CN115739083A - Hydrothermal carbon catalyst, preparation method thereof and preparation method of primary imine compound - Google Patents
Hydrothermal carbon catalyst, preparation method thereof and preparation method of primary imine compound Download PDFInfo
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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
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of a hydrothermal carbon microsphere loaded transition metal catalyst. The hydrothermal carbon microsphere supported transition metal catalyst comprises hydrothermal carbon microspheres and transition metal supported on the carbon microspheres, and the preparation method comprises the following steps: 1) Mixing a carbon source, metal salt and absolute ethyl alcohol, fully stirring for 30 min, carrying out hydrothermal carbonization under subcritical conditions, and then washing, filtering and freeze-drying a product to obtain a hydrothermal carbon catalyst; 2) And (3) carrying out reduction treatment on the hydrothermal carbon catalyst to obtain a reduced hydrothermal carbon catalyst. The hydrothermal carbon microsphere supported transition metal catalyst can selectively synthesize corresponding primary amine or imine from aldehyde compounds through reductive amination, has the advantages of high catalytic activity, wide substrate application range, easiness in recycling, mild reaction conditions, green and environment-friendly reaction solvent and the like, and is simple in preparation process, easy in raw material obtaining and low in production cost.
Description
Technical Field
The invention belongs to the technical field of reductive amination of aldehyde and ketone compounds, and particularly relates to a preparation method and application of a hydrothermal carbon microsphere supported transition metal catalyst.
Background
The amine compound is an important intermediate and a basic raw material for light industrial production, can be divided into primary amine and imine according to the difference of substituted hydrogen atoms, and various introduced functional groups can change the physiological activity of the amine compound to different degrees, thereby showing unique functional characteristics in the fields of pharmacy, chemical industry, materials and the like.
The reductive amination of aldehydes and ketones is a typical route for the synthesis of amines, and the basic process comprises: the amino and carbonyl groups undergo nucleophilic addition to give imines which are subsequently hydrogenated to the corresponding primary amine-based compounds.
If the selective synthesis of imine is desired, catalysts with different reaction activities are usually matched to regulate and control the reaction process, but the existing catalyst has two problems, firstly, noble metals are adopted as active phases, so that the large-scale application of the catalyst is limited; secondly, the carbon source of the catalyst carrier is mostly derived from petrochemical derivatives, resulting in the unsustainability of the process.
Based on this, there is a need to develop a method for preparing a catalyst with high economic value and sustainable use, and the method can be successfully applied to the selective synthesis of various amine compounds.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention aims to solve the defects in the prior art and provides a hydrothermal carbon catalyst and a preparation method thereof;
it is also an object of the present invention to provide a method for preparing a primary imine compound suitable for use in the hydrothermal carbon catalyst of the present invention.
The technical scheme of the invention is as follows: the invention discloses a preparation method of a hydrothermal carbon catalyst, which comprises the steps of mixing a carbon source, metal salt and absolute ethyl alcohol, and fully and uniformly stirring until a solution is transparent; then carrying out hydrothermal carbonization under subcritical conditions; and finally, washing, filtering and freeze-drying the hydrothermal carbonized product to obtain the hydrothermal carbon catalyst.
Further, the method comprises the following steps of,
s1, adding 100 g.L of carbon source and iron salt -1 :72g·L -1 Adding the concentration ratio into 30mL of absolute ethyl alcohol;
s2, transferring the solution into a closed reaction kettle, and carrying out carbonization reaction in a nitrogen atmosphere; carbonizing at 150-210 deg.C for 2-24hr;
and S3, after the reaction is finished, sequentially carrying out centrifugal filtration separation, washing to be neutral, vacuum freeze drying, crushing and screening on the solid product serving as a target to obtain the hydrothermal carbon catalyst.
Further, carrying out high-temperature reduction reaction on the hydrothermal carbon catalyst, and cooling to obtain the reduced hydrothermal carbon catalyst.
Further, the carbon source is glucose, the nitrogen source is ferric nitrate, the hydrothermal carbonization reaction temperature is 180 ℃, and the carbonization time is 16hr;
furthermore, in the high-temperature reduction reaction, the reduction atmosphere is nitrogen or hydrogen, the reduction temperature is 400-800 ℃, and the reduction time is 4-12hr.
