CN114230469A - Synthesis of load type nano ruthenium zirconium tin composite oxide and application of load type nano ruthenium zirconium tin composite oxide in benzylamine synthesis through benzaldehyde amination - Google Patents

Synthesis of load type nano ruthenium zirconium tin composite oxide and application of load type nano ruthenium zirconium tin composite oxide in benzylamine synthesis through benzaldehyde amination Download PDF

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CN114230469A
CN114230469A CN202111545913.8A CN202111545913A CN114230469A CN 114230469 A CN114230469 A CN 114230469A CN 202111545913 A CN202111545913 A CN 202111545913A CN 114230469 A CN114230469 A CN 114230469A
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ruthenium
zirconium
tin
benzylamine
composite oxide
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CN114230469B (en
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黄家辉
张少华
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/624—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with germanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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Abstract

The invention discloses a synthesis of a load type nano ruthenium-zirconium-tin composite oxide and a method for synthesizing benzylamine by applying the load type nano ruthenium-zirconium-tin composite oxide in benzylamine amination synthesis, wherein benzaldehyde, an amination reagent and hydrogen are used as raw materials, and benzylamine is prepared by hydrogenation amination reaction under the action of a catalyst; the catalyst comprises an active component and a carrier, wherein the active component is composite nano ruthenium-zirconium-tin oxide particles, and the molar ratio of Ru to Zr to Sn is (0.01-10) to (1-20); the carrier is at least one of alumina and silicon dioxide. The ruthenium-zirconium-tin composite oxide prepared by the method has fine crystal grains, and an active center is increased; the interaction between the carrier and the metal composite oxide enhances the contact area with reactants and improves the reaction yield; the method has simple and feasible process and is easy for large-scale preparation.

