CN109999821A - A kind of preparation and its application of the aluminium alloy catalyst of surface treatment - Google Patents

A kind of preparation and its application of the aluminium alloy catalyst of surface treatment Download PDF

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CN109999821A
CN109999821A CN201910186718.7A CN201910186718A CN109999821A CN 109999821 A CN109999821 A CN 109999821A CN 201910186718 A CN201910186718 A CN 201910186718A CN 109999821 A CN109999821 A CN 109999821A
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cyclohexene
aluminium alloy
alloy catalyst
catalyst
reaction kettle
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CN109999821B (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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Inner Mongolia University of Technology
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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
    • B01J23/85—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

Abstract

The present invention relates to the preparations and its application of a kind of aluminium alloy catalyst of surface treatment.Surface treatment is divided into surface alkali process and surface acid etching, and the ingredient of the aluminium alloy catalyst of surface alkali process is aluminium, copper, cobalt, mol ratio are as follows: AlxCuyCo100‑x‑y, x value is that 50~70, y value is 10~(90-x), and the mass fraction of NaOH solution used is 0.1%~20%；The ingredient of the aluminium alloy catalyst of surface acid etching is aluminium, copper, chromium, mol ratio are as follows: AlxCuyCr100‑x‑y, x value is that 30~70, y value is 10~(90-x), HNO used3The mass fraction of solution is 1%~5%.The raw material of the aluminium alloy catalyst of surface treatment is cheap and easy to get, whole preparation process is simple, for being catalyzed in cyclohexene oxide reaction, its reaction condition is mild, it is environmentally friendly, and by adjusting the component in aluminium alloy, proportion and the concentration of surface processing solution, the conversion ratio of cyclohexene or the selectivity of product 2- cyclohexene -1- ketone can be effectively improved.

Description

A kind of preparation and its application of the aluminium alloy catalyst of surface treatment
Technical field
The present invention relates to the preparations and its application of a kind of aluminium alloy catalyst of surface treatment.
Background technique
Cyclohexene oxide is that alkene hydrocarbon is made to be converted into the oxygen-containing derivative such as epoxide, alcohol, ketone, carboxylic acid, aldehyde The important reaction of object, obtained containing oxygen derivative can be applied to pesticide, medicine, fragrance, surface as organic chemical industry's intermediate The field of fine chemical such as activating agent and high molecular material, for example, 2- cyclohexene -1- ketone, 2- cyclohexene -1- alcohol, 7-oxa-bicyclo[4.1.0, The products such as adipic acid can be used for producing perfume, nylon -66 and medicine etc..At present the oxidant of cyclohexene oxide be mainly oxygen, Hydrogen peroxide and tert-butyl hydroperoxide, wherein being widely used since oxygen is cheap and easy to get.China is special disclosed in 2017 In sharp CN107051562A and CN104226313B, it is prepared for graphene-based carbonic acid Co catalysts and electroless copper catalyst respectively For being catalyzed cyclohexene oxide, but whole preparation method is complicated, higher cost, therefore when developing new catalyst, answers This considers low-cost synthesis material and simple and easy preparation method first.
Metal aluminum alloy is since density is small, anticorrosive, electrical and thermal conductivity is good, mainly as structural metallic materials for navigating The fields such as sky, space flight, automobile, machinery.However in some special compositions and the aluminium alloy of proportion, it is capable of forming intermetallic Object, since its special electronic structure and valence link form, intermetallic compound has apparent brittleness at room temperature, and at this moment aluminium alloy can Crushed easily as particle, by surface treatment, a large amount of active site is exposed, can be used as catalysis materials'use. So far, the metal aluminum alloy after not being surface-treated both at home and abroad is used to be catalyzed the report of cyclohexene oxide as catalysis material Road.The present invention makes it have good catalysis cyclohexene oxide by carrying out simple soda acid processing to part aluminum alloy surface Activity, widened the application field of part aluminium alloy, realize part aluminium alloy catalysisization utilization.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of the aluminium alloy catalyst of surface treatment and its in catalysis ring Application in hexene oxidation.