When the high-temperature reduction reaction adopts a nitrogen atmosphere, the reduction temperature is 700 ℃, and the reduction time is 4hr.
When the high-temperature reduction reaction adopts a hydrogen atmosphere, the reduction temperature is 400 ℃, and the reduction time is 12hr.
The invention also discloses a hydrothermal carbon catalyst, which comprises hydrothermal carbon microspheres and transition metal loaded on the carbon microspheres; the carbon microspheres are obtained by carrying out hydrothermal carbonization on glucose, sucrose or fructose; the transition metal is iron element, cobalt element or nickel element.
Furthermore, the hydrothermal carbon catalyst is prepared based on the preparation method of the hydrothermal carbon catalyst.
The invention also discloses a preparation method of the primary imine compound, which comprises a preparation method of the primary amine compound and a preparation method of the imine compound;
the imine compound preparation method comprises the steps of adding the hydrothermal carbon catalyst prepared by the hydrothermal carbon catalyst preparation method according to claim 2 into a high-pressure reaction kettle by taking an aldehyde compound as a raw material and taking an ammonia-containing methanol solution as a solvent, and carrying out reductive amination reaction on the raw material in a hydrogen environment to generate an imine compound;
the preparation method of the primary amine compound comprises the steps of adding the hydrothermal carbon catalyst prepared by the preparation method of the hydrothermal carbon catalyst according to claim 3 into a high-pressure reaction kettle by using an aldehyde compound as a raw material and using an ammonia-containing methanol solution as a solvent, and carrying out reductive amination reaction on the raw material in a hydrogen environment to generate the primary amine compound.
Further, the reductive amination reaction temperature is 90-110 ℃; the reaction time is 4hr, and the hydrogen pressure of the reaction system is 2MPa; the reaction concentration ratio of the aldehyde compound raw material, the hydrothermal carbon catalyst and the ammonia methanol is 0.5mmol:10mg:7mol.
Further, in the preparation of the primary amine compound, the reductive amination reaction temperature is 110 ℃; in the preparation of the imine compound, the reaction temperature is 90 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the hydrothermal carbon catalyst can selectively synthesize corresponding primary amine or imine from aldehyde compounds through reductive amination, has the advantages of high catalytic activity, wide substrate application range, easiness in recycling, mild reaction conditions, green and environment-friendly reaction solvent and the like, and is simple in preparation process, easy in raw material obtaining and low in production cost.
Drawings
FIG. 1 is an SEM, TEM, and EDS image of a hydrothermal carbon catalyst in example 1 of the present invention.
Fig. 2 is an XRD pattern of the hydrothermal carbon catalyst in example 1 of the present invention.
FIG. 3 is SEM, TEM and EDS images of a reduced hydrothermal carbon catalyst in example 23 of the present invention.
FIG. 4 is an XRD pattern of the reduced form of the hydrothermal carbon catalyst of example 23 of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product takes imine as a main material, and the preparation method specifically comprises the following steps:
s1, uniformly mixing 3.0g of glucose, 2.16g of ferric nitrate and 30mL of absolute ethyl alcohol, transferring the mixture into a hydrothermal kettle, sealing the kettle, introducing nitrogen, repeatedly purging the kettle to provide an inert atmosphere, and then heating to 180 ℃ and continuously carbonizing for 16 hours. After the reaction is finished, separating a solid-liquid product, washing the solid-phase product for multiple times until the solid-phase product is neutral, carrying out vacuum freeze drying, crushing, and sieving by a 80-mesh sieve to obtain the hydrothermal carbon catalyst;
s2, adding 0.5mmol of benzaldehyde into 5mL of solution with the concentration of 7 mol.L -1 Ammonia methanol ofThe solution and 10mg of hydrothermal carbon catalyst are mixed and added into a high-pressure reaction kettle, hydrogen is filled in the high-pressure reaction kettle, the pressure of the system is controlled to be 2MPa, and the nitrogen benzyl butylamine can be finally obtained under the other operation conditions of stirring speed of 300rpm, temperature of 110 ℃ and time of 4 hours. Wherein, the N-benzylidenebutylamine is the corresponding imine of benzaldehyde, and the yield is 94.1%.
