CN109999821B - Preparation and application of surface-treated aluminum alloy catalyst - Google Patents

Preparation and application of surface-treated aluminum alloy catalyst Download PDF

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CN109999821B
CN109999821B CN201910186718.7A CN201910186718A CN109999821B CN 109999821 B CN109999821 B CN 109999821B CN 201910186718 A CN201910186718 A CN 201910186718A CN 109999821 B CN109999821 B CN 109999821B
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cyclohexene
aluminum alloy
reaction kettle
catalyst
pressure
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CN109999821A (en
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郝剑敏
张琳林
连旭
韩利民
魏晓贺
魏志强
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Inner Mongolia University of Technology
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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
    • B01J23/70—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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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Abstract

The invention relates to a preparation method and application of a surface-treated aluminum alloy catalyst. The surface treatment comprises surface alkali treatment and surface acid treatment, the aluminum alloy catalyst for the surface alkali treatment comprises the following components in molar ratio: al (Al)xCuyCo100‑x‑yThe value of x is 50-70, the value of y is 10-90-x, and the mass fraction of the NaOH solution is 0.1-20%; the aluminum alloy catalyst for surface acid treatment comprises the following components in molar ratio: al (Al)xCuyCr100‑x‑yX is 30-70, y is 10 to (90-x), and HNO is used3The mass fraction of the solution is 1-5%. The surface-treated aluminum alloy catalyst has the advantages of cheap and easily-obtained raw materials, simple integral preparation process, mild reaction conditions and environmental friendliness, is used for catalyzing cyclohexene oxidation reaction, and can effectively improve the conversion rate of cyclohexene or the selectivity of the product 2-cyclohexene-1-ketone by adjusting the components and the proportion in the aluminum alloy and the concentration of a surface treatment solution.

Description

Preparation and application of surface-treated aluminum alloy catalyst
Technical Field
The invention relates to a preparation method and application of a surface-treated aluminum alloy catalyst.
Background
Cyclohexene oxidation is an important reaction for converting olefin hydrocarbon into oxygen-containing derivatives such as epoxy compounds, alcohols, ketones, carboxylic acids, aldehydes and the like, and the obtained oxygen-containing derivatives can be used as organic chemical intermediates in the fine chemical fields such as pesticides, medicines, perfumes, surfactants, high molecular materials and the like, for example, products such as 2-cyclohexene-1-one, 2-cyclohexene-1-alcohol, cyclohexene oxide, adipic acid and the like can be used for producing perfumes, nylon-66, medicines and the like. The current oxidants for cyclohexene oxidation are mainly oxygen, hydrogen peroxide and tert-butyl hydroperoxide, among which oxygen is widely used because it is cheap and readily available. In chinese patents CN107051562A and CN104226313B published in 2017, a graphene-based cobalt carbonate catalyst and an electroless copper plating catalyst are prepared for catalyzing cyclohexene oxidation, but the overall preparation method is complex and the cost is high, so when developing a novel catalyst, a low-cost synthesis raw material and a simple and easy preparation method should be considered first.
The metal aluminum alloy is mainly used as a metal structure material in the fields of aviation, aerospace, automobiles, machinery and the like due to small density, corrosion resistance, good electric and thermal conductivity. However, in some aluminum alloys with special compositions and ratios, intermetallic compounds can be formed, and due to the special electronic structure and valence bond composition of the aluminum alloys, the intermetallic compounds have obvious room temperature brittleness, so that the aluminum alloys can be easily crushed into particles, and a large number of active sites are exposed through surface treatment, and the aluminum alloys can be used as catalytic functional materials. So far, no report that the metal aluminum alloy after surface treatment is used as a catalytic material for catalyzing cyclohexene oxidation is available at home and abroad. According to the invention, through simple acid-base treatment on the surface of part of the aluminum alloy, the surface of the aluminum alloy has good activity of catalyzing cyclohexene oxidation, the application field of part of the aluminum alloy is widened, and the catalytic functional utilization of part of the aluminum alloy is realized.
