CN113262781B - 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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- CN113262781B CN113262781B CN202110615945.4A CN202110615945A CN113262781B CN 113262781 B CN113262781 B CN 113262781B CN 202110615945 A CN202110615945 A CN 202110615945A CN 113262781 B CN113262781 B CN 113262781B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 80
- 239000002184 metal Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000005984 hydrogenation 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 41
- 238000001035 drying Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- -1 polyethylene Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 14
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 10
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 229920000428 triblock copolymer Polymers 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 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 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 24
- 239000011148 porous material Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 11
- 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
- 238000001000 micrograph Methods 0.000 description 7
- 230000004075 alteration Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000013335 mesoporous material 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
- 230000015572 biosynthetic process Effects 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
- 238000002474 experimental method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 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
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification 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
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- 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
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- Ceramic Engineering (AREA)
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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 nano cluster or monoatomic form. 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 selectively hydrogenating 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-added-value products such as essence, perfume, medicine and the like. The unsaturated alcohol is mainly prepared by selective hydrogenation of unsaturated aldehyde in the prior industry, a homogeneous phase system is mostly adopted in the process, and metal hydrides such as lithium aluminum hydride, aluminum isopropoxide and the like are used as reducing agents. Compared with a homogeneous catalyst, the heterogeneous catalyst has the advantages of easy separation, repeated utilization, green environment protection and the like, and researchers at home and abroad aim to develop heterogeneous supported catalysts to replace reducing agents in the prior homogeneous system. However, the heterogeneous catalyst has the design difficulty that the bond energy of C=C and the free energy enthalpy change of hydrogenation in unsaturated aldehyde molecules are lower than C=O, and when the traditional supported catalyst is adopted, the C=C can be preferentially hydrogenated to form saturated aldehyde or fully hydrogenated to form saturated alcohol due to more active sites, so that the unsaturated alcohol of a target product is difficult to obtain. In addition, in the traditional supported catalyst, the problems of low metal utilization rate and poor stability exist.
In summary, developing a high-dispersion supported platinum catalyst improves the catalytic activity and the selectivity of unsaturated alcohols in the hydrogenation reaction of unsaturated aldehydes, and simultaneously improves the metal utilization rate, thus having important research significance in the fields of heterogeneous catalysis and fine chemical industry.
Disclosure of Invention
The invention aims to overcome the defects of low unsaturated alcohol selectivity, low metal utilization rate, low catalyst activity and poor stability of a heterogeneous catalyst in the reaction of synthesizing unsaturated alcohol by selectively hydrogenating unsaturated aldehyde in the prior art, and provides a metal platinum catalyst, a preparation method and application thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the carrier of the catalyst is mesoporous alumina, the active component is metal platinum, and the mesoporous alumina is prepared by a sol-gel method.
Preferably, the loading of the platinum metal is 0.01wt% to 0.02wt%. The load capacity is calculated in the invention: load= (mass of platinum/mass of support) ×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 method comprises the steps of,
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 proportion relation is g/mL;
in the step 2), the ratio of the inorganic acid, aluminum alkoxide and 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 4-5h.
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 supported on the mesoporous alumina carrier in the form of nanoclusters or monoatoms.
The invention also provides a preparation method of the metal platinum catalyst, which comprises the following steps:
s1, preparing mesoporous alumina;
s2, mixing a metal platinum precursor and an organic alcohol solvent to prepare a metal platinum-containing solution;
and S3, mixing and impregnating the metal platinum-containing solution and the mesoporous alumina by adopting an impregnation method 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 includes 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 proportion relation is g/mL;
in the step 2), the ratio of the inorganic acid, aluminum alkoxide and 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 4-5h.
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 concentration of the metal platinum in the metal platinum-containing solution in the step S2 is 18-20mmol/L, and the metal platinum precursor is chloroplatinic acid;
the impregnation method in step S3 is an isovolumetric impregnation method.
