CN117861650A - Preparation method and application of heat treatment modified palladium catalyst - Google Patents
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of catalysts, and provides a preparation method and application of a heat treatment modified palladium catalyst. Adding palladium catalyst and polymer which can be decomposed into volatile micromolecules by heating in the heat treatment process, and treating for 5-300min at 30-600 ℃ to obtain the heat treatment modified palladium catalyst. The palladium catalyst comprises a supported or encapsulated catalyst with different carrier materials, structures and surface morphologies. The polymers include resins, biomass molecules and polymeric compounds that decompose into volatile small molecule low alkanes, alkenes and alkynes during heat treatment. The catalyst prepared by the method has the advantages of simple process, low preparation cost and easy scale-up production. When the modified catalyst is applied to liquid-phase phenol hydrogenation, the selectivity of cyclohexanone of more than 90% can be realized while the reaction conversion rate of more than 99% is ensured, and the catalyst has better stability, can be recycled for multiple times and has good application prospect in industrial production.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a preparation method of a heat treatment modified palladium catalyst, and particularly relates to a method for synthesizing cyclohexanone by catalyzing phenol to selectively hydrogenate.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Substances containing c=o are an important class of chemicals, for example cyclohexanone is an important class of chemical production platform molecules and organic reagents, and is an important raw material for preparing caprolactam and adipic acid, key intermediates for nylon 6 and nylon 66. At present, two methods are mainly adopted in the industrial production of cyclohexanone, one is a cyclohexane oxidation method and the other is a phenol selective hydrogenation method. The former needs high-temperature high-pressure reaction conditions, the production cost and the energy consumption are high, the selectivity of target products is low, and the subsequent recovery and separation difficulty of cyclohexanone is high. Compared with the cyclohexane oxidation method, the one-step method for preparing cyclohexanone by phenol hydrogenation has the advantages of simple production process, high atom economy, low energy consumption, less byproducts and the like, and has higher industrial production potential and application prospect. At present, the main problem of the production path is that cyclohexanone is unstable and is easy to continue to react to form cyclohexanol as an excessive hydrogenation product. The preparation of a catalyst with high phenol conversion and cyclohexanone selectivity is therefore critical for studying the process.
The supported palladium catalyst is widely reported in the reaction of preparing cyclohexanone by phenol hydrogenation, and has good activity and selectivity (CN 110898853A). In order to further improve the selectivity of cyclohexanone, the spatial adsorption mode of cyclohexanone on the active component is changed to inhibit excessive hydrogenation by adding an acid-base additive into the reaction system (CN 101709027A). However, catalytic reactions require the presence of organic reagents or CO 2 The method is carried out in the system, and meanwhile, the addition of the additive influences the subsequent separation and purification process of cyclohexanone, so that the method does not accord with the aim of green chemistry. Patent CN103831099a discloses a method for modifying palladium catalyst by using alkyne, and the modified palladium catalyst has better catalytic effect on catalytic hydrogenation reaction of styrene, but the inventor researches find that: the selectivity and conversion rate of the modified palladium catalyst for preparing cyclohexanone by phenol hydrogenation are still to be improved.
Disclosure of Invention
The invention aims to provide a synthesis method of a heat treatment modified palladium catalyst aiming at the problems of complex production process, low cyclohexanone yield and the like in the preparation of cyclohexanone by phenol hydrogenation, and the synthesis method is applied to the process of preparing cyclohexanone by hydrogen selective reduction and shows good catalytic performance. The invention utilizes a simple heat treatment technology, and adopts micromolecular volatile gas generated by polymer decomposition in the pyrolysis process to crack, deposit and infiltrate on the surface of the palladium catalyst, thereby changing the valence state and coordination environment of palladium metal. The thermal modified palladium metal catalyst obtained through subsequent activation and reduction treatment has the advantages of high specific surface area, high stability, high cyclohexanone selectivity prepared by phenol hydrogenation and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing a heat-treated modified palladium catalyst, comprising:
the palladium catalyst and the polymer which can be decomposed into volatile micromolecules by heating are directly introduced into the catalyst, or carbon-containing micromolecule gas is directly introduced into the catalyst, and the catalyst and the polymer are subjected to heat treatment together in an inert atmosphere to obtain a product B;
and (3) activating, drying and reducing the product B to obtain the product.