Disclosure of Invention
The invention aims to provide a preparation method of a surface-treated aluminum alloy catalyst and application of the surface-treated aluminum alloy catalyst in catalyzing cyclohexene oxidation.
The invention provides a preparation method of a surface-treated aluminum alloy catalyst, which comprises the following conditions and steps:
1, preparing the aluminum alloy catalyst with the alkali-treated surface. (1) Weighing 10g of mixture of aluminum, copper and cobalt metal raw materials according to a certain molar ratio, and placing the mixture in a vacuum arcAnd vacuumizing the cavity of the electric arc furnace on a copper bed of the furnace, introducing argon, repeatedly vacuumizing and introducing the argon for 3 times, and finally maintaining the pressure of the argon in the cavity to be 0.01-0.04 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 50-200A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles with the particle size of more than 500 meshes. The molar ratio of the aluminum to the copper to the cobalt alloy is as follows: al (Al)xCuyCo100-x-yThe value of x is 50 to 70, and the value of y is 10 to (90-x). (2) The prepared Al with the mass of 100-200 mgxCuyCo100-x-yPutting the alloy particles into a 200ml round-bottom flask, adding 50g of NaOH solution with the mass fraction of 0.1-20%, putting the round-bottom flask into a constant-temperature water bath at 35 ℃, stirring for 1-3 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surfacexCuyCo100-x-yAn alloy catalyst.
2, preparing the aluminum alloy catalyst with the acid treated surface. (1) Weighing 10g of mixture of aluminum, copper and chromium metal raw materials according to a certain molar ratio, placing the mixture on a copper bed of a vacuum arc furnace, vacuumizing a cavity of the arc furnace, introducing argon, repeatedly vacuumizing and introducing the argon for 3 times, and finally maintaining the pressure of the argon in the cavity to be 0.01-0.04 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 50-200A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles with the particle size of more than 500 meshes. The molar ratio of the aluminum to the copper to the chromium alloy is as follows: al (Al)xCuyCr100-x-yThe value of x is 30 to 70, and the value of y is 10 to (90-x). (2) The prepared Al with the mass of 100-200 mgxCuyCr100-x-yAlloy particles are put into 2Adding 50g of 1-5 mass percent HNO into a 00ml round bottom flask3Putting a round-bottom flask into a constant-temperature water bath at 30 ℃, and stirring for 1-3 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surfacexCuyCr100-x-yAn alloy catalyst.
The invention provides an application of a surface-treated aluminum alloy catalyst in catalyzing cyclohexene oxidation, and the conditions and the steps are as follows:
weighing 5ml of cyclohexene and a certain mass of catalyst, putting the cyclohexene and the catalyst into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to be stabilized at 70-80 ℃, filling oxygen with the pressure of 1-2 MPa, starting stirring and reacting for 4-6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, carrying out gas chromatography analysis on the filtrate, and calculating the conversion rate of the cyclohexene and the selectivity of the product.
The invention has the beneficial effects that: the aluminum alloy catalyst obtained by surface treatment has the advantages of cheap and easily-obtained raw materials, simple integral preparation process and higher utilization efficiency. The surface-treated aluminum alloy catalyst is used for catalyzing cyclohexene oxidation reaction, the reaction condition is mild, the environment is protected, and the conversion rate of cyclohexene or the selectivity of the product 2-cyclohexene-1-ketone can be effectively improved by adjusting the components and the proportion in the aluminum alloy and the concentration of the surface treatment solution.
Detailed Description
Example 1
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al50Cu40Co10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting copper by adopting high-temperature argon arcThe current of the metal raw material mixture on the bed is 80A, the current is cut off after 2 minutes of smelting, an aluminum alloy ingot is formed under the cooling effect of circulating water, the aluminum alloy ingot is turned over, and the process is repeated again for smelting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles A with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg50Cu40Co10The alloy particles A are put into a 200ml round-bottom flask, 50g of NaOH solution with the mass fraction of 0.1 percent is added, the round-bottom flask is put into a constant-temperature water bath with the temperature of 35 ℃, and the mixture is stirred for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface50Cu40Co10Alloy catalyst A-SHST-0.1%.