Preferably, in step S3, the metal-containing platinum solution is diluted with water to an equal volume to that of the mesoporous alumina (the equal volume is relative to the pore volume of the mesoporous alumina), and then the diluted metal-containing platinum solution and the mesoporous alumina are mixed and stirred, and the obtained mixture is subjected to ultrasonic treatment, 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 2-3h; the aging temperature is 20-30 ℃ and the aging time is 8-12h; the drying temperature is 80-100 ℃ and the drying time is 8-12h; roasting at 350-450 deg.c for 4-5 hr; the reduction temperature is 350-450 ℃, and the reduction time is 3-5h.
The invention also provides an 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 3.0-4.0MPa.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides a metal platinum catalyst, the carrier of the catalyst is mesoporous alumina, the active component is metal platinum, the mesoporous alumina is prepared by a sol-gel method, and mesoporous Al 2 O 3 Al of (C) 3+ Has three coordination modes of four coordination, five coordination and eight coordination, wherein, five coordination Al 3+ In coordination unsaturated state, can be used for fixing nanoclusters or monoatoms, and mesoporous alumina contains Lewis acid sites, and can also be used as electrophilic sites of C=O bonds in unsaturated aldehyde hydrogenation reaction, so that the selectivity of unsaturated alcohols is improved, and the mesoporous alumina prepared by a sol-gel method is used as a carrier, and has a large amount of five-coordination Al 3 The unsaturated coordination environment and uniform active site are matched with the supported metal platinum and the metal-carrier interaction, so that the catalyst has excellent catalytic activity and stability, and is applied to unsaturated alcohol selection in the reaction of synthesizing unsaturated alcohol by the selective hydrogenation of unsaturated aldehydeHigh performance and high metal utilization rate.
Compared with the existing nano catalyst, the high-dispersion metal platinum catalyst provided by the invention not only can improve the metal utilization rate and reduce the catalyst preparation cost, but also has obviously changed geometric and electronic structures, so that the catalyst has a series of properties different from the nano catalyst, and has higher thermal stability after being subjected to high-temperature roasting treatment in the preparation process, and the phenomenon of catalyst deactivation caused by agglomeration of metal particles is not easy to occur under the reaction condition.
2) The 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 five-coordination Al in coordination unsaturated state 3+ The catalyst can be used as an anchor point of high-dispersion metal and used for fixing high-dispersion platinum atoms or platinum nanoclusters, and has higher hydrogenation activity and unsaturated alcohol selectivity in unsaturated aldehyde hydrogenation reaction as a high-dispersion supported platinum catalyst capable of catalyzing unsaturated aldehyde selective hydrogenation to synthesize unsaturated alcohol. The utilization rate of the high-dispersion platinum catalyst metal in the invention is close to 100%, and the catalytic sites are highly uniform.
3) According to the preparation method of the metal platinum catalyst, mesoporous alumina synthesized by a sol-gel method is used as a carrier, precious metal platinum is loaded on the mesoporous alumina by an isovolumetric impregnation method, and the mesoporous alumina loaded high-dispersion platinum catalyst is obtained through roasting and reduction treatment. The catalyst has higher catalytic activity and cinnamyl alcohol selectivity in the reaction of synthesizing the cinnamyl alcohol by selective hydrogenation of the cinnamyl aldehyde. The catalyst has the advantages of simple synthesis process, convenient operation and easy mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b);
FIG. 2 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Is an electron microscope image of (a): (a) a HAADF-STEM map, (b) a O, al and Pt three element map in HAADF-STEM mode, (c) an Al element map in HAADF-STEM mode, (d) an O element map in HAADF-STEM mode, and (e) a Pt element map in HAADF-STEM mode;
FIG. 3 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Spherical aberration electron microscope images at different magnifications;
FIG. 4 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Catalytic performance in cinnamaldehyde hydrogenation;
FIG. 5 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b);
FIG. 6 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 A spherical aberration electron microscope image of different parts;
FIG. 7 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 Catalytic performance in cinnamaldehyde hydrogenation reactions.
