CN115974655B - Application of high-load copper monoatomic catalyst in preparation of phenol by hydrogen peroxide - Google Patents
Application of high-load copper monoatomic catalyst in preparation of phenol by hydrogen peroxide Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 156
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
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- 238000011068 loading method Methods 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims description 5
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims description 5
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 5
- 229960003767 alanine Drugs 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 229940068041 phytic acid Drugs 0.000 claims description 5
- 235000002949 phytic acid Nutrition 0.000 claims description 5
- 239000000467 phytic acid Substances 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 230000003647 oxidation Effects 0.000 abstract description 12
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 229960002163 hydrogen peroxide Drugs 0.000 description 33
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005805 hydroxylation reaction Methods 0.000 description 5
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FYABMGZBIRRBQY-UHFFFAOYSA-N benzene;hydrogen peroxide Chemical compound OO.C1=CC=CC=C1 FYABMGZBIRRBQY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- -1 hydrogen peroxide benzene oxide Chemical compound 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical group N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
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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 an application of a high-load copper monoatomic catalyst in preparing phenol by hydrogen peroxide. The invention provides a preparation method of phenol, which comprises the following steps: in the presence of a copper monoatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained through extraction; the copper monoatomic catalyst has Cu 1 ‑N 3 O 1 An atomic coordination structure; the loading of copper single atoms is 20% -30%. According to the invention, the copper monoatomic catalyst with a unique coordination structure is used in the reaction of oxidizing benzene with hydrogen peroxide, so that the benzene oxidation selectivity and the hydrogen peroxide utilization rate can be remarkably improved.
Description
Technical Field
The invention belongs to the technical field of benzene hydroxylation reaction, and particularly relates to application of a high-loading copper monoatomic catalyst in preparation of phenol from hydrogen peroxide.
Background
Phenol is an important raw material and intermediate in chemical industry, and has wide application in the production of synthetic resins, dyes, nylons, medicines, pesticides, and the like. At present, more than 90 percent of phenol comes from the traditional three-step isopropylbenzene method, and the process is complex, the yield is low and the environmental pollution is large. The method for preparing phenol by directly oxidizing benzene through hydrogen peroxide one-step method is an alternative method, and the reaction condition is mild and the phenol yield is high in the process. Accordingly, an increasing number of catalysts have been developed to facilitate this reaction, including molecular sieves, doped carbon materials, and transition metal nanomaterials, among others. However, low conversion and active sites do not clearly hinder the development of this reaction for oxydol to oxidize benzene.
The single-atom catalyst (SACs) becomes the best candidate catalyst for the current oxydol benzene oxidation reaction because of the characteristics of unique electronic structure, definite reaction site, 100% of atom utilization rate and the like. However, SACs have been reported to exhibit two major problems: (1) The hydrogen peroxide utilization rate is low due to the excessive hydrogen peroxide; (2) Low metal loadings result in low catalyst mass specific activity. For example, deng Dehui et al (Sc/. Adv.2015,1, e 1500462) supported 2.5wt% Fe monoatoms on graphene, and had a hydrogen peroxide utilization of 1.8% and a mass specific activity of 0.88mmol/g/h in the benzene hydroxylation reaction. Li Yadong group (Nat. Commu/.,2018,9,3861) reports a cocoon silk chemistry strategy, which synthesizes 0.6wt% of Co monoatoms, wherein the hydrogen peroxide utilization rate in benzene hydroxylation reaction is 4.7%, and the mass specific activity is 0.64mmol/g/h. Clearly, these SACs are far from practical application in benzene hydroxylation reactions. Therefore, developing a catalyst with high loading of monoatomic catalyst and improving hydrogen peroxide utilization rate is the biggest challenge of hydroxylation reaction.
Disclosure of Invention
The invention aims to provide a novel phenol preparation method. By using the copper monoatomic catalyst with a unique coordination structure in the reaction of oxidizing benzene with hydrogen peroxide, the benzene oxidation selectivity and the hydrogen peroxide utilization rate are obviously improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing phenol, comprising the steps of: in the presence of a copper monoatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained through extraction;
the copper monoatomic catalyst has Cu 1 -N 3 O 1 An atomic coordination structure; the loading of copper single atoms is 20% -30%.