Example 2
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al50Cu40Co10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 80A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles A with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg50Cu40Co10The alloy particles A are put into a 200ml round-bottom flask, 50g of NaOH solution with the mass fraction of 1 percent is added, the round-bottom flask is put into a constant-temperature water bath with the temperature of 35 ℃, and the mixture is stirred for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface50Cu40Co10Alloy catalyst A-SHST-1%.
Example 3
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al50Cu40Co10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 80A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles A with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg50Cu40Co10The alloy particles A are put into a 200ml round-bottom flask, 50g of NaOH solution with the mass fraction of 10% is added, the round-bottom flask is put into a constant-temperature water bath with the temperature of 35 ℃, and the mixture is stirred for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface50Cu40Co10Alloy catalyst A-SHST-10%.
Example 4
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al50Cu40Co10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 80A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles A with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg50Cu40Co10Alloy particlesA is put into a 200ml round bottom flask, 50g of NaOH solution with the mass fraction of 20 percent is added, the round bottom flask is put into a constant temperature water bath with the temperature of 35 ℃, and the mixture is stirred for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface50Cu40Co10Alloy catalyst A-SHST-20%.
Example 5
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al60Cu20Co20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.03 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 85A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles B with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg60Cu20Co20The alloy particles B are placed into a 200ml round-bottom flask, 50g of NaOH solution with the mass fraction of 1 percent is added, the round-bottom flask is placed into a constant-temperature water bath with the temperature of 35 ℃, and the mixture is stirred for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface60Cu20Co20Alloy catalyst B-SHST-1%.
Example 6
Preparing the aluminum alloy catalyst with alkali-treated surface. (1) The metal raw materials of aluminum, copper and cobalt are mixed according to Al70Cu20Co10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. MiningHeating and melting the metal raw material mixture on the copper bed by using a high-temperature argon arc at the current of 82A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles C with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 120mg7oCu20Co10Placing the alloy particles C into a 200ml round-bottom flask, adding 50g of NaOH solution with the mass fraction of 1%, placing the round-bottom flask into a constant-temperature water bath with the temperature of 35 ℃, stirring for 2 hours after the temperature is stable. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 8 hours at room temperature to obtain Al with alkali treatment on the surface70Cu20Co10Alloy catalyst C-SHST-1%.
Example 7
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al40Cu40Cr20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 95A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles D with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg40Cu40Cr20Placing the alloy particles D into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 1%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface40Cu40Cr20Alloy catalyst D-NAST-1%.
Example 8
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al40Cu40Cr20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 95A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles D with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg40Cu40Cr20Placing the alloy particles D into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 3%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface40Cu40Cr20Alloy catalyst D-NAST-3%.
Example 9
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al40Cu40Cr20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 95A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles D with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg40Cu40Cr20Placing the alloy particles D into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 5%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface40Cu40Cr20Alloy catalyst D-NAST-5%.
Example 10
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al30Cu50Cr20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.03 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 92A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles E with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg30Cu50Cr20Placing the alloy particles E into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 1%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface30Cu50Cr20Alloy catalyst E-NAST-1%.
Example 11
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al50Cu20Cr30Weighing 10g of the mixture according to the molar ratio, placing the mixture on a copper bed of a vacuum arc furnace, vacuumizing the cavity of the arc furnace, introducing argon, and repeatedly vacuumizingVacuum and introducing argon for 3 times, and finally maintaining the pressure of the argon in the cavity to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 98A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. Taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles F with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg50Cu20Cr30Placing the alloy particles F into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 1%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface50Cu20Cr30Alloy catalyst F-NAST-1%.