FIG. 8 is a catalyst of comparative example 1, 0.1wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b);
FIG. 9 is a comparative example 1 catalyst 0.1wt% Pt/Al 2 O 3 Is a spherical aberration electron microscope image;
FIG. 10 is a catalyst of comparative example 1, 0.1wt% Pt/Al 2 O 3 Catalytic performance in cinnamaldehyde hydrogenation;
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
This example provides a metal platinum catalyst (0.01 wt% Pt/Al 2 O 3 ) The catalyst carrier is mesoporous alumina, the active component is metal platinum, and the loading capacity of the metal platinum is 0.01wt%;
the preparation method of the metal platinum catalyst comprises the following steps:
s1, preparing a mesoporous alumina carrier by adopting a sol-gel method: 4.2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, PEO-PPO-PEO) was dissolved in 40mL of ethanol to form a solution A; 6.4mL of nitric acid with 67% mass fraction and 8.16g of aluminum isopropoxide are dissolved 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 at 25 ℃ for 48 hours, and then placing the mixed solution into a blast drying oven at 60 ℃ for drying for 48 hours; roasting the dried gel in a muffle furnace at a heating rate of 1 ℃/mi1, a roasting temperature of 400 ℃ and a roasting time of 4 hours, and naturally cooling to room temperature after roasting to obtain the mesoporous alumina.
S2, preparing a metal platinum-containing solution: will H 2 PtCl 6 ·6H 2 O is dissolved in ethanol to obtain a solution containing metal platinum, and the concentration is 19.3mmol/L;
s3, preparing a mesoporous alumina loaded high-dispersion platinum catalyst by adopting an isovolumetric impregnation method: diluting 0.05mL of the metal-containing platinum solution prepared in the step S2 to 1.5mL with water to obtain a diluted metal-containing platinum solution (the concentration of metal platinum is 0.643 mmol/L); dripping 1.5mL of the diluted solution containing the metal platinum into 2.0g (the pore volume is 1.5 mL) of the mesoporous alumina carrier obtained in the step S1, fully and uniformly stirring the mixture by using a glass rod, and carrying out ultrasonic treatment on the obtained mixture, wherein the ultrasonic power is 200W, the ultrasonic treatment time is 2h, so that the metal precursor is uniformly distributed in the pore channels of the carrier; aging the mixture at 25 ℃ for 12 hours after the ultrasonic treatment is finished, and then drying the mixture in an 80 ℃ blast drying oven for 12 hours; transferring the dried mixture into a muffle furnace for roasting, wherein the heating rate is 1 ℃/mi1, the roasting temperature is 400 ℃, the roasting time is 4 hours, and naturally cooling to room temperature after roasting; finally, reducing gas with the flow rate of 50mL/mi1 (reducing gas is changed from H 2 And N 2 The composition, wherein the volume ratio of hydrogen is 20 percent, is reduced at 400 ℃ for 3 hours to obtain the metal platinum catalyst (0.01 weight percent Pt/Al) 2 O 3 )。
Performance verification
FIG. 1 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b);
as can be seen from FIG. 1, the catalyst has an isothermal line of type IV, H 2 A hysteresis loop indicating that the catalyst is a mesoporous material; the specific surface area 371m of the catalyst was calculated by the Bru auer-Emmett-Teller (BET) method 2 /g; the pore diameter and pore volume of the catalyst were calculated to be 7.0.1 m and 0.68cm, respectively, using the Barrett-Joy1er-Hale1da (BJH) method 3 /g。
FIG. 2 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Is an electron microscope image of (a): (a) a HAADF-STEM map, (b) a O, al and Pt three element map in HAADF-STEM mode, (c) an Al element map in HAADF-STEM mode, (d) an O element map in HAADF-STEM mode, and (e) a Pt element map in HAADF-STEM mode; it can be seen from FIG. 2 that the metal Pt is uniformly distributed in Al 2 O 3 And (3) on a carrier.
FIG. 3 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Spherical aberration electron microscope images at different magnifications; in fig. 3, isolated bright spots appear, indicating that the metallic platinum exists in the form of a single atom.
FIG. 4 is a high dispersion Pt catalyst synthesized in example 1, 0.01wt% Pt/Al 2 O 3 Catalytic performance in cinnamaldehyde hydrogenation; the reaction conditions were 0.3g of the reactant cinnamaldehyde, 30mL of solvent ethanol, 0.3g of catalyst 0.01wt% Pt/Al 2 O 3 The reaction temperature is 80 ℃, and the hydrogen pressure is 3.0MPa; as can be seen from the reaction results of FIG. 4, the selectivity of cinnamyl alcohol was as high as 97.6% when the conversion rate of cinnamyl aldehyde was 98%.
