CN116459825A - Composite catalyst and preparation method and application thereof - Google Patents

Composite catalyst and preparation method and application thereof Download PDF

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Publication number
CN116459825A
CN116459825A CN202310436089.5A CN202310436089A CN116459825A CN 116459825 A CN116459825 A CN 116459825A CN 202310436089 A CN202310436089 A CN 202310436089A CN 116459825 A CN116459825 A CN 116459825A
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composite catalyst
cyclohexylbenzene
cerium
copper
oxide
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陈秉辉
严聿捷
张诺伟
王结祥
谢建榕
叶松寿
郑进保
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Xiamen University
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Xiamen University
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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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/72—Copper
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy 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
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a composite catalyst and a preparation method and application thereof. The low-valence cerium oxide and the low-valence copper oxide on the surface of the composite catalyst can improve the transmission and activation performance of the composite catalyst to oxygen; the electron transfer in the oxidation reaction is critical, and the introduction of the carbon material with reducibility can effectively stabilize copper and cerium on the surface of the catalyst in a low valence state, wherein the copper is mostly stabilized in +1 valence, and the cerium is mostly stabilized in +3 valence, thereby being beneficial to the electron transfer in the oxidation reaction, improving the utilization rate of activated oxygen species of the composite catalyst and enabling the composite catalyst to have high catalytic activity and high selectivity. The composite catalyst provided by the invention is used for catalyzing and oxidizing the cyclohexylbenzene, the main product is cyclohexylbenzene hydrogen peroxide, the selectivity can reach 90.4%, and the conversion rate of the cyclohexylbenzene can reach 34.2%.

Description

Composite catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a composite catalyst and a preparation method and application thereof.
Background
Phenol, an important chemical intermediate, can be prepared by catalytic oxidation of cyclohexylbenzene, and mainly comprises two reactions: (1) The method comprises the steps of (1) carrying out an oxidation reaction on cyclohexylbenzene and oxygen under the action of a catalyst to generate cyclohexylbenzene hydroperoxide (CHBHP); (2) And (3) carrying out acidolysis reaction on the CHBHP under an acidic condition to obtain cyclohexanone and phenol. The method has the advantages that the condition required by the whole reaction process is mild, toxic and harmful waste is not generated, the consumed raw materials can be completely converted into phenol and cyclohexanone, the environment-friendly requirement of green chemical industry is met, and the atomic utilization rate and the economic benefit of the reaction are extremely high, so that the method has extremely wide application prospect and extremely high industrial value. Among them, the step (1) is a radical reaction, which is the most important step in the process route, and the highly selective directional oxidation of cyclohexylbenzene to CHBHP is a difficulty in the current research.
Currently, the catalytic oxidation of cyclohexylbenzene is mainly carried out with N-hydroxyphthalimide (NHPI) or metal oxides as catalysts. When NHPI is used for catalytic oxidation of cyclohexylbenzene, the low oxygen activation ability of the NHPI leads to relatively low catalytic activity; however, when the metal oxide is used for catalytic oxidation of cyclohexylbenzene, the disadvantage of long reaction time is unavoidable, and the catalytic activity is also insufficient.
In summary, the existing catalysts are not high enough in catalytic activity and selectivity for cyclohexylbenzene.
Disclosure of Invention
The invention aims to provide a composite catalyst, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite catalyst, which comprises a reduction component and a metal oxide component supported on the reduction component; the metal oxide component comprises cerium oxide and/or copper oxide; the average valence of cerium in the cerium oxide is greater than +3 and less than +4; the average valence of copper in the copper oxide is greater than +1 and less than +2; the reducing component is carbon.
Preferably, the mass ratio of the metal oxide component to the reducing component is 10-70:30-90.
Preferably, the metal oxide component comprises cerium oxide and copper oxide, and the molar ratio of the cerium oxide to the copper oxide is 1-10:1-10.
The invention also provides a preparation method of the composite catalyst, which comprises the following steps:
mixing the carbon material mixed solution, metal salt, complexing agent and alkaline solution, performing hydrothermal reaction under a closed condition, and calcining to obtain a composite catalyst;
the metal salt comprises one or more of copper salt and cerium salt.
Preferably, the copper salt comprises one or more of nitrate and chloride; the cerium salt comprises one or more of nitrate and chloride;
the concentration of the carbon material mixed solution is 4.375-17.5 wt%.
Preferably, the temperature of the hydrothermal reaction is 70-130 ℃, and the heat preservation time is 12-48 h.
Preferably, the calcining atmosphere is air, the temperature is 300-500 ℃, and the heat preservation time is 2-8 h.