According to the invention, the palladium catalyst is mixed with the polymer which can be decomposed into volatile micromolecules by heating in the heat treatment process, the nonmetallic carbon element modifies the surface and subsurface of palladium metal crystals, the valence state and coordination environment of active center palladium particles are changed, the purposes of regulating the adsorption of intermediate C=O groups and inhibiting the generation of beta-hydrides are achieved, and the purpose of preparing cyclohexanone by phenol high-selectivity hydrogenation is realized. The catalyst adopts non-metal carbon as an electronic auxiliary agent, has wide sources, is cheap and easy to obtain, has simple operation process and technology, and is suitable for green and efficient large-scale production.
In a second aspect of the present invention, there is provided a heat-treated modified palladium catalyst prepared by the above-described method.
In a third aspect, the invention provides an application of the heat treatment modified palladium catalyst in catalytic selective hydrogenation to obtain a high-selectivity c=o product in the presence of a multifunctional group.
The beneficial effects of the invention are that
(1) The invention realizes non-metal carbon deposition/doping of active sites of metal particles by modifying the palladium catalyst through a thermal treatment vapor deposition technology, and has the characteristics of uniform dispersion of metal particles, multiple active sites, good stability and the like.
(2) The heat treatment modified palladium catalyst is applied to preparing cyclohexanone by phenol hydrogenation, the conversion rate of phenol is more than 99%, the selectivity of cyclohexanone is more than 90%, the one-step conversion of phenol is realized, and the catalyst has the advantages of simple production process, low cost, mild reaction conditions and the like, and is easy for industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a TEM image of a palladium on carbon catalyst;
FIG. 2 is a TEM image of the heat-treated modified palladium catalyst prepared in example 1;
FIG. 3 is a TEM image of the heat-treated modified palladium catalyst prepared in example 2;
fig. 4 is a TEM photograph of the heat-treated modified palladium catalyst prepared in example 3.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
A catalyst for preparing cyclohexanone by hydrogenating phenol uses all catalysts containing zero-valent palladium as precursors, the palladium metal load is 1% -30%, and the specific surface area is 200-1000m 2 And/g. The polymer is a substance which can be decomposed into volatile small-molecular low-alkane, alkene and alkyne under heating.
Studies have shown that: compared with the direct gas inlet mode, the mode of utilizing the polymer to be heated and decomposed has the advantages that the polymer raw materials are cheap and easy to obtain, the whole modified product is low in cost, meanwhile, the possible danger in the gas transportation process is avoided, the method is safer and more convenient, and the selectivity and the conversion rate of preparing cyclohexanone by catalyzing phenol hydrogenation are also improved.
Specifically, the synthesis method of the cyclohexanone catalyst prepared by phenol hydrogenation comprises the following steps: the palladium catalyst and a polymer which can be decomposed into volatile micromolecules by heating are placed in a tubular furnace together to prepare the modified palladium catalyst by adopting a heat treatment mode, then the embedded metal active site is properly stripped under the oxidation condition, and the heat treatment modified palladium catalyst with the exposed active site is obtained by subsequent heat reduction, so that the modified palladium catalyst is applied to the process of synthesizing cyclohexanone by a phenol hydrogenation one-step method.
In some embodiments, the palladium catalyst is selected from all catalysts containing zero-valent palladium, and is not limited to supported or encapsulated catalysts having different support materials, structures, and surface morphologies, such as commercial palladium on carbon catalysts and commercial palladium alumina catalysts.
In some embodiments, the palladium catalyst mass is 100% and the palladium loading is selected from 1% to 30%.
In some embodiments, the polymer is selected from the group consisting of materials that decompose to volatile small molecule low alkanes, alkenes, and alkynes upon heating, such as resins, biomass molecules, and high polymeric compounds.
In some embodiments, the small carbon-containing molecule is at least one of a low paraffin, an olefin, or a carbohydrate.
In some embodiments, the mass ratio of palladium catalyst to polymer that is thermally decomposable into volatile small molecules is selected from 1:0.1-1:1.
in some embodiments, the heat treatment temperature is selected from 30-600deg.C, the rate of temperature rise is 0.5-5deg.C/min, and the treatment time is 5-300min.
In some embodiments, the heat treatment atmosphere is one or a combination of argon, nitrogen or helium in any ratio.
