CN115974655A - Application of high-load copper monatomic catalyst in preparation of phenol by using hydrogen peroxide - Google Patents
Application of high-load copper monatomic catalyst in preparation of phenol by using hydrogen peroxide Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
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- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 claims description 2
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses application of a high-load copper monatomic catalyst in preparation of phenol by using hydrogen peroxide. The invention provides a preparation method of phenol, which comprises the following steps: in the presence of a copper monatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained by extraction; the copper monatomic catalyst has Cu 1 ‑N 3 O 1 An atom coordination structure; the load of the copper single atom is 20-30%. The invention can obviously improve the oxidation selectivity of benzene and the utilization rate of hydrogen peroxide by using the copper monatomic catalyst with a unique coordination structure in the reaction of oxidizing benzene by hydrogen peroxide.
Description
Technical Field
The invention belongs to the technical field of benzene hydroxylation reaction, and particularly relates to an application of a high-load copper monatomic catalyst in preparation of phenol by using hydrogen peroxide.
Background
Phenol is an important chemical industrial raw material and intermediate, and has wide application in the production of synthetic resins, dyes, nylon, medicines, pesticides and the like. At present, more than 90% of phenol comes from the traditional three-step cumyl benzene method, and the process is complex, low in yield and large in environmental pollution. The method for preparing phenol by directly oxidizing benzene with a hydrogen peroxide one-step method becomes an alternative method, and the reaction condition in the process is mild, and the yield of phenol is high. Therefore, more and more catalysts are being developed to promote this reaction, including molecular sieves, doped carbon materials, and transition metal nanomaterials, among others. However, the low conversion and the unclear active site have prevented the development of the reaction of oxidizing benzene with hydrogen peroxide.
The monatomic catalysts (SACs) become the best candidate catalysts for the current oxydol benzene oxidation reaction due to the characteristics of unique electronic structures, clear reaction sites, 100% atom utilization rate and the like. However, SACs have been reported to exhibit two major problems: (1) The use of excessive hydrogen peroxide causes low utilization rate of hydrogen peroxide; (2) Low metal loading results in low specific activity of the catalyst mass. For example, dunde et al (Sc/. Adv.2015,1, e1500462) loaded 2.5wt% Fe single atom on graphene, had a hydrogen peroxide utilization of 1.8% in benzene hydroxylation reaction and a specific mass activity of 0.88mmol/g/h. The Liyadona task group (nat. Commu/.,2018,9, 3861) reported a cocoon silk chemistry strategy, synthesizing 0.6wt% Co single atom, with a hydrogen peroxide utilization of 4.7% in the benzene hydroxylation reaction and a mass specific activity of 0.64mmol/g/h. Obviously, these SACs are far from practical use in benzene hydroxylation reactions. Therefore, developing a method for preparing a high-loading monatomic catalyst and improving the utilization rate of hydrogen peroxide are the biggest challenges of hydroxylation reaction.
Disclosure of Invention
The invention aims to provide a novel phenol preparation method. The copper monatomic catalyst with a unique coordination structure is used in the reaction of oxidizing benzene by hydrogen peroxide, so that the oxidation selectivity of benzene and the utilization rate of hydrogen peroxide are obviously improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing phenol, comprising the steps of: in the presence of a copper monatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained by extraction;
the copper monoatomicThe catalyst has Cu 1 -N 3 O 1 An atom coordination structure; the load of the copper single atom is 20-30%.
The copper monatomic catalyst consists of a two-dimensional layered carrier and a copper monatomic loaded on the two-dimensional layered carrier; wherein the two-dimensional layered carrier is a nitrogen-oxygen doped carbon material; the aperture of the two-dimensional layered carrier is 0.5-5/m, the specific surface area is 350-500m 2 /g。
The copper monatomic catalyst is prepared according to the following steps:
s1, in the presence of a solvent, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid to obtain a two-dimensional layered carrier, and recording the two-dimensional layered carrier as a 2D-polymer;
s2, adding a precursor containing copper metal salt into the 2D-polymer, and stirring to obtain a polymer containing copper metal, and recording the polymer as Cu @2D-polymer;
s3, freeze-drying the Cu @2D-polyme to obtain Cu @2D-polyme powder;
and S4, carrying out high-temperature treatment on the Cu @2D-polyme powder to obtain the copper monatomic catalyst.