The invention also provides an application of the composite catalyst in the scheme or the composite catalyst obtained by the preparation method in the scheme in preparing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene.
Preferably, the preparation of cyclohexylbenzene hydroperoxide by catalytic oxidation of cyclohexylbenzene comprises the following steps:
and mixing the composite catalyst, the cyclohexylbenzene and the oxidant for oxidation reaction to obtain the cyclohexylbenzene hydroperoxide.
Preferably, the mass ratio of the composite catalyst to the cyclohexylbenzene is 0.001-0.002:1; the flow rate of the oxidant is 60-140 mL/min.
The invention provides a composite catalyst, which comprises a reduction component and a metal oxide component supported on the reduction component; the metal oxide component comprises cerium oxide and/or copper oxide; the average valence of cerium in the cerium oxide is greater than +3 and less than +4; the average valence of copper in the copper oxide is greater than +1 and less than +2; the reducing component is carbon. The low-valence cerium oxide and the low-valence copper oxide on the surface of the composite catalyst improve the transmission and activation performance of the composite catalyst to oxygen; because the electron transfer is critical in the oxidation reaction, and the introduction of the carbon material with reducibility can effectively stabilize copper and cerium on the surface of the catalyst in a low valence state, wherein most of copper is stabilized in +1 valence, most of cerium is stabilized in +3 valence, and the electron transfer in the oxidation reaction is facilitated, so that the utilization rate of activated oxygen species of the composite catalyst is improved; meanwhile, as the metal oxide components are highly dispersed on the carrier, the interaction and aggregation phenomena among the components can be reduced, so that the occurrence of side reactions and the degradation of products are reduced; and compared with high-valence metal cations, the low-valence metal cations have weak oxidizing property, so that deep oxidation is avoided, the selectivity of the catalyst is improved, and the composite catalyst has high catalytic activity and high selectivity. The composite catalyst provided by the invention is used for catalyzing and oxidizing the cyclohexylbenzene, the main product is cyclohexylbenzene hydrogen peroxide, the selectivity can reach 90.4%, the conversion rate of the cyclohexylbenzene can reach 34.2%, and the catalyst has high catalytic activity and high selectivity.
The invention also provides a preparation method of the composite catalyst. The method provided by the invention has the advantages of simple steps, convenient operation and low cost, and is suitable for large-scale production.
The invention also provides an application of the composite catalyst in the scheme or the composite catalyst obtained by the preparation method in the scheme in preparing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene. After the composite catalyst provided by the invention is added into a cyclohexylbenzene reaction system, the cyclohexylbenzene is oxidized to generate cyclohexylbenzene hydroperoxide, and the method has the advantages of rapid reaction, high conversion rate and high selectivity.
Furthermore, the composite catalyst provided by the invention has small dosage, is favorable for further reducing the production cost of the cyclohexylbenzene hydroperoxide, and has good economic and social benefits.
Detailed Description
The invention provides a composite catalyst, which comprises a reduction component and a metal oxide component supported on the reduction component; the metal oxide component comprises cerium oxide and/or copper oxide; the average valence of cerium in the cerium oxide is greater than +3 and less than +4; the average valence of copper in the copper oxide is greater than +1 and less than +2; the reducing component is carbon.
The composite catalyst provided by the invention comprises a metal oxide component loaded on the reduction component; the cerium oxide preferably includes cerium oxide having an oxygen defect; the average valence of cerium in the cerium oxide is more than +3 and less than +4, preferably +3.70 to +3.98; the copper oxide preferably includes copper oxide having oxygen defects; the average valence of copper in the copper oxide is more than +1 and less than +2, preferably +1.70 to +1.95; the metal oxide component preferably includes cerium oxide and copper oxide, and the molar ratio of the cerium oxide to the copper oxide is preferably 1 to 10:1 to 10, more preferably 2 to 8:2 to 8, and further preferably 4 to 6:4 to 6.
The composite catalyst provided by the invention comprises a reduction component; the mass ratio of the metal oxide component to the reducing component is preferably 10 to 70:30 to 90, more preferably 30 to 60:40 to 70, and even more preferably 40 to 50:50 to 60.
In the present invention, the composite catalyst is preferably a cerium oxide-carbon composite catalyst (CeO) 2 /C), copper oxide-carbon composite catalyst (CuO/C) or copper cerium composite oxide-carbon composite catalyst (CuO-CeO) 2 /C)。
The invention also provides a preparation method of the composite catalyst, which comprises the following steps:
mixing the carbon material mixed solution, metal salt, complexing agent and alkaline solution, performing hydrothermal reaction under a closed condition, and calcining to obtain a composite catalyst;
the metal salt comprises one or more of copper salt and cerium salt.