The copper monoatomic catalyst consists of a two-dimensional layered carrier and copper monoatoms loaded on the two-dimensional layered carrier; wherein the two-dimensional layered carrier is a nitrogen-oxygen doped carbon material; the pore diameter of the two-dimensional lamellar carrier is 0.5-5/m, and the specific surface area is 350-500m 2 /g。
The copper monoatomic catalyst is prepared according to the following steps:
s1, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid in the presence of a solvent to obtain a two-dimensional layered carrier, namely a 2D-polymer;
s2, adding a precursor containing copper metal salt into the 2D-polymer, and stirring to obtain a polymer containing copper metal, namely Cu@2D-polymer;
s3, freeze-drying the Cu@2D-polyme to obtain Cu@2D-polyme powder;
s4, carrying out high-temperature treatment on the Cu@2D-polyme powder to obtain the copper monoatomic catalyst.
In step S1, the solvent is at least one selected from deionized water, ethanol and acetone; deionized water is preferred to ensure higher and more uniform loading of copper monoatoms.
In the step S1, the mass-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) μL; preferably 1g: (1-2) g: (1-2) g: (350-400) mu L.
In step S1, the conditions of the polycondensation reaction are: the temperature is 90-150deg.C, preferably 100-110deg.C, and the time is 1-1.5 hr, preferably 1 hr.
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 (a) and (b); preferably Cu (NO) 3 ) 2 ·4H 2 And compared with other precursors, the O has higher loading capacity and more uniform distribution.
In the step S2, the mass ratio of the precursor containing copper metal salt to the melamine is (0.1-0.5): 1, a step of; preferably (0.1-0.3): 1.
in step S2, the stirring causes the reaction system to be in a mud-like state.
In step S3, the conditions of the freeze-drying are as follows: under vacuum condition, the temperature is-10-20deg.C, preferably-10-15deg.C, and the time is 15-22 hr, preferably 20-22 hr.
In step S4, the conditions of the pyrolysis are: under the inert gas atmosphere, the temperature is 600-800 ℃, preferably 700-750 ℃, the temperature rising rate is 2-5 ℃/m/, preferably 2-3 ℃/m/, and the time is 1-3 hours, preferably 2 hours.
In step S4, the inert gas is Ar gas, N 2 At least one of the gases.
In the above phenol preparation method, the molar ratio of benzene to hydrogen peroxide is 1: (0.5-10), preferably 1: (0.5-1), more preferably 1:1.
In the above phenol production method, the oxidation reaction conditions are as follows: the temperature is 55-65deg.C, preferably 60-65deg.C, and the time is 1-144 hr, preferably 95-144 hr.
In the above method for preparing phenol, the solvent is at least one of acetonitrile, tetrahydrofuran and pyridine.
The beneficial effects of the invention are as follows:
the copper monoatomic catalyst provided by the invention has 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 monoatoms change the reaction path of the hydrogen peroxide and inhibit the generation of oxygen in side reaction, thereby improving the utilization rate of the hydrogen peroxide in the benzene oxidation reaction.
Drawings
FIG. 1 is a spherical aberration correcting high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of a copper monoatomic catalyst prepared in example 1 of the present invention.
FIG. 2 is a facial sweep plot of a copper monoatomic catalyst prepared in example 1 of the present invention.
FIG. 3 is a chart showing the K-edge EXAFS Fourier transform of Cu of the copper monoatomic catalyst prepared in example 1 of the present invention.
FIG. 4 is a graph showing the comparison of the catalytic effect of benzene oxydol to phenol in examples 1-4.