Example 12
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al60Cu30Cr10The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.02 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 96A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles G with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg60Cu30Cr10Placing the alloy particles G into a 200ml round-bottom flask, adding 50G of HNO with the mass fraction of 1%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then carrying out centrifugal separation, repeatedly washing and centrifuging the solid particles for 3 times by using absolute ethyl alcohol, and naturally airing at room temperature for 24 hours to obtain the surfaceAcid treated Al60Cu30Cr10Alloy catalyst G-NAST-1%.
Example 13
Preparing the aluminum alloy catalyst with the acid treated surface. (1) The metal raw materials of aluminum, copper and chromium are mixed according to Al70Cu10Cr20The mixture of 10g is weighed according to the molar ratio, the mixture is placed on a copper bed of a vacuum arc furnace, the cavity of the arc furnace is vacuumized, argon is introduced, the vacuumizing and the argon introduction are repeated for 3 times, and finally the pressure of the argon in the cavity is maintained to be 0.03 MPa. Heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 95A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling effect of circulating water, turning over the aluminum alloy ingot, and repeating the process again to perform melting and cooling. And taking out the aluminum alloy ingot, polishing the surface, crushing and screening to obtain aluminum alloy particles H with the granularity of more than 500 meshes. (2) The prepared Al with the mass of 150mg70Cu10Cr20Placing the alloy particles H into a 200ml round-bottom flask, adding 50g of HNO with the mass fraction of 1%3Solution, put round bottom flask into 30 deg.C constant temperature water bath, after temperature stabilization stir for 2 hours. Then centrifugal separation is carried out, the solid particles are repeatedly washed and centrifuged for 3 times by absolute ethyl alcohol, and then the solid particles are naturally dried for 24 hours at room temperature to obtain Al with acid treated surface70Cu10Cr20Alloy catalyst H-NAST-1%.
Example 14
Measuring 5ml of cyclohexene, putting the cyclohexene into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle without adding a catalyst, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 5.6%, the selectivity of the 2-cyclohexene-1-ketone is 23.9%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 73.0%.
Example 15
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles A, putting the cyclohexene and the aluminum alloy particles A into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 26.6%, the selectivity of the 2-cyclohexene-1-ketone is 25.9%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 66.2%.
Example 16
Weighing 5ml of cyclohexene and 20mg of catalyst A-SHST-0.1%, putting the cyclohexene and the catalyst A-SHST-0.1% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to be stabilized at 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 44.1%, the selectivity of the 2-cyclohexene-1-ketone is 32.5%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 51.3%.
Example 17
Weighing 5ml of cyclohexene and 20mg of catalyst A-SHST-1%, putting the cyclohexene and the catalyst A-SHST-1% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, charging oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 52.9%, the selectivity of the 2-cyclohexene-1-ketone is 34.8%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 48.1%.
Example 18
Weighing 5ml of cyclohexene and 20mg of catalyst A-SHST-10%, putting the cyclohexene and the catalyst A-SHST-10% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, charging oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 46.7%, the selectivity of the 2-cyclohexene-1-ketone is 33.1%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 50.2%.
Example 19
Weighing 5ml of cyclohexene and 20mg of catalyst A-SHST-20%, putting the cyclohexene and the catalyst A-SHST-20% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, charging oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 44.8%, the selectivity of the 2-cyclohexene-1-ketone is 31.6%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 52.5%.
Example 20
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles B, placing the cyclohexene and the aluminum alloy particles B into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 21.9%, the selectivity of the 2-cyclohexene-1-ketone is 23.2%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 70.5%.
Example 21
Weighing 5ml of cyclohexene and 20mg of catalyst B-SHST-1%, putting the cyclohexene and the catalyst B-SHST-1% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, charging oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 43.4%, the selectivity of the 2-cyclohexene-1-ketone is 31.9%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 52.6%.
Example 22
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles C, putting the cyclohexene and the aluminum alloy particles C into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 13.9%, the selectivity of the 2-cyclohexene-1-ketone is 21.6%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 75.9%.