The present invention provides a kind of preparation method of the aluminium alloy catalyst of surface treatment, condition and steps are as follows:
1, the preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to certain mole Proportion weighs and obtains the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then be passed through Argon gas vacuumizes repeatedly and leads to argon gas 3 times, and finally maintaining the pressure of argon gas in cavity is 0.01~0.04MPa.Using High Temperature Argon Raw metal mixture on arc heating fusing solid brass bed, electric current is 50~200A, and melting cut off electric current after 2 minutes, in recirculated water Aluminium alloy ingot bar is formed under cooling effect, overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium is taken out to close Golden ingot bar, surface of polishing, crushes, and screening obtains the aluminum alloy granule of 500 mesh or more.The mol ratio of aluminium, copper, cobalt alloy are as follows: AlxCuyCo100-x-y, x value is that 50~70, y value is 10~(90-x).It (2) is 100~200mg's by the above-mentioned quality prepared AlxCuyCo100-x-yAlloying pellet is put into the round-bottomed flask of 200ml, and it is 0.1%~20% that 50g mass fraction, which is added, NaOH solution is put into round-bottomed flask in 35 DEG C of water bath with thermostatic control, and temperature stirs 1~3 hour after stablizing.Then carry out centrifugation point From washing centrifugation 3 times repeatedly with dehydrated alcohol to solid particle, then naturally dry 8 hours at room temperature, obtain at the alkali of surface The Al of reasonxCuyCo100-x-yAlloy catalyst.
2, the preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to certain mole Proportion weighs and obtains the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then be passed through Argon gas vacuumizes repeatedly and leads to argon gas 3 times, and finally maintaining the pressure of argon gas in cavity is 0.01~0.04MPa.Using High Temperature Argon Raw metal mixture on arc heating fusing solid brass bed, electric current is 50~200A, and melting cut off electric current after 2 minutes, in recirculated water Aluminium alloy ingot bar is formed under cooling effect, overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium is taken out to close Golden ingot bar, surface of polishing, crushes, and screening obtains the aluminum alloy granule of 500 mesh or more.The mol ratio of aluminium, copper, evanohm are as follows: AlxCuyCr100-x-y, x value is that 30~70, y value is 10~(90-x).It (2) is 100~200mg's by the above-mentioned quality prepared AlxCuyCr100-x-yAlloying pellet is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1%~5% is added3It is molten Liquid is put into round-bottomed flask in 30 DEG C of water bath with thermostatic control, and temperature stirs 1~3 hour after stablizing.Then it is centrifuged, it is right Solid particle washs centrifugation 3 times with dehydrated alcohol repeatedly, then naturally dry 24 hours at room temperature, obtains surface acid etching AlxCuyCr100-x-yAlloy catalyst.
The present invention provides a kind of application of the aluminium alloy catalyst of surface treatment, is applied to catalysis cyclohexene oxide, condition With steps are as follows:
The catalyst for measuring 5ml cyclohexene and certain mass is put into polytetrafluoroethyllining lining, cyclohexene and catalyst Mass ratio is (100: 1)~(400: 1), in a high pressure reaction kettle by liner sealing, heats reaction kettle and stablizes at 70~80 DEG C, Charged pressure is the oxygen of 1~2MPa, opens and stirs and react 4~6h.After reaction, cooling reaction kettle delays to room temperature Slow pressure release opens reaction kettle, is separated by filtration catalyst solid and liquid, carries out gas chromatographic analysis to filtrate, calculates cyclohexene Conversion ratio and product selectivity.
Beneficial effects of the present invention: by being surface-treated obtained aluminium alloy catalyst, raw material is cheap and easy to get, whole to make Standby simple process, utilization efficiency are higher.The aluminium alloy catalyst of surface treatment is for being catalyzed in cyclohexene oxide reaction, reaction Mild condition, it is environmentally friendly, and by adjusting the component in aluminium alloy, proportion and the concentration of surface processing solution, energy Enough effectively improve the conversion ratio of cyclohexene or the selectivity of product 2- cyclohexene -1- ketone.