Fig. 5 shows the stability of the copper monoatomic catalyst prepared in example 1 of the present invention in the reaction of oxidizing benzene with hydrogen peroxide to prepare phenol.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of phenol by Hydrogen peroxide one-step direct Oxidation of benzene
The method comprises the following specific steps:
(1) Preparation of Cu monoatomic catalyst:
adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into deionized water serving as a solvent, and carrying out in-situ polycondensation for 1h at the temperature of 100 ℃ to obtain a 2D-polymer; 270mg Cu (NO) 3 ) 2 ·4H 2 O, stirring to mud to obtain a Cu-containing 2D-polymer; placing the obtained Cu-containing 2D-polyme in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Cu@2D-polyme powder; under the protection of argon, the Cu@2D-polymer powder is heated to 700 ℃ at the speed of 2 ℃/m// and naturally cooled after being kept for 2 hours, and then the Cu monoatomic catalyst with high load is obtained, wherein the load is 22 weight percent.
The spherical aberration correcting high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of the resulting copper monoatomic catalyst, as shown in fig. 1, demonstrates that copper exists in monoatomic form.
The scanning distribution diagram of the obtained copper monoatomic catalyst is shown as figure 2, which proves that copper elements are uniformly distributed in the catalyst material; through detection, the pore diameter of the two-dimensional lamellar 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 monoatomic catalyst is shown in FIG. 3, which proves that copper has Cu-N 3 O 1 Coordination structure.
(2) Preparing phenol by oxidizing benzene with hydrogen peroxide:
in a 25mL sealed glass reactor, 10mg of the Cu monoatomic catalyst prepared in the step (1), 0.3mL of benzene and H are added 2 O 2 (30%) 0.4mL (benzene with H 2 O 2 Molar ratio of (3)1:1), acetonitrile 3.0mL, starting the reaction at 60 ℃ for 144h; after the reaction, the reaction product was filtered by a filter membrane, and ethyl acetate was added to extract the catalytic product.
Example 2 preparation of phenol by Hydrogen peroxide one-step direct Oxidation of benzene
Phenol was prepared as described in example 1, except that H 2 O 2 (30%) 0.2mL of benzene with H 2 O 2 The molar ratio of (2) is 1:0.5.
Example 3 preparation of phenol by Hydrogen peroxide one-step direct Oxidation of benzene
Phenol was prepared as described in example 1, except that H 2 O 2 (30%) 0.8mL of benzene with H 2 O 2 The molar ratio of (2) is 1:2.
Example 4 preparation of phenol by Hydrogen peroxide one-step direct Oxidation of benzene
Phenol was prepared as described in example 1, except that H 2 O 2 (30%) 4mL of benzene with H 2 O 2 The molar ratio of (2) is 1:10.
Effect verification 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, where benzene and H 2 O 2 When the molar ratio of the catalyst is 1:0.5, the conversion rate of benzene is 27.2%, the oxidation selectivity of benzene is 99.75%, and the utilization rate of hydrogen peroxide is 54.4%;
benzene and H 2 O 2 When the molar ratio of (1) to (1) is 1:1, the conversion rate of benzene is 50.1%, the oxidation selectivity of benzene is 99.25%, and the hydrogen peroxide utilization rate is 50.1%;
benzene and H 2 O 2 When the molar ratio of (2) is 1:2, the conversion rate of benzene is 59.8%, the oxidation selectivity of benzene is 94.5%, and the utilization rate of hydrogen peroxide is 29.4%;
benzene and H 2 O 2 When the molar ratio of (2) is 1:10, the conversion rate of benzene is 78.2%, the oxidation selectivity of benzene is 90.5%, and the utilization rate of hydrogen peroxide is7.8％。
From this, it can be obtained that the oxidation selectivity of benzene and the utilization rate of hydrogen peroxide can be remarkably improved by using a high-loading copper monoatomic catalyst in the reaction of preparing phenol by directly oxidizing benzene with hydrogen peroxide by a one-step method.