Example 23
Weighing 5ml of cyclohexene and 20mg of catalyst C-SHST-1%, putting the cyclohexene and the catalyst C-SHST-1% into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, charging oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 34.6%, the selectivity of the 2-cyclohexene-1-ketone is 30.3%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 58.4%.
Example 24
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles D, putting the cyclohexene and the aluminum alloy particles D into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 35.3%, the selectivity of the 2-cyclohexene-1-ketone is 23.6%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 58.4%.
Example 25
5ml of cyclohexene and 20mg of catalyst D-NAST-1% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 43.6%, the selectivity of the 2-cyclohexene-1-ketone is 49.3%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 41.6%.
Example 26
5ml of cyclohexene and 20mg of catalyst D-NAST-3% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 45.4%, the selectivity of the 2-cyclohexene-1-ketone is 48.1%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 41.8%.
Example 27
5ml of cyclohexene and 20mg of catalyst D-NAST-5% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 46.6%, the selectivity of the 2-cyclohexene-1-ketone is 45.3%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 43.0%.
Example 28
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles E, putting the cyclohexene and the aluminum alloy particles E into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 25.8%, the selectivity of the 2-cyclohexene-1-ketone is 20.6%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 65.5%.
Example 29
5ml of cyclohexene and 20mg of catalyst E-NAST-1% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction, the reaction kettle is cooled to room temperature, pressure is slowly released, the reaction kettle is opened, the catalyst solid and liquid are filtered and separated, and gas chromatography analysis is carried out on the filtrate, wherein the conversion rate of the cyclohexene is 35.8%, the selectivity of the 2-cyclohexene-1-ketone is 42.3%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 49.4%.
Example 30
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles F, putting the cyclohexene and the aluminum alloy particles F into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 23.5%, the selectivity of the 2-cyclohexene-1-ketone is 22.4%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 64.8%.
Example 31
5ml of cyclohexene and 20mg of catalyst F-NAST-1% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 34.7%, the selectivity of the 2-cyclohexene-1-ketone is 43.4%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 48.7%.
Example 32
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles G, putting the cyclohexene and the aluminum alloy particles G into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 21.3%, the selectivity of the 2-cyclohexene-1-ketone is 24.9%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 59.6%.
Example 33
5ml of cyclohexene and 20mg of catalyst G-NAST-1% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 32.6%, the selectivity of the 2-cyclohexene-1-ketone is 41.5%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 50.3%.
Example 34
Weighing 5ml of cyclohexene and 20mg of aluminum alloy particles H, putting the cyclohexene and the aluminum alloy particles H into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle to 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours. After the reaction, the reaction kettle is cooled to room temperature, pressure is slowly released, the reaction kettle is opened, the catalyst solid and liquid are filtered and separated, gas chromatography analysis is carried out on the filtrate, the conversion rate of the cyclohexene is 18.5%, the selectivity of the 2-cyclohexene-1-ketone is 20.7%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 69.6%.
Example 35
5ml of cyclohexene and 20mg of catalyst H-NAST-1% are weighed and put into a polytetrafluoroethylene lining, the lining is sealed in a high-pressure reaction kettle, the reaction kettle is heated and stabilized at 75 ℃, oxygen with the pressure of 2MPa is filled, stirring is started, and the reaction lasts for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography analysis on the filtrate, wherein the conversion rate of the cyclohexene is 30.7%, the selectivity of the 2-cyclohexene-1-ketone is 40.3%, and the total selectivity of other C6 products (2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide) is 52.8%.