Specific embodiment
Embodiment 1
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al50Cu40Co10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 80A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule A of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al50Cu40Co10Alloying pellet A is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 0.1% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, temperature stirs 2 hours after stablizing.It is then centrifuged, to solid Grain wash repeatedly with dehydrated alcohol and is centrifuged 3 times, and then naturally dry 8 hours at room temperature, obtain surface alkali process Al50Cu40Co10Alloy catalyst A-SHST-0.1%.
Embodiment 2
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al50Cu40Co10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 80A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule A of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al50Cu40Co10Alloying pellet A is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 1% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 8 hours at room temperature, obtains surface alkali process Al50Cu40Co10Alloy catalyst A-SHST-1%.
Embodiment 3
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al50Cu40Co10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 80A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule A of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al50Cu40Co10Alloying pellet A is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 10% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 8 hours at room temperature, obtains surface alkali process Al50Cu40Co10Alloy catalyst A-SHST-10%.
Embodiment 4
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al50Cu40Co10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 80A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule A of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al50Cu40Co10Alloying pellet A is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 20% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 8 hours at room temperature, obtains surface alkali process Al50Cu40Co10Alloy catalyst A-SHST-20%.
Embodiment 5
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al60Cu20Co20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.03MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 85A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule B of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al60Cu20Co20Alloying pellet B is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 1% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 8 hours at room temperature, obtains surface alkali process Al60Cu20Co20Alloy catalyst B-SHST-1%.
Embodiment 6
The preparation of the aluminium alloy catalyst of surface alkali process.(1) by aluminium, copper, cobalt raw metal according to Al70Cu20Co10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 82A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule C of 500 mesh or more.It (2) is 120mg's by the above-mentioned quality prepared Al7oCu20Co10Alloying pellet C is put into the round-bottomed flask of 200ml, and the NaOH solution that 50g mass fraction is 1% is added, Round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 8 hours at room temperature, obtains surface alkali process Al70Cu20Co10Alloy catalyst C-SHST-1%.
Embodiment 7
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al40Cu40Cr20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 95A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule D of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al40Cu40Cr20Alloying pellet D is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al40Cu40Cr20Alloy catalyst D-NAST-1%.
Embodiment 8
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al40Cu40Cr20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 95A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule D of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al40Cu40Cr20Alloying pellet D is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 3% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al40Cu40Cr20Alloy catalyst D-NAST-3%.
Embodiment 9
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al40Cu40Cr20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 95A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule D of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al40Cu40Cr20Alloying pellet D is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 5% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al40Cu40Cr20Alloy catalyst D-NAST-5%.
Embodiment 10
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al30Cu50Cr20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.03MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 92A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule E of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al30Cu50Cr20Alloying pellet E is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al30Cu50Cr20Alloy catalyst E-NAST-1%.
Embodiment 11
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al50Cu20Cr30's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 98A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule F of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al50Cu20Cr30Alloying pellet F is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al50Cu20Cr30Alloy catalyst F-NAST-1%.
Embodiment 12
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al60Cu30Cr10's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.02MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 96A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule G of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al60Cu30Cr10Alloying pellet G is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al60Cu30Cr10Alloy catalyst G-NAST-1%.