In step S1, the solvent is selected from at least one of deionized water, ethanol, and acetone; deionized water is preferred to ensure higher and more uniform loading of the copper monoatomic load.
In the step S1, the mass-to-volume ratio of the melamine, the cyanuric acid, the L-alanine and the phytic acid is as follows: 1g: (0.5-2) g: (0.5-2) g: (200-400) μ L; preferably 1g: (1-2) g: (1-2) g: and (350-400) mu L.
In step S1, the conditions of the polycondensation reaction are: the temperature is 90-150 deg.C, preferably 100-110 deg.C, and the time is 1-1.5h, preferably 1h.
In step S2, the precursor containing copper metal salt is selected from Cu (NO) 3 ) 2 ·4H 2 O、CuCl 2 And Cu (acac) 2 At least one of; preferably Cu (NO) 3 ) 2 ·4H 2 And O, compared with other precursors, the supported amount is higher, and the distribution is more uniform.
In step S2, the mass ratio of the precursor containing copper metal salt to the melamine is (0.1-0.5): 1; preferably (0.1-0.3): 1.
in step S2, the reaction system is made to be a sludge by the stirring.
In step S3, the conditions of freeze-drying are as follows: under vacuum condition, the temperature is-10 to-20 ℃, preferably-10 to-15 ℃, and the time is 15 to 22 hours, preferably 20 to 22 hours.
In step S4, the conditions of the high-temperature pyrolysis are: under inert gas atmosphere, the temperature is 600-800 ℃, preferably 700-750 ℃, the heating rate is 2-5 ℃/m//, preferably 2-3 ℃/m//, and the time is 1-3h, preferably 2h.
In step S4, the inert gas is Ar gas or N 2 At least one of gas.
In the preparation method of the phenol, the molar ratio of the benzene to the hydrogen peroxide is 1: (0.5-10), preferably 1: (0.5-1), more preferably 1.
In the above phenol production method, the oxidation reaction conditions are as follows: the temperature is 55-65 deg.C, preferably 60-65 deg.C, and the time is 1-144h, preferably 95-144h.
In the above method for producing phenol, the solvent is at least one of acetonitrile, tetrahydrofuran and pyridine.
The invention has the following beneficial effects:
the copper monatomic catalyst provided by the invention shows higher conversion rate and hydrogen peroxide utilization rate in the hydrogen peroxide benzene oxidation reaction; the reason for this is probably that the high-density copper monoatomic changes the reaction path of the hydrogen peroxide and inhibits the generation of the side reaction oxygen, thereby improving the utilization rate of the hydrogen peroxide in the benzene oxidation reaction.
Drawings
FIG. 1 is a photograph of a spherical aberration corrected high angle annular dark field scanning transmission electron microscope (HAADF-STEM) of a copper monatomic catalyst prepared in example 1 of the present invention.
FIG. 2 is a surface-scanning distribution diagram of a copper monatomic catalyst prepared in example 1 of the present invention.
FIG. 3 is a K-edge EXAFS Fourier transform spectrum of Cu of the copper monatomic catalyst prepared in example 1 of the present invention.
FIG. 4 is a graph showing the comparative effect of the hydrogen peroxide on benzene oxidation to phenol as described in examples 1-4.
Fig. 5 shows the stability of the copper monatomic catalyst prepared in example 1 of the present invention in the reaction of oxidizing benzene with hydrogen peroxide to prepare phenol.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of phenol by one-step method of direct oxidation of benzene with hydrogen peroxide
The method comprises the following specific steps:
(1) Preparation of Cu monatomic catalyst:
adding 2g of melamine, 2g of cyanuric acid, 2g of L-alanine and 400 mu L of phytic acid into solvent deionized water, and carrying out in-situ polycondensation at 100 ℃ for 1h to obtain a 2D-polymer; 270mg of Cu (NO) were added 3 ) 2 ·4H 2 O, then stirring the mixture to be mud-shaped to obtain a 2D-polymer containing Cu; placing the obtained 2D-polyme containing Cu in a vacuum drier, freeze-drying at-10 ℃ for 22h, and removing the solvent to obtain Cu @2D-polymer powder; under the protection of argon, heating Cu @2D-polymer powder to 700 ℃ at the speed of 2 ℃/m// and naturally cooling after keeping for 2h to obtain the Cu monatomic catalyst with high load, wherein the load is 22wt%.