In the present invention, the concentration of the carbon material solution is preferably 4.375 to 17.5wt%, more preferably 5 to 15wt%, still more preferably 7 to 12wt%; the carbon material of the carbon material mixed solution preferably comprises one or two of activated carbon and carbon nano tubes; the carbon nanotubes are preferably one or more of multi-wall, few-wall and single-wall, more preferably multi-wall carbon nanotubes; the length of the carbon nanotubes is preferably 5-800 μm, more preferably 10-600 μm, and the tube diameter is preferably 5-100 nm, more preferably 10-80 nm; the particle diameter of the carbon material is preferably 250 to 630. Mu.m, more preferably 300 to 600. Mu.m, still more preferably 400 to 500. Mu.m; the carbon material is preferably ground and then sieved before being mixed; the pore diameter of the sieving screen preferably corresponds to the particle diameter of the carbon material.
In the present invention, the alkaline solution is preferably one or both of sodium hydroxide and sodium carbonate solution; the concentration of the alkaline solution is preferably 2 to 4mol/L, more preferably 2.3 to 3.7mol/L, and still more preferably 2.8 to 3.3mol/L.
In the present invention, the copper salt preferably includes one or more of nitrate and chloride, more preferably Cu (NO 3 ) 2 ·3H 2 O; the cerium salt preferably includes one or more of nitrate and chloride, more preferably Ce (NO 3 ) 3 ·6H 2 O。
In the present invention, the complexing agent is preferably sodium citrate. The complexing agent is added, so that the metal ions can be dispersed, and smaller nano particles can be formed.
In the invention, the mass ratio of the carbon material mixed solution to the metal salt is preferably 10-200:1-20, more preferably 15-190:2-18; the mass ratio of the metal salt to the complexing agent is preferably 10-100:12-120, more preferably 12-95:15-110; the mass ratio of the complexing agent to the alkaline solution is preferably 5-100:100-1000, more preferably 8-95:105-950.
In the present invention, the carbon material mixture, the metal salt, the complexing agent and the alkaline solution are preferably mixed as follows: adding metal salt and complexing agent into the carbon material mixed solution for premixing, and then mixing the obtained premix with alkaline solution; the premixing mode is preferably stirring; the stirring time is preferably not less than 10min, more preferably 10-30 min; the premix and alkaline solution are preferably mixed by stirring; the stirring time is preferably not less than 30min, more preferably 30-40 min; the pH of the mixed solution obtained by mixing the carbon material mixed solution, the metal salt, the complexing agent and the alkaline solution is preferably 8 to 12, more preferably 10. The invention precipitates metal ions by the above mixing to obtain metal hydroxide.
In the present invention, the temperature of the hydrothermal reaction is preferably 70 to 130 ℃, more preferably 80 to 120 ℃, still more preferably 90 to 110 ℃, and the holding time is preferably 12 to 48 hours, more preferably 24 to 36 hours; the device for the hydrothermal reaction is preferably a polytetrafluoroethylene-lined stainless steel autoclave.
In the present invention, the product obtained after the hydrothermal reaction is preferably cooled, filtered, washed and dried; the cooling mode is preferably natural cooling; the final temperature of the cooling is preferably room temperature; the washing reagent is preferably one or two of water and absolute ethyl alcohol; the washing preferably washes the product to a pH of less than 9, more preferably 7; the number of times of washing is preferably not less than 5 times, more preferably 5 to 10 times; the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 60 to 80 ℃, the pressure is preferably 0.01 to 0.05MPa, more preferably 0.01 to 0.03MPa, and the time is preferably 12 to 24 hours, more preferably 15 to 20 hours.
In the present invention, the calcination atmosphere is preferably nitrogen, the temperature is preferably 300 to 500 ℃, more preferably 350 to 450 ℃, further preferably 400 ℃, and the heat preservation time is preferably 2 to 8 hours, more preferably 4 to 6 hours; the calcination apparatus is preferably a muffle furnace. The invention decomposes hydroxide into metal oxide by calcination.
The invention also provides an application of the composite catalyst in the scheme or the composite catalyst obtained by the preparation method in the scheme in preparing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene.
In the present invention, the preparation of cyclohexylbenzene hydroperoxide by catalytic oxidation of cyclohexylbenzene preferably comprises the steps of: and mixing the composite catalyst, the cyclohexylbenzene and the oxidant for oxidation reaction to obtain the cyclohexylbenzene hydroperoxide.