Embodiment 13
The preparation of the aluminium alloy catalyst of surface acid etching.(1) by aluminium, copper, chromium raw metal according to Al70Cu10Cr20's Mol ratio weighs to obtain the mixture of 10g, is placed on the solid brass bed of vacuum arc furnace ignition, vacuumizes to the cavity of electric arc furnaces, then It is passed through argon gas, vacuumize repeatedly and is led to argon gas 3 times, finally maintaining the pressure of argon gas in cavity is 0.03MPa.Using high temperature argon arc Raw metal mixture on heating fusing solid brass bed, electric current 95A, melting cut off electric current after 2 minutes, acted in circulating water Lower formation aluminium alloy ingot bar overturns aluminium alloy ingot bar, repeats the above process carry out melting cooling again.Aluminium alloy ingot bar is taken out, Polishing surface, crushes, and screening obtains the aluminum alloy granule H of 500 mesh or more.It (2) is 150mg's by the above-mentioned quality prepared Al70Cu10Cr20Alloying pellet H is put into the round-bottomed flask of 200ml, and the HNO that 50g mass fraction is 1% is added3Solution, Round-bottomed flask is put into 30 DEG C of water bath with thermostatic control, and temperature stirs 2 hours after stablizing.It is then centrifuged, to solid particle It washs centrifugation 3 times repeatedly with dehydrated alcohol, then naturally dry 24 hours at room temperature, obtains surface acid etching Al70Cu10Cr20Alloy catalyst H-NAST-1%.
Embodiment 14
It measures 5ml cyclohexene to be put into polytetrafluoroethyllining lining, catalyst is not added, liner is sealed in autoclave In, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, Cooling reaction kettle is to room temperature, and slow pressure release opens reaction kettle, is separated by filtration catalyst solid and liquid, to filtrate progress gas phase Chromatography, the conversion ratio of cyclohexene are that the selectivity of 5.6%, 2- cyclohexene -1- ketone is 23.9%, other C6 product (2- rings Hexen-1-ol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) selective summation be 73.0%.
Embodiment 15
The aluminum alloy granule A for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 26.6%, 2- cyclohexene -1- ketone is 25.9%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 66.2%.
Embodiment 16
The catalyst A-SHST-0.1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is close Envelope in a high pressure reaction kettle, heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 44.1%, 2- cyclohexene -1- ketone is 32.5%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 51.3%.
Embodiment 17
The catalyst A-SHST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 52.9%, 2- cyclohexene -1- ketone is 34.8%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 48.1%.
Embodiment 18
The catalyst A-SHST-10% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 46.7%, 2- cyclohexene -1- ketone is 33.1%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 50.2%.
Embodiment 19
The catalyst A-SHST-20% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 44.8%, 2- cyclohexene -1- ketone is 31.6%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 52.5%.
Embodiment 20
The aluminum alloy granule B for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 21.9%, 2- cyclohexene -1- ketone is 23.2%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 70.5%.
Embodiment 21
The catalyst B-SHST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 43.4%, 2- cyclohexene -1- ketone is 31.9%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 52.6%.
Embodiment 22
The aluminum alloy granule C for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 13.9%, 2- cyclohexene -1- ketone is 21.6%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 75.9%.
Embodiment 23
The catalyst C-SHST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 34.6%, 2- cyclohexene -1- ketone is 30.3%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 58.4%.
Embodiment 24
The aluminum alloy granule D for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 35.3%, 2- cyclohexene -1- ketone is 23.6%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 58.4%.
Embodiment 25
The catalyst D-NAST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 43.6%, 2- cyclohexene -1- ketone is 49.3%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 41.6%.
Embodiment 26
The catalyst D-NAST-3% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 45.4%, 2- cyclohexene -1- ketone is 48.1%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 41.8%.
Embodiment 27
The catalyst D-NAST-5% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 46.6%, 2- cyclohexene -1- ketone is 45.3%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 43.0%.
Embodiment 28
The aluminum alloy granule E for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 25.8%, 2- cyclohexene -1- ketone is 20.6%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 65.5%.
Embodiment 29
The catalyst E-NAST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 35.8%, 2- cyclohexene -1- ketone is 42.3%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 49.4%.
Embodiment 30
The aluminum alloy granule F for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 23.5%, 2- cyclohexene -1- ketone is 22.4%, and other C6 are produced The selective summation of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 64.8%.
Embodiment 31
The catalyst F-NAST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 34.7%, 2- cyclohexene -1- ketone is 43.4%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 48.7%.
Embodiment 32
The aluminum alloy granule G for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 21.3%, 2- cyclohexene -1- ketone is 24.9%, and other C6 are produced The selective summation 59.6% of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0).