Example 2
This example provides a metal platinum catalyst (0.02 wt% Pt/Al 2 O 3 ) The catalyst carrier is mesoporous alumina, the active component is metal platinum, and the loading capacity of the metal platinum is 0.02wt%;
the preparation method of the metal platinum catalyst comprises the following steps:
s1, preparing a mesoporous alumina carrier by adopting a sol-gel method: 4.2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, PEO-PPO-PEO) was dissolved in 40mL of ethanol to form a solution A; 6.4mL of nitric acid with 67% mass fraction and 8.16g of aluminum isopropoxide are dissolved 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 at 25 ℃ for 48 hours, and then placing the mixed solution into a 40 ℃ blast drying box for drying for 72 hours; roasting the dried gel in a muffle furnace at a heating rate of 3 ℃/mi1 and a roasting temperature of 350 ℃ for 5 hours, and naturally cooling to room temperature after roasting to obtain the mesoporous alumina.
S2, preparing a platinum solution containing noble metals: will H 2 PtCl 6 ·6H 2 O is dissolved in ethanol to obtain a solution containing metal platinum, and the concentration is 19.3mmol/L;
s3, preparing a mesoporous alumina loaded high-dispersion platinum catalyst by adopting an isovolumetric impregnation method: 0.10mL of the metal-containing platinum prepared in step S2 was reacted withDiluting the solution with water to 1.5mL to obtain a diluted metal platinum-containing solution (the concentration of the metal platinum is 1.287 mmol/L); dripping 1.5mL of the diluted solution containing the metal platinum into 2.0g (the pore volume is 1.5 mL) of the mesoporous alumina carrier obtained in the step S1, fully and uniformly stirring the mixture by using a glass rod, and carrying out ultrasonic treatment on the obtained mixture, wherein the ultrasonic power is 200W, the ultrasonic treatment time is 2h, so that the metal precursor is uniformly distributed in the pore channels of the carrier; aging the mixture at 25 ℃ for 12 hours after the ultrasonic treatment is finished, and then drying the mixture in a 100 ℃ blast drying oven for 8 hours; transferring the dried mixture into a muffle furnace for roasting, wherein the heating rate is 3 ℃/mi1, the roasting temperature is 350 ℃, the roasting time is 5 hours, and naturally cooling to room temperature after roasting; finally, reducing gas with the flow rate of 50mL/mi1 (reducing gas is changed from H 2 And N 2 The composition, wherein the volume ratio of hydrogen is 20 percent, is reduced at the temperature of 450 ℃ for 4 hours to obtain the metal platinum catalyst (0.02 wt percent Pt/Al) 2 O 3 )。
FIG. 5 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b); as can be seen from FIG. 5, the catalyst has an isothermal line of type IV, H 2 A hysteresis loop indicating that the catalyst is a mesoporous material; calculation of the specific surface area 362m of the catalyst by BET method 2 /g; the pore diameter and pore volume of the catalyst were calculated to be 6.61m and 0.61cm, respectively, using the BJH method 3 /g。
FIG. 6 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 A spherical aberration electron microscope image of different parts; some isolated bright spots appear in fig. 6, indicating that the metallic platinum exists in the form of a single atom.
FIG. 7 is a high dispersion Pt catalyst synthesized in example 2, 0.02wt% Pt/Al 2 O 3 Catalytic Performance in cinnamaldehyde hydrogenation reaction under reaction conditions of 0.3g reactant cinnamaldehyde, 30mL solvent ethanol, 0.15g catalyst 0.02wt% Pt/Al 2 O 3 The reaction temperature is 90 ℃, and the hydrogen pressure is 4.0MPa; as can be seen from the reaction results of fig. 7, when the conversion rate of cinnamaldehyde is 71%, the selectivity of cinnamyl alcohol is as high as 89.7%.