Claims (1)

1. The application of the surface-treated aluminum alloy catalyst in catalyzing cyclohexene oxidation is characterized in that the prepared catalyst has high conversion rate and high 2-cyclohexene-1-ketone selectivity when being applied to catalyzing cyclohexene oxidation: (1) preparation of surface alkali treated aluminum alloy catalyst: the metal raw materials of aluminum, copper and cobalt are mixed according to Al50Cu40Co10Weighing 10g of mixture according to the molar ratio, placing the mixture on a copper bed of a vacuum arc furnace, vacuumizing a cavity of the arc furnace, introducing argon, repeatedly vacuumizing and introducing the argon for 3 times, finally maintaining the pressure of the argon in the cavity to be 0.02MPa, heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 80A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling action of circulating water, turning over the aluminum alloy ingot, repeating the above process again for melting and cooling, taking out the aluminum alloy ingot, polishing the surface, crushing, sieving to obtain more than 500-mesh aluminum alloy particles, taking out 120mg of the aluminum alloy particles, placing the aluminum alloy particles into a 200ml round-bottomed flask, adding 50g of NaOH solution with the mass fraction of 1%, and placing the round flask into a vacuum arc furnacePlacing the bottom flask into a constant-temperature water bath at 35 ℃, stirring for 2 hours after the temperature is stable, then centrifugally separating, repeatedly washing and centrifuging the solid particles for 3 times by using absolute ethyl alcohol, and naturally airing for 8 hours at room temperature to obtain the Al with alkali treated surface50Cu40Co10An alloy catalyst; (2) preparation of surface acid treated aluminum alloy catalyst: the metal raw materials of aluminum, copper and chromium are mixed according to Al40Cu40Cr20Weighing 10g of mixture according to the molar ratio, placing the mixture on a copper bed of a vacuum arc furnace, vacuumizing a cavity of the arc furnace, introducing argon, repeatedly vacuumizing and introducing the argon for 3 times, finally maintaining the pressure of the argon in the cavity to be 0.02MPa, heating and melting the metal raw material mixture on the copper bed by adopting high-temperature argon arc, wherein the current is 95A, cutting off the current after melting for 2 minutes, forming an aluminum alloy ingot under the cooling action of circulating water, turning over the aluminum alloy ingot, repeating the above process again for melting and cooling, taking out the aluminum alloy ingot, polishing the surface, crushing, sieving to obtain aluminum alloy particles of more than 500 meshes, taking out 150mg of the aluminum alloy particles, placing the aluminum alloy particles into a 200ml round-bottomed flask, adding 50g of HNO with the mass fraction of 1 percent, and adding the HNO3Putting a round-bottom flask into a constant-temperature water bath at 30 ℃, stirring for 2 hours after the temperature is stable, then centrifugally separating, repeatedly washing and centrifuging solid particles for 3 times by using absolute ethyl alcohol, and naturally airing for 24 hours at room temperature to obtain the surface acid treated Al40Cu40Cr20An alloy catalyst; (3) 5ml of cyclohexene and 20mg of surface alkali treated Al were metered in50Cu40Co10Putting an alloy catalyst into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle, stabilizing the temperature at 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours, cooling the reaction kettle to room temperature after the reaction is finished, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography on filtrate to obtain a filtrate, wherein the conversion rate of cyclohexene is 52.9%, the selectivity of 2-cyclohexene-1-ketone is 34.8%, and the sum of the selectivity of 2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide is 48.1%; (4) 5ml of cyclohexene and 20mg of surface acid-treated Al were metered in40Cu40Cr20Alloy catalystPutting the reaction kettle into a polytetrafluoroethylene lining, sealing the lining in a high-pressure reaction kettle, heating the reaction kettle, stabilizing the temperature at 75 ℃, filling oxygen with the pressure of 2MPa, starting stirring and reacting for 6 hours, cooling the reaction kettle to room temperature after the reaction is finished, slowly releasing pressure, opening the reaction kettle, filtering and separating catalyst solid and liquid, and performing gas chromatography on filtrate to obtain the product with the conversion rate of cyclohexene of 43.6%, the selectivity of 2-cyclohexene-1-ketone of 49.3%, and the sum of the selectivity of 2-cyclohexene-1-alcohol, 2-cyclohexene-1-hydrogen peroxide and cyclohexene oxide of 41.6%.
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