CN114618518A - Supported bimetallic catalyst and preparation and application thereof - Google Patents
Supported bimetallic catalyst and preparation and application thereof Download PDFInfo
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- CN114618518A CN114618518A CN202011456203.3A CN202011456203A CN114618518A CN 114618518 A CN114618518 A CN 114618518A CN 202011456203 A CN202011456203 A CN 202011456203A CN 114618518 A CN114618518 A CN 114618518A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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Abstract
The invention relates to a preparation method of a supported bimetallic catalyst. The catalyst is a bimetallic single-atom catalyst which is rich in unsaturated coordination alumina load, wherein one metal is noble metal such as Ru, Rh, Pd and the like, and the other metal is non-noble metal such as Fe, Bi, Cu, Co and the like. The catalyst is suitable for selective hydrogenation reaction, shows excellent hydrogenation activity and selectivity, and is simple to operate and easy to realize.
Description
Technical Field
The invention relates to a preparation method of a supported bimetallic catalyst, in particular to a bimetallic monatomic catalyst supported by alumina rich in unsaturated coordination, which is widely used in a selective hydrogenation reaction process.
Background
Catalysis is the pillar of modern chemistry and is a crucial field in modern chemistry and chemical engineering. 85% of chemical industrial reactions all over the world are carried out under the action of catalysts, and the catalysts with high activity, high selectivity and long service life have great contribution to the aspects of reducing raw material and energy consumption, improving production economy, preventing environmental pollution and the like. In order to obtain the supported metal catalyst meeting the actual production requirement, a catalyst modification method for regulating and controlling the morphology and the size of metal particles and the carrier energy is developed. However, single metal component catalysts still have difficulty meeting the ever-increasing demands of catalytic applications. The second metal is used for forming a bimetal structure, and the performance of the catalyst can be effectively improved through the synergistic effect of the two metals. Thus, bimetallic catalysts have led to extensive research in the field of catalysis. At present, the preparation of the bimetallic catalyst generally has the defects of low catalyst activity, low utilization rate of active metal, high cost, inconvenience for large-scale production, popularization and application and the like. Therefore, it is necessary to develop a preparation method of a bimetallic catalyst with high activity and high metal utilization rate, and to apply the method reasonably.
Disclosure of Invention
The invention aims to solve the technical problems of low activity, low utilization rate of active metal and complicated preparation process of the supported bimetallic catalyst in the prior art, and provides a preparation method of the supported bimetallic catalyst, which is simple to operate and has the utilization rate of the active metal component close to 100 percent. In addition, the supported bimetallic catalyst prepared by the invention can be applied to hydrogenation reaction and shows excellent activity and selectivity.
Based on the purpose, the invention adopts the technical scheme that:
a preparation method of a supported bimetallic catalyst mainly comprises the following steps:
A) mixing a surfactant, nitrate and/or chloride of non-noble metal Fe, Co, Bi or Cu, acid, an aluminum source and alcohol to prepare a non-noble metal alcohol solution;
B) mixing acid, an aluminum source and alcohol to prepare an alcohol solution;
C) mixing the alcoholic solutions obtained in the step A) and the step B), and then continuously stirring for 2-10 hours;
D) evaporating the alcohol solvent of the solution obtained in the step C), and then continuing aging for 36-72 h;
E) roasting the solid substance obtained in the step D); obtaining a solid sample;
F) loading precious metals such as Ru, Rh and Pd on the solid sample obtained in the step E) by adopting an isometric immersion method;
G) roasting and reducing the solid sample obtained in the step F); obtaining the unsaturated alumina supported bimetallic monatomic catalyst.
The raw materials in the steps A) and B) comprise the following components in parts by mass: 15-25 parts of surfactant, 30-40 parts of acid and 40-50 parts of aluminum source; the content of non-noble metal in the supported bimetallic catalyst is 0.5-5 wt%.
Wherein the surfactant is one or the combination of more than two of nonionic surfactants P123, F127 and F68;
the acid is one or the combination of more than two of concentrated nitric acid, oxalic acid, citric acid and malic acid with the mass concentration of 65%;
the aluminum source is one or the combination of more than two of aluminum nitrate, aluminum chloride, aluminum isopropoxide and aluminum sec-butoxide;
the solvent alcohol is one or more of methanol, ethanol and propanol;
the molar concentration of aluminum in the solvent was 1 mol/L.