In the invention, the mass ratio of the composite catalyst to the cyclohexylbenzene is preferably 0.001-0.002:1, more preferably 0.0012-0.0018:1, and even more preferably 0.0014-0.0016:1; the flow rate of the oxidizing agent is preferably 60 to 140mL/min, more preferably 80 to 120mL/min, and even more preferably 90 to 110mL/min; the flow rate of the oxidizing agent is preferably kept constant; the oxidizing agent preferably includes one or both of oxygen and air.
In the present invention, the temperature of the oxidation reaction is preferably 80 to 120 ℃, more preferably 90 to 110 ℃, and the holding time is preferably 3 to 10 hours, more preferably 5 to 7 hours. The composite catalyst provided by the invention is used for carrying out contact reaction on the cyclohexylbenzene and the oxidant, and a reaction equation is shown as a formula I.
When the composite catalyst provided by the invention is used for catalyzing and oxidizing cyclohexylbenzene, the main oxidation product is cyclohexylbenzene hydrogen peroxide, the selectivity can reach 90.4%, the conversion rate of cyclohexylbenzene can reach 34.2%, the catalyst consumption is less, and the catalyst can be recycled.
The following describes the invention in detail with reference to examples for further illustration of the invention, but they should not be construed as limiting the scope of the invention.
Example 1
1.736g Ce (NO) 3 ) 3 ·6H 2 O and 2.352g sodium citrate were added to 10mL deionized water containing 1.750g activated carbon and stirred for 10min;
in another vessel, 19.2g naoh was dissolved in 70mL deionized water and stirred until the solution became clear and transparent;
mixing and stirring the two solutions for 30min, pouring the obtained mixed solution into a polytetrafluoroethylene lining stainless steel autoclave, heating to 100 ℃ and reacting for 24h;
cooling to room temperature, suction filtering the solution, washing with deionized water for 10 times, drying the precipitate at 60deg.C under 0.01MPa for 12 hr, and calcining at 400deg.C for 4 hr to obtain cerium oxide-carbon composite catalyst (CeO) 2 /C)。
Example 2
1.930g Cu (NO) 3 ) 2 ·3H 2 O and 2.352g sodium citrate were added to 40mL of absolute ethanol containing 1.750g carbon nanotubes and stirred for 10min;
then, in the process of continuously stirring, dropwise adding 40mL of 10mol/LNaOH aqueous solution, continuously stirring for 30min to obtain dark blue suspension, pouring the obtained suspension into a polytetrafluoroethylene lining stainless steel autoclave, and heating to 100 ℃ for reaction for 6h;
after cooling to room temperature, the solution was suction-filtered and washed with deionized water and absolute ethanol 10 times, and then the obtained precipitate was dried at 60 ℃ under a pressure of 0.01MPa for 12 hours and calcined at 350 ℃ for 3 hours to obtain a copper oxide-carbon composite catalyst (CuO/C).
Example 3
0.868g Cu (NO) 3 ) 2 ·3H 2 O、0.965g Ce(NO 3 ) 3 ·6H 2 O and 2.352g sodium citrate were added to 40mL deionized water containing 1.750g carbon nanotubes and stirred for 10min;
dropwise adding 2mol/L NaOH aqueous solution to the pH=10 in the continuous stirring process, continuously stirring for 2 hours, transferring the obtained solution to a polytetrafluoroethylene lining stainless steel autoclave, heating to 180 ℃ and reacting for 12 hours;
cooling to room temperature, filtering the solution, washing with deionized water to pH=7, vacuum drying the precipitate at 80deg.C under 0.01MPa for 12 hr, and calcining at 500deg.C for 4 hr to obtain copper-cerium composite oxide-carbon composite catalyst (CuO-CeO) 2 /C)。
Example 4
0.05g of CeO prepared as in example 1 was reacted with 2 Adding a catalyst/C into 50mL of cyclohexylbenzene, heating to 100 ℃, introducing oxygen at a flow rate of 100mL/min, and continuously stirring for reaction for 4 hours to obtain cyclohexylbenzene hydrogen peroxide; wherein the conversion rate of the cyclohexylbenzene is 29.2%, and the selectivity of the cyclohexylbenzene hydroperoxide is 88.9%.
Example 5
0.02g of the CuO/C catalyst prepared according to the method of example 2 is added into 50mL of cyclohexylbenzene, oxygen is introduced at a flow rate of 100mL/min after the catalyst is heated to 100 ℃, and the reaction is continuously stirred for 4 hours to obtain cyclohexylbenzene hydroperoxide; wherein the conversion of cyclohexylbenzene was 34.2%, and the selectivity of cyclohexylbenzene hydroperoxide was 81.2%.