In some embodiments, the oxidant in the activation treatment process is selected from one or more of hydrogen peroxide, sodium hypochlorite or perchloric acid, and the oxidant is combined according to any proportion.
In some embodiments, the vacuum drying temperature is 50-80 ℃, the vacuum drying time is 0.5-10 hours, and the vacuum degree is-0.05 to-0.1 MPa.
In some embodiments, the reduction treatment temperature is 100-300 ℃, the temperature rise rate is 0.5-5 ℃/min, and the reduction time is 0.5-8 hours.
In some embodiments, the reducing atmosphere is a hydrogen-argon mixture, the ratio of hydrogen to argon being 1:20-1:4.
the invention also provides a heat treatment modified palladium catalyst prepared by the method.
The invention provides application of the catalyst in preparing cyclohexanone by phenol hydrogenation.
In some embodiments, the catalytic solvent is one or more of water, ethanol, methylene chloride, cyclohexane, or n-heptane.
In some embodiments, the phenol hydrogenation reaction is carried out in a stainless steel autoclave at a temperature of 30-200 ℃, a hydrogen pressure of 0.1-4MPa, a time of 0.5-9 hours, and a stirring rate of 200-400rpm: the mass ratio of the catalyst to phenol is 1:10-1:1.
in some embodiments, after the catalytic hydrogenation reaction is completed, the cleaning agent for recovering and reusing the catalyst is water, ethanol, cyclohexane or ethyl acetate.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
In the following examples, the palladium on carbon catalyst was a 10% commercial palladium on carbon catalyst, available from Aizhu (Shanghai) chemical technology Co., ltd.
Example 1
100mg of a 10% palladium-carbon catalyst and 50mg of resorcinol-formaldehyde resin which can be decomposed into volatile small molecules by heating are placed in a quartz boat inner tube furnace together, wherein a polymer is placed at an upper air port through which gas passes, and the palladium-carbon catalyst is placed at a lower air port through which gas passes, and reacted for 2 hours at 500 ℃ under inert atmosphere argon. 200mg of the above-obtained material and 20ml of hydrogen peroxide were weighed and stirred in a round bottom flask at 60℃for 4 hours. And (3) centrifugally filtering, and reducing the material subjected to vacuum drying at 50 ℃ for 2 hours at 300 ℃ for 6 hours under a mixed atmosphere of 10% hydrogen and argon to obtain the heat treatment modified palladium catalyst.
1mmol of phenol and 50mg of the heat treatment modified palladium catalyst are weighed and added into a 25ml reaction kettle, 5ml of deionized water is taken as a solvent, hydrogen is introduced to replace the solvent for 3 times, the air in the reaction kettle is exhausted, the hydrogen pressure is maintained to be 1MPa, and the reaction is carried out for 3 hours at 160 ℃. After cooling in ice water bath, separating, extracting with ethyl acetate, adding n-hexadecane as an internal standard, and analyzing the sample by adopting gas chromatography. The experimental results show that: the phenol conversion was 99% and the cyclohexanone selectivity was 93%. Under the same experimental conditions, the selectivity of the cyclohexanone after the heat treatment modification is improved from 40% to 93%.
Example 2
100mg of a 10% commercial palladium-carbon catalyst and 25mg of cellulose which can be decomposed into volatile small molecules by heating are placed in a quartz boat inner tube furnace together, wherein the cellulose is placed in an upper air port through which gas passes, the palladium-carbon catalyst is placed in a lower air port through which gas passes, and the mixture is reacted for 2 hours at 400 ℃ under inert atmosphere argon. 200mg of the obtained material and 20ml of hydrogen peroxide are weighed and stirred in a round bottom flask for 4 hours at 80 ℃. And (3) centrifugally filtering, and reducing the material subjected to vacuum drying at 50 ℃ for 2 hours at 300 ℃ for 4 hours under a mixed atmosphere of 10% hydrogen and argon to obtain the heat treatment modified palladium catalyst.
