing a metal platinum catalyst according to claim 7 or 8, wherein the ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the organic alcohol solvent in step 1) is 1: (8-10), the ratio is g/mL;
in the step 2), the ratio of the inorganic acid to the aluminum alkoxide to the organic alcohol solvent is (3-4): (4-5): 20, the proportion relation is mL/g/mL;
in the step 3), the stirring temperature is 20-30 ℃, the stirring time is 48-60h, the drying temperature is 40-60 ℃, the drying time is 48-72h, the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h.
10. The method for preparing a platinum metal catalyst according to any one of claims 7 to 9, wherein the organic alcohol solvent is ethanol; the inorganic acid is nitric acid, and the mass fraction of the nitric acid is 60-70%; the aluminum alkoxide is aluminum isopropoxide.
11. The method for preparing a platinum metal catalyst according to any one of claims 7 to 10, wherein the concentration of platinum metal in the solution containing platinum metal in step S2 is 18 to 20mmol/L, and the precursor of platinum metal is chloroplatinic acid;
the impregnation method in step S3 is an isometric impregnation method.
12. The method for preparing a platinum metal catalyst according to any one of claims 7 to 11, wherein the platinum metal catalyst is obtained by diluting a solution containing platinum metal with water to an equal volume with mesoporous alumina, mixing and stirring the diluted solution containing platinum metal with mesoporous alumina, and subjecting the mixture to ultrasound, aging, drying and calcining in step S3.
13. The method for preparing the platinum catalyst as claimed in any one of claims 7 to 12, wherein in the step S3, the ultrasonic power is 100-250W, and the ultrasonic time is 2-3 h; aging at 20-30 deg.C for 8-12 h; the drying temperature is 80-100 ℃, and the drying time is 8-12 h; the roasting temperature is 350-450 ℃, and the roasting time is 4-5 h; the reduction temperature is 350 ℃ and 450 ℃, and the reduction time is 3-5 h.
14. Use of the platinum metal catalyst according to any one of claims 1 to 6 or the platinum metal catalyst obtained by the preparation method according to any one of claims 7 to 13 in hydrogenation of unsaturated aldehydes.
15. The use of claim 14, wherein the metal platinum catalyst is used in a reaction for hydrogenation of unsaturated aldehydes to produce unsaturated alcohols.
16. Use according to claim 15, wherein the reaction temperature is 70-90 ℃ and the hydrogen pressure is 3.0-4.0 MPa.
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