Example 6
0.05g of Cu prepared as in example 3 was admixed 0.1 Ce 0.9 Adding the O/C catalyst into 50mL of cyclohexylbenzene, heating to 100 ℃, introducing oxygen at a flow rate of 100mL/min, and continuously stirring for reaction for 4 hours to obtain cyclohexylbenzene hydrogen peroxide; wherein the conversion rate of the cyclohexylbenzene is 28.4%, and the selectivity of the cyclohexylbenzene hydroperoxide is 90.4%.
Example 7
0.05g of Cu prepared as in example 3 was admixed 0.2 Ce 0.8 Adding the O/C catalyst into 50mL of cyclohexylbenzene, heating to 100 ℃, introducing oxygen at a flow rate of 100mL/min, and continuously stirring for reaction for 4 hours to obtain cyclohexylbenzene hydrogen peroxide; wherein the conversion rate of the cyclohexylbenzene is 29.8%, and the selectivity of the cyclohexylbenzene hydroperoxide is 87.9%.
Example 8
0.05g is mixed according toEXAMPLE 3 Cu prepared by the procedure 0.3 Ce 0.7 Adding the O/C catalyst into 50mL of cyclohexylbenzene, heating to 100 ℃, introducing oxygen at a flow rate of 100mL/min, and continuously stirring for reaction for 4 hours to obtain cyclohexylbenzene hydrogen peroxide; wherein the conversion rate of the cyclohexylbenzene is 30.1%, and the selectivity of the cyclohexylbenzene hydroperoxide is 89.7%.
Example 9
0.05g of Cu prepared as in example 3 was admixed 0.4 Ce 0.6 Adding the O/C catalyst into 50mL of cyclohexylbenzene, heating to 100 ℃, introducing oxygen at a flow rate of 100mL/min, and continuously stirring for reaction for 4 hours to obtain cyclohexylbenzene hydrogen peroxide; wherein the conversion rate of the cyclohexylbenzene is 32.1%, and the selectivity of the cyclohexylbenzene hydroperoxide is 84.3%.
As can be seen from the above examples, the composite catalyst provided by the invention has the advantages of rapid reaction, high conversion rate and high selectivity, and the cyclohexylbenzene is oxidized to generate cyclohexylbenzene hydroperoxide after being added into a cyclohexylbenzene reaction system.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (10)

1. A composite catalyst comprising a reducing component and a metal oxide component supported on the reducing component; the metal oxide component comprises cerium oxide and/or copper oxide; the average valence of cerium in the cerium oxide is greater than +3 and less than +4; the average valence of copper in the copper oxide is greater than +1 and less than +2; the reducing component is carbon.
2. The composite catalyst according to claim 1, wherein the mass ratio of the metal oxide component and the reducing component is 10 to 70:30 to 90.
3. The composite catalyst according to claim 1 or 2, wherein the metal oxide component comprises cerium oxide and copper oxide in a molar ratio of 1-10:1-10.
4. A method for preparing the composite catalyst according to any one of claims 1 to 3, comprising the steps of:
mixing the carbon material mixed solution, metal salt, complexing agent and alkaline solution, performing hydrothermal reaction under a closed condition, and calcining to obtain a composite catalyst;
the metal salt comprises one or more of copper salt and cerium salt.
5. The method according to claim 4, wherein the copper salt comprises one or more of nitrate and chloride; the cerium salt comprises one or more of nitrate and chloride;
the concentration of the carbon material mixed solution is 4.375-17.5 wt%.
6. The method according to claim 4, wherein the hydrothermal reaction is carried out at a temperature of 70 to 130 ℃ for a period of 12 to 48 hours.
7. The method according to claim 4, wherein the calcination atmosphere is air, the temperature is 300-500 ℃, and the heat preservation time is 2-8 hours.
8. Use of a composite catalyst according to any one of claims 1 to 3 or a composite catalyst obtained by a preparation method according to any one of claims 4 to 7 in the preparation of cyclohexylbenzene hydroperoxide by catalytic oxidation of cyclohexylbenzene.
9. The use according to claim 8, wherein the catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene hydroperoxide comprises the steps of:
and mixing the composite catalyst, the cyclohexylbenzene and the oxidant for oxidation reaction to obtain the cyclohexylbenzene hydroperoxide.
10. The use according to claim 9, wherein the mass ratio of the composite catalyst to cyclohexylbenzene is 0.001-0.002:1; the flow rate of the oxidant is 60-140 mL/min.
CN202310436089.5A 2023-04-21 2023-04-21 Composite catalyst and preparation method and application thereof Pending CN116459825A (en)

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