The spherical aberration corrected high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of the resulting copper monatomic catalyst, as shown in FIG. 1, demonstrates that copper is present in a monatomic form.
The surface scanning distribution diagram of the obtained copper monatomic catalyst, as shown in FIG. 2, proves that the copper element is in the catalyst materialUniformly distributing; through detection, the aperture of the two-dimensional layered carrier is 3/m, and the specific surface area is 350m 2 /g。
The K-edge EXAFS Fourier transform spectrum of Cu of the obtained copper monatomic catalyst is shown in figure 3, and the fact that the copper has Cu-N is proved 3 O 1 A coordination structure.
(2) Preparing phenol by oxidizing benzene with hydrogen peroxide:
in a 25mL sealed glass reactor, 10mg of the Cu monatomic catalyst prepared in step (1), 0.3mL of benzene and H were added 2 O 2 (30%) 0.4mL (benzene and H) 2 O 2 The molar ratio of (1); after the reaction is finished, filtering the reaction product by using a filter membrane, and adding ethyl acetate to extract the catalytic product.
Example 2 preparation of phenol by one-step method of direct oxidation of benzene with hydrogen peroxide
Phenol was prepared by the method described in example 1, except that H was 2 O 2 (30%) 0.2mL, i.e., benzene and H 2 O 2 Is 1.
Example 3 preparation of phenol by one-step method of direct oxidation of benzene with hydrogen peroxide
Phenol was prepared by the method described in example 1, except that H was 2 O 2 (30%) 0.8mL, i.e., benzene and H 2 O 2 In a molar ratio of 1.
Example 4 preparation of phenol by one-step method of direct oxidation of benzene with hydrogen peroxide
Phenol was prepared by the method described in example 1, except that H was 2 O 2 (30%) 4mL, i.e., benzene and H 2 O 2 Is 1.
The catalytic products obtained in examples 1 to 4 were analyzed by gas chromatography (GC, sh/madzu, GC2010 plus) and gas mass spectrometry (GCMS, sh/madzu, GCMS-QP 2010S) using n-tridecane as an internal standard, respectively.
The results are shown in FIG. 4, benzene and H 2 O 2 When the molar ratio of (1)The water utilization rate is 54.4%;
benzene and H 2 O 2 When the molar ratio of (1);
benzene and H 2 O 2 When the molar ratio of (1);
benzene and H 2 O 2 When the molar ratio of (1).
Therefore, the high-load copper monatomic catalyst is used in the reaction for preparing phenol by directly oxidizing benzene with the hydrogen peroxide one-step method, so that the oxidation selectivity of benzene and the utilization rate of hydrogen peroxide can be obviously improved.
The stability test of the copper monatomic catalyst prepared in the example 1 in the reaction of preparing phenol by oxidizing benzene with hydrogen peroxide comprises the following steps:
(1) Preparing phenol by oxidizing benzene with hydrogen peroxide:
in a 25mL sealed glass reactor, 10mg of the Cu monatomic catalyst obtained in step (1) of example 1, 0.3mL of benzene 2 O 2 (30%) 0.4mL (benzene and H) 2 O 2 The molar ratio of (1); after the reaction is finished, filtering the reaction product by using a filter membrane, and adding ethyl acetate to extract a catalytic product;
(2) Regeneration of the Cu monatomic catalyst:
separating the reaction liquid after the reaction of the step (1) for 24 hours, washing the reaction liquid with ethyl acetate for three times, and carrying out vacuum drying at the temperature of 60 ℃ for 2 hours to obtain a regenerated Cu monatomic catalyst;
(3) In a 25mL sealed glass reactor, 10mg of the regenerated Cu monatomic catalyst obtained in the above step (2), 0.3mL of benzene 2 O 2 (30%) 0.4mL (benzene and H) 2 O 2 The molar ratio of (1); reaction ofAfter the reaction, the reaction product was filtered through a filtration membrane, and ethyl acetate was added to extract the catalytic product.
(4) And (3) repeating the step (1) to obtain the regenerated Cu monatomic catalyst, and recycling for 10 times.
The catalytic product obtained in each time is analyzed by gas chromatography (GC, sh/madzu, GC2010 plus) and gas mass spectrometry (GCMS, sh/madzu, GCMS-QP 2010S) by taking n-tridecane as an internal standard.