The active component precursor in the step F) is Ru-containing3+、Rh3+、Pd2+The soluble inorganic metal salt of (a); the content of the metal active component in the supported metal catalyst is 0.05-1 wt%.
The stirring time in the step C) is 2-10h, preferably 5-7 h; the evaporation and aging temperature of the solvent alcohol in the step D) is 50-80 ℃, preferably 60 ℃, and the aging time is 36-72h, preferably 48 h.
The temperature rising rate in the roasting of the steps E) and G) is 0.5-2 ℃/min, the temperature is raised from room temperature to the roasting temperature, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 h.
The reduction in step G) is a gas phase reduction; wherein the gas-phase reducing atmosphere is H2H with the volume content of 50-100%2/N2Mixed gas or H2The reduction temperature is 200-400 ℃ and the time is 1-4 h.
The loaded noble metal and non-noble metal components of the bimetallic monatomic catalyst rich in unsaturated coordination alumina prepared by the method are in monatomic dispersion scale, the utilization rate of active metal is close to 100%, and the activity and selectivity of the loaded bimetallic catalyst applied to selective hydrogenation of diene and selective hydrogenation of nitrostyrene are far higher than those of the bimetallic catalyst loaded on commercial alumina. In addition, the preparation method is simple to operate and easy to realize.
Detailed Description
To further illustrate the present invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1
a. Weighing 2.0g P123, dissolving in 20ml absolute ethyl alcohol, adding 18.9mg Bi (NO)3)3Stirring and dissolving to obtain an alcohol solution.
b. 3ml of concentrated nitric acid is added dropwise into 20ml of absolute ethyl alcohol, 4.08g of aluminum isopropoxide is added under vigorous stirring, and the mixture is stirred vigorously to completely dissolve the aluminum isopropoxide.
c. The alcoholic solutions obtained in a and b were mixed and vigorous stirring was continued for 6 h.
d. And (d) aging the solution obtained in the step (c) in an oven at 60 ℃ for 48 h.
e. Heating the solid in the step d to 400 ℃ at the speed of 1 ℃/min and roasting for 4h to obtain Bi/Al2O3,Al2O3The content of the medium unsaturated pentacoordinate Al is about 20 percent.
f. 12.8mgRhCl3·3H2O was dissolved in 0.7ml of water and added dropwise to 1gZn/Al2O3Drying the solid in a 120 deg.C oven for 12H, heating to 400 deg.C at 1 deg.C/min, calcining for 4H, and heating to 200 deg.C under high temperature2Reducing for 2h under atmosphere to obtain RhBi/Al2O3The catalyst has Rh loading of 0.5 wt% and Bi loading of 1 wt%, and Rh and Bi are dispersed in the catalyst in single atom scale and rich in Bi as shown by electron microscopeNot containing coordinated Al2O3The above.
Example 2
Except that 72.1mgFe (NO) was used in step a3)3·9H2O, prepared in the same manner as described in example 1 to give a bimetallic catalyst RhFe/Al2O3。
Example 3
Except that 46.2mCu (NO) was used in step a3)2·6H2O in addition, prepared in the same manner as described in example 1 to give a bimetallic catalyst RhCu/Al2O3。
Example 4
Except that 49.3mgCo (NO) was used in step a3)2·6H2O in addition, prepared in the same manner as described in example 1 to give a bimetallic catalyst RhCo/Al2O3。
Example 5
Except that 12.4mgPd (NH) was used in step f3)4Cl2In addition, the bimetallic catalyst PdBi/Al was obtained by the same method as that described in example 12O3。
Example 6
Except that 13.1mgRuCl was used in step f3·3H2O, prepared in the same manner as described in example 1, to give a bimetallic catalyst RuBi/Al2O3。
Example 7
The catalyst prepared in example 1 was used in the preparation of 10mg of RhBi/Al2O3Placing the mixture into a 50ml three-neck flask, carrying out pre-reduction for 1h at 200 ℃, cooling to room temperature, adding 5ml of tetrahydrofuran and 0.2mmol of 1, 4-hexadiene to react for 1h at 25 ℃, and detecting the hydrogenation result of the 1, 4-hexadiene by GC-FID to obtain the 1, 4-hexadiene with the hydrogenation conversion rate of 100% and the 2-hexene selectivity of 95%.