Description

Synthesis of load type nano ruthenium zirconium tin composite oxide and application of load type nano ruthenium zirconium tin composite oxide in benzylamine synthesis through benzaldehyde amination
Technical Field
The invention belongs to the field of catalysis, and particularly relates to synthesis of a supported nano ruthenium-zirconium-tin composite oxide and application of the supported nano ruthenium-zirconium-tin composite oxide in benzylamine synthesis by benzaldehyde amination.
Background
Benzylamine is a very important organic intermediate, which is widely usedThe preparation of dyes, pesticides, medicines, and other chemicals can be widely applied to synthetic drugs (medicines and pesticides), dyes, artificial resins, anticorrosion inhibitors and functional additives, explosives, chemical reagents, and CO2Absorbent, curing agent (stabilizer) for curing rubber and plastics, such as intermediate for preparing insecticide imidacloprid and acetamiprid, and intermediate for preparing medicine sulfamylon.
The industrial production method of benzylamine in China mainly comprises the following steps: halide ammonolysis, hydroammoniation, nitrile hydrogenation, aminolysis of alcohol compounds, etc. The halohydrocarbon ammonolysis is not adopted at home and abroad due to serious equipment corrosion and three wastes, low yield and poor product quality, but is mainly produced by a clean process such as a hydroammonia process and the like, and the method has high reaction pressure, so that the production cost of the benzylamine is increased, and the yield of the benzylamine is not high.
The benzyl chloride (chlorobenzyl) ammoniation method is used for industrial production. The technical process of chloridebenzylation ammoniation is as follows: adding a mixture of ethanol, benzyl chloride and urotropine (ammonium hydroxide or ammonium bicarbonate can be used for replacing the ethanol, benzyl chloride and urotropine) into a reaction kettle, reacting at the temperature of 30-35 ℃ for 4 hours, adding hydrochloric acid, reacting at the temperature of 45-50 ℃ for 2 hours, cooling, filtering, removing ethanol, distilling under reduced pressure, and adding an alkali solution to free benzylamine. The reaction process has the participation of acid and alkali, which means that the requirement on equipment is high, and the process has complicated steps and complicated process.
The large theory of continuous engineering is in the benzaldehyde ammoniation hydrogenation method which takes Raney Ni catalyst as catalyst, the synthesis steps of benzylamine are less, the efficiency is high, but the yield of benzylamine is up to 84%, and the reaction is completed under the high pressure condition of 7.5 MPa.
Kliger et al prepared benzylamine by benzyl alcohol amination over Fe catalyst. Ammonia gas is used as reaction gas in the two preparation processes of benzaldehyde ammoniation and benzyl alcohol ammoniation, and the benzylamine yield of the two preparation processes is generally low (75-84%).
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a synthesis method of a supported nano ruthenium-zirconium-tin composite oxide, and the supported nano ruthenium-zirconium-tin composite oxide is used for catalyzing benzaldehyde to be hydrogenated and aminated to prepare benzylamine. The preparation method of the catalyst provided by the invention is simple and easy to operate, and the catalyst is used for catalyzing the amination of benzaldehyde to synthesize aniline, and compared with the traditional catalyst, the catalyst has the advantages of relatively mild reaction temperature and relatively high yield.
The technical scheme of the invention is as follows:
a method for synthesizing benzylamine comprises using benzaldehyde, amination reagent and hydrogen as raw materials, and preparing benzylamine by hydrogenation amination reaction under the action of catalyst; the catalyst comprises an active component and a carrier, wherein the active component comprises composite nano ruthenium-zirconium-tin oxide particles, and the molar ratio of Ru to Zr to Sn is (0.01-10) to (1-20); the carrier comprises at least one of alumina and silica, and the mass ratio of the composite oxide to the carrier is 1-20%. The general procedure for benzylamine synthesis was: adding benzaldehyde, a catalyst and a solvent into a reaction kettle at a certain temperature, introducing excessive ammonia gas and hydrogen gas, reacting for a certain time, and analyzing a reaction product.
Based on the scheme, the particle size of the ruthenium-zirconium-tin oxide particles is preferably in the range of 1nm to 20nm, and the molar ratio of Ru to Zr to Sn is (1-5) to (1-5); the alumina comprises alpha-Al2O3、β-Al2O3、γ-Al2O3And at least one of amorphous alumina, wherein the silica comprises at least one of microporous silica and mesoporous silica, and the mass ratio of the composite oxide to the carrier is 5-15%.
Based on the scheme, preferably, the alumina is gamma-Al2O3(ii) a The silicon oxide is mesoporous silicon dioxide.
Based on the scheme, preferably, the amination reagent is one of liquid ammonia or ammonia gas, the reaction takes alcohol or benzene series as a solvent, wherein the alcohol comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol, and the benzene series comprises one or more of benzene, toluene, ethylbenzene, xylene and trimethylbenzene.
Based on the scheme, preferably, the reaction temperature is 50-150 ℃, the reaction time is 1-24h, the pressure of hydrogen is 1-10MPa, and the molar weight ratio of the amination reagent to benzaldehyde is 1: 1-100: 1.
Based on the scheme, the reaction temperature is 110 ℃, the reaction time is 4h, the pressure of hydrogen is 3MPa, and the molar weight ratio of the amination reagent to the benzaldehyde is 10: 1.
Based on the scheme, the stirring speed is preferably 100-2000r/min during the reaction.
According to the preparation method of the catalyst, the supported nano ruthenium-zirconium-tin composite oxide catalyst is synthesized by adopting metal salt for co-reaction, adding the carrier for solidification, and roasting at high temperature to obtain the supported ruthenium-zirconium-tin composite oxide catalyst. The method specifically comprises the following steps:
(1) preparing a ruthenium-zirconium-tin mixed solution: respectively dissolving ruthenium salt, zirconium salt and tin salt in a mixed solvent of alcohol and water, and mixing after dissolving to obtain a ruthenium-zirconium-tin mixed solution;
(2) and adding a carrier into the mixed solution for impregnation, drying and roasting after a period of time to obtain the catalyst.
Based on the scheme, preferably, in the step (1), the ruthenium salt is one or more of ruthenium trichloride, tris (triphenylphosphine) ruthenium dichloride and ruthenium acetylacetonate compounds, the zirconium salt is zirconium oxychloride or zirconium tetrachloride, the tin salt is one or more of tin dichloride, tin tetrachloride, stannous sulfate or stannous nitrate, the alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol, and the molar ratio of the alcohol to the water is 5: 1-1: 5; in the step (2), the dipping time is 4-24h, the drying temperature is 50-150 ℃, the roasting temperature is 300-600 ℃, and the roasting time is 2-6 h.
Based on the scheme, preferably, in the step (1), the ruthenium salt is ruthenium trichloride, the zirconium salt is ruthenium tetrachloride, the tin salt is tin tetrachloride, the ratio of the alcohol to the water is 2: 1-1: 2, in the step (2), the impregnation time is 12 hours, the drying temperature is 80-100 ℃, the roasting temperature is 400-500 ℃, and the roasting time is 4 hours.