Effect verification 2
The stability test of the copper single-atom 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 monoatomic catalyst obtained in the step (1) of example 1, 0.3mL of benzene and H were charged 2 O 2 (30%) 0.4mL (benzene with H 2 O 2 The molar ratio of (1:1), acetonitrile 3.0mL, starting the reaction at 60 ℃ for 24 hours; filtering the reaction product by using a filtering membrane after the reaction is finished, and adding ethyl acetate to extract a catalytic product;
(2) Regeneration of Cu monoatomic catalyst:
separating the reaction liquid after 24 hours of the reaction in the step (1), washing with ethyl acetate for three times, and vacuum drying at 60 ℃ for 2 hours to obtain a regenerated Cu monoatomic catalyst;
(3) 10mg of the regenerated Cu monoatomic catalyst obtained in the step (2) and 0.3mL of benzene and H are added into a 25mL sealed glass reactor 2 O 2 (30%) 0.4mL (benzene with H 2 O 2 The molar ratio of (1:1), acetonitrile 3.0mL, starting the reaction at 60 ℃ for 24 hours; after the reaction, the reaction product was filtered by a filter membrane, and ethyl acetate was added to extract the catalytic product.
(4) And (3) repeating the step (1) to obtain the regenerated Cu monoatomic catalyst, and recycling for 10 times.
The catalytic products obtained each time 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.
The stability of the circularly regenerated Cu monoatomic catalyst in the reaction of hydrogen peroxide benzene oxide is shown in figure 5, and the catalyst is prepared by reacting benzene and H 2 O 2 Molar ratio of (2) isUnder the condition of 1:1, the conversion rate of benzene is kept at about 21%, the oxidation selectivity of benzene is kept at about 99.7, and the corresponding hydrogen peroxide utilization rate is kept at about 21%. Therefore, the high-load Cu monoatomic catalyst provided by the invention can be recycled for more than 10 times, and has good recycling performance.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for preparing phenol, comprising the steps of: in the presence of a copper monoatomic catalyst, benzene and hydrogen peroxide are subjected to oxidation reaction in a solvent, and phenol is obtained through extraction;
the copper monoatomic catalyst has Cu 1 -N 3 O 1 An atomic coordination structure; the loading of copper single atoms is 20% -30%;
the copper monoatomic catalyst is prepared according to the following steps:
s1, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid in the presence of a solvent to obtain a two-dimensional layered carrier, namely a 2D-polymer;
s2, adding a precursor containing copper metal salt into the 2D-polymer, and stirring to obtain a polymer containing copper metal, namely Cu@2D-polymer;
s3, freeze-drying the Cu@2D-polyme to obtain Cu@2D-polyme powder;
s4, carrying out high-temperature treatment on the Cu@2D-polyme powder to obtain the copper monoatomic catalyst;
in step S4, the conditions of the high temperature treatment are as follows: under the inert gas atmosphere, the temperature is 600-800 ℃, the temperature rising rate is 2-5 ℃/min, and the time is 1-3h.
2. The method for producing phenol according to claim 1, characterized in that: in step S1, the solvent is at least one selected from 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) μL;
the conditions of the polycondensation reaction are as follows: the temperature is 90-150 ℃ and the time is 1-1.5h.
3. The method for producing phenol according to claim 2, 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 (a) and (b);
the mass ratio of the precursor containing copper metal salt to the melamine is (0.1-0.5): 1, a step of;
the stirring makes the reaction system mud-like.
4. A process for producing phenol according to claim 3, characterized in that: in step S3, the conditions of the freeze-drying are as follows: under the vacuum condition, the temperature is between-10 ℃ and-20 ℃ and the time is between 15 and 22 hours.
5. The method for producing phenol according to any one of claims 1 to 4, wherein: the molar ratio of benzene to hydrogen peroxide is 1: (0.5-10).
6. The method for producing phenol according to claim 5, wherein: the solvent is at least one of acetonitrile, tetrahydrofuran and pyridine.
7. The method for producing phenol according to claim 6, wherein: the conditions of the oxidation reaction are as follows: the temperature is 55-65 ℃ and the time is 1-144h.
8. The method for producing phenol according to claim 7, wherein: the solvent used for the extraction is at least one of ethyl acetate, dichloromethane and n-hexane.
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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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| Ionic-liquid-assisted synthesis of metal single-atom catalysts for benzene oxidation to phenol;Qikai Shen，等;Sci China Mater;第65卷(第1期);全文 * |
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