The stability of the cyclically regenerated Cu monatomic catalyst in the benzene oxidation reaction by hydrogen peroxide is shown in figure 5 between benzene and H 2 O 2 Under the condition that the molar ratio of (1). Therefore, the high-load Cu monatomic catalyst provided by the invention can be circulated for more than 10 times, and has good circulation performance.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for preparing phenol, comprising the steps of: in the presence of a copper monatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained by extraction;
the copper monatomic catalyst has Cu 1 -N 3 O 1 An atom coordination structure; the load of the copper single atom is 20-30%.
2. The process for producing phenol according to claim 1, characterized in that: the copper monatomic catalyst is prepared according to the following steps:
s1, in the presence of a solvent, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid to obtain a two-dimensional layered carrier, and recording the two-dimensional layered carrier as a 2D-polymer;
s2, adding a precursor containing copper metal salt into the 2D-polymer, and stirring to obtain a polymer containing copper metal, and recording the polymer as Cu @2D-polymer;
s3, freeze-drying the Cu @2D-polyme to obtain Cu @2D-polyme powder;
and S4, carrying out high-temperature treatment on the Cu @2D-polyme powder to obtain the copper monatomic catalyst.
3. The process for producing phenol according to claim 2, characterized in that: in step S1, the solvent is selected from at least one of deionized water, ethanol, and acetone;
the mass-volume ratio of the melamine to the cyanuric acid to the L-alanine to the phytic acid is as follows: 1g: (0.5-2) g: (0.5-2) g: (200-400) μ L;
the conditions of the polycondensation reaction are as follows: the temperature is 90-150 ℃ and the time is 1-1.5h.
4. The process for producing phenol according to claim 2 or 3, characterized in that: in step S2, the precursor containing copper metal salt is selected from Cu (NO) 3 ) 2 ·4H 2 O、CuCl 2 And Cu (acac) 2 At least one of;
the mass ratio of the precursor containing copper metal salt to the melamine is (0.1-0.5): 1;
the stirring makes the reaction system be in a mud shape.
5. The process for producing phenol according to any one of claims 2 to 4, characterized in that: in step S3, the conditions of freeze-drying are as follows: under vacuum condition, the temperature is-10- -20 deg.C, and the time is 15-22h.
6. The process for producing phenol according to any one of claims 2 to 5, characterized in that: in step S4, the conditions of the high-temperature pyrolysis are: under the inert gas atmosphere, the temperature is 600-800 ℃, the heating rate is 2-5 ℃/m//, and the time is 1-3h.
7. The process for producing phenol according to any one of claims 1 to 6, characterized in that: the molar ratio of the benzene to the hydrogen peroxide is 1: (0.5-10).
8. The process for producing phenol according to any one of claims 1 to 7, characterized in that: the solvent is at least one of acetonitrile, tetrahydrofuran and pyridine.
9. The process for producing phenol according to any one of claims 1 to 8, characterized in that: the conditions of the oxidation reaction are as follows: the temperature is 55-65 ℃ and the time is 1-144h.
10. The process for producing phenol according to any one of claims 1 to 9, characterized in that: the solvent used for extraction is at least one of ethyl acetate, dichloromethane and n-hexane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116813449A (en) * | 2023-06-21 | 2023-09-29 | 中国科学院化学研究所 | Phosphorus coordinated iridium monoatomic catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde |
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| CN104801330A (en) * | 2015-03-25 | 2015-07-29 | 嘉兴学院 | Supported type mesoporous molecular sieve catalyst and application thereof |
| CN105521825A (en) * | 2014-09-30 | 2016-04-27 | 中国石油天然气股份有限公司 | Catalyst for preparing phenol by benzene oxidation, and preparation method and application thereof |
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| CN105521825A (en) * | 2014-09-30 | 2016-04-27 | 中国石油天然气股份有限公司 | Catalyst for preparing phenol by benzene oxidation, and preparation method and application thereof |
| CN104801330A (en) * | 2015-03-25 | 2015-07-29 | 嘉兴学院 | Supported type mesoporous molecular sieve catalyst and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116813449A (en) * | 2023-06-21 | 2023-09-29 | 中国科学院化学研究所 | Phosphorus coordinated iridium monoatomic catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde |
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