Comparative example 1
This comparative example provides a metal platinum catalyst of 0.1wt% Pt/Al 2 O 3 The only difference from example 1 is that the catalyst support was selected from commercially available mesoporous alumina (available from Alfa Aesar company, particle size 40-80 mesh) with Pt loading of 0.1wt%; other preparation conditions were the same as in example 1.
FIG. 8 is a catalyst of comparative example 1, 0.1wt% Pt/Al 2 O 3 Nitrogen adsorption and desorption curves (a) and pore size distribution curves (b); as can be seen from FIG. 8, the catalyst has an isothermal line of type IV, H 2 A hysteresis loop indicating that the catalyst is a mesoporous material; calculation of the specific surface area 264m of the catalyst by BET method 2 /g; the pore diameter and pore volume of the catalyst were calculated to be 5.71m and 0.38cm, respectively, using the BJH method 3 And/g. FIG. 9 is a comparative example 1 metallic platinum catalyst 0.1wt% Pt/Al 2 O 3 From the spherical aberration electron microscope of (2), it can be seen that the metal Pt is distributed on the alumina carrier in the form of nano particles, and the distribution range of particle size is wider.
The test was conducted under the same reaction conditions as in example 1, with the catalyst of this comparative example being 0.1wt% Pt/Al 2 O 3 In the unsaturated aldehyde hydrogenation reaction, the selectivity to the target unsaturated alcohol is low, and when the conversion rate of cinnamaldehyde is 20.7%, the selectivity to cinnamyl alcohol is only 34.5%, and the result is shown in fig. 10.
In conclusion, the mesoporous alumina prepared by the sol-gel method is in the coordination unsaturated state of penta-coordination Al 3+ The method has the advantages of interaction with metal atoms, synthesis of a high-dispersion platinum catalyst by using an impregnation method, simple operation and easy mass production.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The application of a metal platinum catalyst in preparing cinnamyl alcohol by selectively hydrogenating cinnamyl aldehyde is characterized in that a carrier of the catalyst is mesoporous alumina, an active component is metal platinum, and the mesoporous alumina is prepared by a sol-gel method;
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.
2. Use according to claim 1, characterized in that the loading of metallic platinum is 0.01-0.02wt%.
3. The use according to claim 1, wherein,
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 proportion relation is g/mL;
in the step 2), the ratio of the inorganic acid, aluminum alkoxide and 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 4-5h.
4. The use according to claim 1, 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.
5. The use according to claim 1, characterized in that the metallic platinum is supported on a mesoporous alumina support in the form of nanoclusters or monoatoms.
6. The use according to any one of claims 1 to 5, wherein the preparation method of the metal platinum catalyst comprises the steps of:
s1, preparing mesoporous alumina;
s2, mixing a metal platinum precursor and an organic alcohol solvent to prepare a metal platinum-containing solution;
and S3, mixing and impregnating the metal platinum-containing solution and the mesoporous alumina by adopting an impregnation method to load the metal platinum on the mesoporous alumina, and then roasting and reducing to obtain the metal platinum catalyst.
7. The use according to claim 6, wherein the metal platinum concentration of the metal platinum-containing solution in step S2 is 18-20mmol/L and the metal platinum precursor is chloroplatinic acid;
the impregnation method in step S3 is an isovolumetric impregnation method.
8. The use according to claim 6, wherein in step S3 the metal-containing platinum solution is diluted with water to the same volume as the mesoporous alumina, and then the diluted metal-containing platinum solution is mixed with the mesoporous alumina and stirred, and the obtained mixture is subjected to ultrasonic treatment, aging, drying and calcination to obtain the metal platinum catalyst.
9. The use according to claim 8, wherein in step S3, the ultrasound power is 100-250W and the ultrasound time is 2-3h; the aging temperature is 20-30 ℃ and the aging time is 8-12h; the drying temperature is 80-100 ℃ and the drying time is 8-12h; roasting at 350-450 deg.c for 4-5 hr; the reduction temperature is 350-450 ℃, and the reduction time is 3-5h.
10. The use according to claim 1, wherein the reaction temperature for the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol is 70-90 ℃ and the hydrogen pressure is 3.0-4.0MPa.
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