Advantageous effects
The nanometer ruthenium zirconium tin oxide particles prepared by the mixed curing method are used as active components, are loaded on the oxide carrier with high specific surface area, and are used for catalyzing the reaction of preparing benzylamine by hydrogenating and aminating benzaldehyde, and the method has the following advantages: (1) firstly, the prepared ruthenium-zirconium-tin composite oxide has fine crystal grains and increases an active center; (2) the active components are mutually synergistic, the ruthenium can effectively activate hydrogen and promote hydrogenation, the tin metal is beneficial to imine activation and improves amination selectivity, and the zirconium oxide active component plays an important role in absorbing reactants to better react on the surfaces of the ruthenium and the tin metal; (3) the interaction between the carrier and the metal composite oxide enhances the contact area with reactants and improves the reaction yield; (4) simple process, easy operation and easy large-scale preparation.
Detailed Description
Comparative example 1
0.2093g of ruthenium trichloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silicon dioxide is added, and the mixture is soaked for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst A1 was obtained.
Comparative example 2
0.2093g of ruthenium trichloride and 0.2330g of zirconium chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst A2 was obtained.
Example 1
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst A was obtained.
Example 2
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of ethanol and water solution, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, and 5g of alpha-Al is added2O3The support was immersed at room temperature for 12 hours with stirring. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst B was obtained.
Example 3
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 4: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst C was obtained.
Example 4
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 120 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst D was obtained.
Example 5
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 600 ℃ for 4 hours. Catalyst E was obtained.
Example 6
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of a solution of propanol and water, wherein the ratio of the propanol to the water is 2: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst F was obtained.
Example 7
0.3984g of ruthenium acetylacetonate, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of a solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after full dissolution, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours at room temperature under stirring. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst G was obtained.
Example 8
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 69.78g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst H was obtained.
Example 9
0.2093g of ruthenium trichloride, 0.2330g of zirconium chloride and 0.3506g of stannic chloride are weighed and respectively dissolved in a solution of 3m1 of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 3.48g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst I is obtained.
Example 10
0.2093g of ruthenium trichloride, 0.4660g of zirconium chloride and 0.7012g of stannic chloride are weighed and respectively dissolved in 3ml of solution of ethanol and water, wherein the ratio of ethanol to water is 1: 1, the three solutions are mixed after being fully dissolved, 6.978g of carrier mesoporous silica is added, and the mixture is immersed for 12 hours under stirring at room temperature. Thereafter, the mixture was dried in an oven at 80 ℃ for 12 hours and finally calcined in a muffle furnace at 400 ℃ for 4 hours. Catalyst J was obtained.
Comparative example 3
0.05g of the catalyst prepared in comparative example 1, 1g of benzaldehyde and 20g of methanol were added together to a reaction kettle, air in the reaction kettle was replaced three times with hydrogen, 3MPa of hydrogen was charged, and finally 6g of liquid ammonia was added, with a stirring speed of 500r/min and a reaction temperature of 110 ℃. The reaction was found to be 4h with 72.2% benzaldehyde conversion and 48.6% benzylamine selectivity.
Comparative example 4
0.05g of the catalyst prepared in example 2, 1g of benzaldehyde and 20g of methanol are added into a reaction kettle together, air in the reaction kettle is replaced by hydrogen for three times, 3MPa of hydrogen is filled, and finally 6g of liquid ammonia is added, the stirring speed is 500r/min, and the reaction temperature is 110 ℃. The reaction was found to be 4h with 80.1% benzaldehyde conversion and 67.4% benzylamine selectivity.
Example 11
0.05g of the catalyst prepared in example 1, 1g of benzaldehyde and 20g of methanol are added into a reaction kettle together, air in the reaction kettle is replaced by hydrogen for three times, 3MPa of hydrogen is filled, and finally 6g of liquid ammonia is added, the stirring speed is 500r/min, and the reaction temperature is 110 ℃. The reaction was found to be 4h with 86.1% benzaldehyde conversion and 89.6% benzylamine selectivity.
Example 12
0.05g of the catalyst prepared in example 2, 1g of benzaldehyde and 20g of methanol are added into a reaction kettle together, air in the reaction kettle is replaced by hydrogen for three times, 3MPa of hydrogen is filled, and finally 6g of liquid ammonia is added, the stirring speed is 500r/min, and the reaction temperature is 110 ℃. The reaction was found to be 4h with a benzaldehyde conversion of 87.5% and benzylamine selectivity of 90.3%.
Example 13
0.05g of the catalyst prepared in example 5, 1g of benzaldehyde and 20g of methanol were added together to a reaction kettle, air in the reaction kettle was replaced three times with hydrogen, 3MPa of hydrogen was charged, and finally 6g of liquid ammonia was added, with a stirring speed of 500r/min and a reaction temperature of 140 ℃. The reaction was found to be 4h with 84.8% benzaldehyde conversion and 89.1% benzylamine selectivity.
Example 14
0.05g of the catalyst prepared in example 8, 1g of benzaldehyde and 20g of methanol were added together to a reaction kettle, air in the reaction kettle was replaced three times with hydrogen, 3MPa of hydrogen was charged, and finally 30g of liquid ammonia was added, with a stirring speed of 500r/min and a reaction temperature of 110 ℃. The reaction was found to be 4h with a benzaldehyde conversion of 36.3 and benzylamine selectivity of 80.5%.
Example 15
0.05g of the catalyst prepared in example 9, 1g of benzaldehyde and 20g of methanol were added together to a reaction kettle, air in the reaction kettle was replaced three times with hydrogen, 1MPa of hydrogen was charged, and finally 6g of liquid ammonia was added, with stirring speed of 500r/min and reaction temperature of 110 ℃. The reaction was found to be 4h with 96.7% benzaldehyde conversion and 98.9% benzylamine selectivity.
Example 16
0.05g of the catalyst prepared in example 10, 1g of benzaldehyde and 20g of methanol were added together to a reaction kettle, air in the reaction kettle was replaced three times with hydrogen, 1MPa of hydrogen was charged, and finally 6g of liquid ammonia was added, with a stirring speed of 500r/min and a reaction temperature of 110 ℃. The reaction was found to be 4h with 95.9% benzaldehyde conversion and 96.8% benzylamine selectivity.