2mmol of phenol and 50mg of the heat treatment modified palladium catalyst are weighed and added into a 25ml reaction kettle, 5ml of the catalyst is taken as a solvent, hydrogen is introduced to replace the solvent for 3 times, the air in the reaction kettle is exhausted, the hydrogen pressure is maintained to be 1MPa, and the reaction is carried out for 6 hours at 160 ℃. After cooling in ice water bath, separating, extracting with ethyl acetate, adding n-hexadecane as an internal standard, and analyzing the sample by adopting gas chromatography. The experimental results show that: the phenol conversion was 99% and the cyclohexanone selectivity was 60%.
Example 3
100mg of a 10% commercial palladium-carbon catalyst and 10mg of polystyrene which can be decomposed into volatile small molecules by heating are placed in a quartz boat inner tube furnace together, wherein the polystyrene is placed in an upper air port through which gas passes, and the palladium-carbon catalyst is placed in a lower air port through which gas passes, and reacted for 4 hours at 300 ℃ under an inert atmosphere of argon. 200mg of the obtained material and 20ml of hydrogen peroxide are weighed and stirred in a round bottom flask for 4 hours at 80 ℃. And (3) centrifugally filtering, and reducing the material subjected to vacuum drying at 50 ℃ for 2 hours at 300 ℃ for 2 hours in a mixed atmosphere of 10% hydrogen and argon to obtain the heat treatment modified palladium catalyst.
1mmol of phenol and 50mg of the heat treatment modified palladium catalyst are weighed and added into a 25ml reaction kettle, and 5ml of the reaction kettle is taken according to the volume ratio of 1:1, introducing hydrogen to replace 3 times, exhausting the air in the reaction kettle, maintaining the hydrogen pressure at 1MPa, and reacting at 160 ℃ for 6 hours. After cooling in ice water bath, separating, extracting with ethyl acetate, adding n-hexadecane as an internal standard, and analyzing the sample by adopting gas chromatography. The experimental results show that: the phenol conversion was 99% and the cyclohexanone selectivity was 83%.
TABLE 1 catalytic hydrogenation Activity of phenol before and after modification of Palladium on carbon catalyst by Heat treatment
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a heat-treated modified palladium catalyst, comprising:
the palladium catalyst and the polymer which can be decomposed into volatile micromolecules by heating are directly introduced into the catalyst, or carbon-containing micromolecule gas is directly introduced into the catalyst, and the catalyst and the polymer are subjected to heat treatment together in an inert atmosphere to obtain a product B;
and (3) activating, drying and reducing the product B to obtain the product.
2. The method for preparing a heat-treated modified palladium catalyst according to claim 1, wherein the polymer is at least one of a resin, a biomass molecule, and a polymer compound.
3. The method of preparing a heat treated modified palladium catalyst according to claim 1, wherein the small carbon-containing molecule is at least one of a low alkane, an alkene, or a carbon oxide.
4. The method for preparing a heat-treated modified palladium catalyst according to claim 2, wherein the polymer is at least one of a phenol resin, cellulose, and polystyrene.
5. The method for preparing a heat-treated modified palladium catalyst according to claim 1, wherein the mass ratio of the palladium catalyst to the polymer which is thermally decomposed into volatile small molecules is 1:0.1 to 1:1.
6. the method for preparing a heat-treated modified palladium catalyst according to claim 1, wherein the heat treatment temperature is 30 to 600 ℃, the heating rate is 0.5 to 5 ℃/min, and the treatment time is 5 to 300min.
7. The method for preparing a heat-treated modified-palladium catalyst according to claim 1, wherein the carbonization atmosphere is at least one of argon, nitrogen, or helium.
8. The method for preparing a heat-treated modified palladium catalyst according to claim 1, wherein the activating treatment and the oxidizing agent are at least one selected from the group consisting of hydrogen peroxide, sodium hypochlorite and perchloric acid;
or the vacuum drying temperature is 50-80 ℃, the vacuum drying time is 0.5-10h, and the vacuum degree is-0.05 to-0.1 MPa;
or the reduction treatment temperature is 100-300 ℃, the heating rate is 0.5-5 ℃/min, and the reduction time is 0.5-8 hours;
or the reduction treatment atmosphere is hydrogen-argon mixed gas, and the ratio of hydrogen to argon is 1:20-1:4.
9. a heat treated modified palladium catalyst prepared by the method of any one of claims 1-8.
10. Use of the heat-treated modified palladium catalyst of claim 9 in the catalytic selective hydrogenation in the presence of multifunctional groups to obtain highly selective c=o products.
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