Embodiment 33
The catalyst G-NAST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 32.6%, 2- cyclohexene -1- ketone is 41.5%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 50.3%.
Embodiment 34
The aluminum alloy granule H for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed in high pressure In reaction kettle, heats reaction kettle and stablize at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.Reaction After, cooling reaction kettle arrives room temperature, slow pressure release, and opening reaction kettle is separated by filtration catalyst solid and liquid, to filtrate into Promoting the circulation of qi analysis of hplc, the conversion ratio of cyclohexene are that the selectivity of 18.5%, 2- cyclohexene -1- ketone is 20.7%, and other C6 are produced The selective summation 69.6% of object (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0).
Embodiment 35
The catalyst H-NAST-1% for measuring 5ml cyclohexene and 20mg is put into polytetrafluoroethyllining lining, and liner is sealed In a high pressure reaction kettle, it heats reaction kettle and stablizes at 75 DEG C, charged pressure is the oxygen of 2MPa, opens and stirs and react 6h.After reaction, cooling reaction kettle opens reaction kettle, is separated by filtration catalyst solid and liquid to room temperature, slow pressure release, Gas chromatographic analysis is carried out to filtrate, the conversion ratio of cyclohexene is that the selectivity of 30.7%, 2- cyclohexene -1- ketone is 40.3%, The selective summation of other C6 products (2- cyclohexene -1- alcohol, 2- cyclohexene -1- hydrogen peroxide and 7-oxa-bicyclo[4.1.0) is 52.8%.

Claims (4)

1. a kind of aluminium alloy catalyst of surface treatment, it is characterised in that: the ingredient of the aluminium alloy catalyst of surface treatment be aluminium, Copper, cobalt or chromium are surface-treated as surface alkali process or surface acid etching, wherein mole of the aluminium alloy catalyst of surface alkali process Proportion are as follows: AlxCuyCo100-x-y, x value is that 50~70, y value is 10~(90-x)；The aluminium alloy catalyst of surface acid etching rubs You match are as follows: AlxCuyCr100-x-y, x value is that 30~70, y value is 10~(90-x).
2. the preparation method for the aluminium alloy catalyst being surface-treated as described in claim 1, it is characterised in that the condition of preparation With steps are as follows: by quality be 100~200mg AlxCuyCo100-x-yAlloying pellet is put into the round-bottomed flask of 200ml, is added Enter the NaOH solution that 50g mass fraction is 0.1%~20%, round-bottomed flask is put into 35 DEG C of water bath with thermostatic control, temperature is stablized It stirs 1~3 hour, is then centrifuged afterwards, centrifugation 3 times is washed repeatedly with dehydrated alcohol to solid particle, then in room Temperature is naturally dry 8 hours lower, obtains the Al of surface alkali processxCuyCo100-x-yAlloy catalyst.
3. the preparation method for the aluminium alloy catalyst being surface-treated as described in claim 1, it is characterised in that the condition of preparation With steps are as follows: by quality be 100~200mg AlxCuyCr100-x-yAlloying pellet is put into the round-bottomed flask of 200ml, is added Enter the HNO that 50g mass fraction is 1%~5%3Solution is put into round-bottomed flask in 30 DEG C of water bath with thermostatic control, and temperature is stirred after stablizing It mixes 1~3 hour, is then centrifuged, centrifugation 3 times is washed repeatedly with dehydrated alcohol to solid particle, then at room temperature Naturally dry 24 hours, obtain the Al of surface acid etchingxCuyCr100-x-yAlloy catalyst.
4. the application for the aluminium alloy catalyst being surface-treated as described in claim 1 is applied to catalysis cyclohexene oxide, special Sign is to be catalyzed the condition of cyclohexene oxide and steps are as follows: the mass ratio that feeds intake of cyclohexene and catalyst be (100: 1)~ (400: 1), reaction temperature are 70~80 DEG C, and oxygen pressure is 1~2MPa, and the reaction time is 4~6 hours.
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