Claims (10)

1. A method for synthesizing benzylamine is characterized in that benzaldehyde, an amination reagent and hydrogen are used as raw materials, and benzylamine is prepared through a hydrogenation amination reaction under the action of a catalyst; the catalyst comprises an active component and a carrier, wherein the active component comprises composite nano ruthenium-zirconium-tin oxide particles, and the molar ratio of Ru to Zr to Sn is (0.01-10) to (1-20); the carrier comprises at least one of alumina and silica, and the mass ratio of the composite oxide to the carrier is 1-20%.
2. The method of synthesizing benzylamine according to claim 1, wherein the ruthenium-zirconium-tin oxide particles have a particle size in a range of 1nm to 20nm, and the ruthenium-zirconium-tin oxide particles are RuThe mol ratio of Zr to Sn is (1-5) to (1-5); the alumina comprises alpha-Al2O3、β-Al2O3、γ-Al2O3And at least one of amorphous alumina, wherein the silica comprises at least one of microporous silica and mesoporous silica, and the mass ratio of the composite oxide to the carrier is 5-15%.
3. The method of synthesizing benzylamine according to claim 2, wherein the alumina is γ -Al2O3(ii) a The silicon oxide is mesoporous silicon dioxide.
4. The method for synthesizing benzylamine according to claim 1, wherein the amination reagent is one of liquid ammonia and ammonia gas, and the reaction uses alcohol or benzene series as solvent, wherein the alcohol includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol, and the benzene series includes one or more of benzene, toluene, ethylbenzene, xylene, and trimethylbenzene.
5. The process for synthesizing benzylamine according to claim 1, wherein the reaction temperature is 50 to 150 ℃, the reaction time is 1 to 24 hours, the pressure of hydrogen is 1 to 10MPa, and the molar ratio of the amination reagent to benzaldehyde is 1: 1 to 100: 1.
6. The method of synthesizing benzylamine according to claim 5, wherein the reaction temperature is 110 ℃ and the reaction time is 4 hours, the pressure of hydrogen is 3MPa, and the molar ratio of the amination reagent to benzaldehyde is 10: 1.
7. The method for synthesizing benzylamine according to claim 1, wherein the stirring speed during the reaction is 100-2000 r/min.
8. A method for preparing the catalyst of any of the methods of claims 1-3, wherein: the method comprises the following steps:
(1) preparing a ruthenium-zirconium-tin mixed solution: respectively dissolving ruthenium salt, zirconium salt and tin salt in a mixed solvent of alcohol and water, and mixing after dissolving to obtain a ruthenium-zirconium-tin mixed solution;
(2) and adding a carrier into the mixed solution for impregnation, drying and roasting after a period of time to obtain the catalyst.
9. The preparation method according to claim 8, wherein in the step (1), the ruthenium salt is one or more of ruthenium trichloride, ruthenium tris (triphenylphosphine) dichloride and ruthenium acetylacetonate, the zirconium salt is zirconium oxychloride or zirconium tetrachloride, the tin salt is one or more of tin dichloride, tin tetrachloride, stannous sulfate or stannous nitrate, the alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol, and the molar ratio of the alcohol to the water is 5: 1-1: 5; in the step (2), the dipping time is 4-24h, the drying temperature is 50-150 ℃, the roasting temperature is 300-600 ℃, and the roasting time is 2-6 h.
10. The method according to claim 9, wherein in the step (1), the ruthenium salt is ruthenium trichloride, the zirconium salt is ruthenium tetrachloride, the tin salt is tin tetrachloride, the ratio of the alcohol to the water is 2: 1 to 1: 2, the impregnation time in the step (2) is 12 hours, the drying temperature is 80 to 100 ℃, the calcination temperature is 400-500 ℃, and the calcination time is 4 hours.
CN202111545913.8A 2021-12-15 2021-12-15 Synthesis of supported nano ruthenium zirconium tin composite oxide and application of supported nano ruthenium zirconium tin composite oxide in synthesis of benzylamine through amination of benzaldehyde Active CN114230469B (en)

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