Comparative example 1
0.5 wt% Rh and 1 wt% Bi were loaded onto commercial Al using an isovolumetric impregnation method2O3As above, RhBi/Al was obtained under the same calcination and reduction conditions as in example 12O3Catalyst, active metal average particle size is 5 nm. The catalyst is applied to the selective hydrogenation reaction of 1, 4-hexadiene, and after 4 hours of reaction, the hydrogenation conversion rate of the 1, 4-hexadiene is 32 percent, and the selectivity of the 2-hexene is 30 percent.
Example 8
Prepared in the same manner as described in example 8, except that 1, 4-hexadiene was replaced with 2, 4-hexadiene, gave a 2, 4-hexadiene hydroconversion of 100% and a 2-hexene selectivity of 99%.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a supported bimetallic catalyst mainly comprises the following steps:
A) mixing a surfactant, nitrate and/or chloride of non-noble metal Fe, Co, Bi or Cu, acid, an aluminum source and alcohol, and then continuously stirring for 2-10 hours; the raw materials comprise the following components in parts by weight: 15-25 parts of surfactant, 30-40 parts of acid and 40-50 parts of aluminum source;
B) evaporating the alcohol solvent of the solution obtained in the step A) to dryness, and then continuing aging for 36-72 h;
C) roasting the solid substance obtained in the step B); obtaining a solid sample;
D) loading noble metals such as Ru, Rh or Pd on the solid sample obtained in the step C) by adopting an isometric impregnation method;
E) roasting and reducing the solid sample obtained in the step D); obtaining the unsaturated alumina supported bimetallic monatomic catalyst.
2. The method of claim 1, wherein: in the step A, the content of non-noble metal in the supported bimetallic catalyst is 0.5-5 wt%;
wherein the surfactant is one or the combination of more than two of nonionic surfactants P123, F127 and F68;
the acid is one or the combination of more than two of concentrated nitric acid, oxalic acid, citric acid and malic acid with the mass concentration of 65%;
the aluminum source is one or the combination of more than two of aluminum nitrate, aluminum chloride, aluminum isopropoxide and aluminum sec-butoxide;
the solvent alcohol is one or more of methanol, ethanol and propanol;
the molar concentration of the aluminum in the solvent is 0.5-3 mol/L.
3. The method of claim 1, wherein: the active component precursor in the step D) is Ru-containing3+、Rh3+Or Pd2+The soluble inorganic metal salt of (a); the content of the metal active component in the supported metal catalyst is 0.05-1 wt%.
4. The method of claim 1, wherein: the stirring time in the step A) is 2-10h, preferably 5-7 h; the evaporation and aging temperature of the solvent alcohol in the step B) is 50-80 ℃, preferably 60 ℃, and the aging time is 36-72h, preferably 48 h.
5. The method of claim 1, wherein: the temperature rising rate in the roasting of the steps C) and E) is 0.5-2 ℃/min, the temperature is raised from room temperature to the roasting temperature, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 h.
6. The method of claim 1, wherein: the reduction in step E) is a gas phase reduction; wherein the gas-phase reducing atmosphere is H2H with the volume content of 50-100%2/N2Mixed gas or H2The reduction temperature is 200-400 ℃ and the time is 1-4 h.
7. An unsaturated coordination alumina-rich bimetallic monatin catalyst obtained by the preparation method described in any one of claims 1 to 6.
8. The catalyst of claim 7 wherein the supported noble and non-noble metal components are both on a monoatomic dispersion scale.
9. A supported bimetallic catalyst as claimed in claim 7 or 8 for use in selective hydrogenation reactions.
10. The method of claim 9, wherein the supported bimetallic catalyst is used in diolefin hydrogenation reactions or nitrostyrene hydrogenation reactions.
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| CN103819295A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application of catalyst to selective hydrogenation reaction of aromatic nitro compound |
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| CN109806885A (en) * | 2019-01-07 | 2019-05-28 | 北京理工大学 | A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection |
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2020
- 2020-12-10 CN CN202011456203.3A patent/CN114618518B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN103084173A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | C4 fraction selective hydrogenation catalyst, preparation method and applications thereof |
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| WO2013175085A1 (en) * | 2012-05-24 | 2013-11-28 | IFP Energies Nouvelles | Process for preparing a catalyst based on a group viii metal and containing silicon and selective hydrogenation process using said catalyst |
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