Example 2
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product is mainly imine, except that 'absolute ethyl alcohol' in step S1 of example 1 is replaced by 'ethylene glycol', the method is completely the same as example 1, and the yield of the final N-benzyl enamine is 92.3%.
Examples 3 to 4
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product is mainly imine, except that the temperature rise to 180 ℃ in the step S1 in the embodiment 1 is replaced by the temperature rise to 150 ℃ or 210 ℃, the other steps are the same as the embodiment 1, and the final yields of the N-benzyl-enamine are 10.8% and 65.9% respectively.
It is explained that 180 ℃ is the optimum carbonization temperature of the hydrothermal carbocatalyst when the imine compound is used as the target product.
Examples 5 to 6
A preparation method of a hydrothermal carbon catalyst is mainly applied to reductive amination of aldehyde compounds, a target product is mainly imine, except that continuous carbonization 16h in step S1 of example 1 is replaced by continuous carbonization 12h or continuous carbonization 20h, the yield of N-benzyl enamine is respectively 74.9% and 89.0% as same as that of example 1.
It is stated that 16h is the optimum carbonization time of the hydrothermal carbocatalyst when an imine compound is the target product.
Examples 7 to 18
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product takes imine as a main component, except that benzaldehyde in a step S2 of an example 1 is replaced by other aldehyde compounds, the other steps are completely the same as the example 1, and the specific aldehyde compounds and corresponding imine yields are shown in the following table:
TABLE 1 yield of aldehydes and corresponding imines
Therefore, the catalyst is not only suitable for benzaldehyde, but also can be used for converting other aldehyde compounds into corresponding imine, and has a certain application range.
EXAMPLE 19 Scale-Up of reductive amination of aldehyde Compounds
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product takes imine as a main component, and the preparation method specifically comprises the following steps:
s1, the step is the same as the step S1 in the embodiment 1;
s2, adding 5mmol of benzaldehyde to 50mL of which the concentration is 7 mol.L -1 The ammonia methanol solution and 100mg of hydrothermal carbon catalyst are mixed and added into a high-pressure reaction kettle, hydrogen is filled, the system pressure is controlled to be 2MPa, and the nitrogen benzyl butylamine can be finally obtained under the other operation conditions of stirring speed of 300rpm, temperature of 110 ℃ and time of 4 hours, wherein the nitrogen benzyl butylamine is corresponding imine of benzaldehyde, and the yield is 90.4%.
Therefore, the catalyst obtained by the invention still has certain catalytic efficiency under the condition of amplification, and has the potential of industrial application.
Examples 20 to 21
A preparation method of a hydrothermal carbon catalyst is mainly applied to reductive amination of aldehyde compounds, a target product is mainly imine, except that benzaldehyde in step 2 of example 19 is replaced by p-methylbenzaldehyde or p-methoxybenzaldehyde, other steps are the same as example 19, and yields of corresponding imine are 71.8% and 86.6%.
From these results, it is clear that the hydrothermal carbon catalyst has excellent performance in the case of application to a large scale of reaction substrates other than benzaldehyde.
EXAMPLE 22 repeatability test for reductive amination of aldehydes
The hydrothermal carbon catalyst of example 1 was separated from the reaction solution and then used for the repeatability test under the same conditions, and the results are shown in the following table:
TABLE 2 results of the repeatability tests
According to the results of the repeatability tests, the catalyst still has certain catalytic efficiency under the condition of multiple cycles, can be repeatedly used and has the potential of industrial application.
Example 23
A preparation method of a hydrothermal carbon catalyst is mainly applied to a reductive amination process of aldehyde compounds, a target product takes primary amine as a main component, and the preparation method specifically comprises the following steps:
s1, uniformly mixing 3.0g of glucose, 2.16g of ferric nitrate and 30mL of absolute ethyl alcohol, transferring the mixture into a hydrothermal kettle, sealing the kettle, introducing nitrogen, repeatedly purging the kettle to provide an inert atmosphere, and then heating to 180 ℃ and continuously carbonizing for 16 hours. After the reaction is finished, separating a solid-liquid product, washing the solid-phase product for multiple times until the solid-phase product is neutral, carrying out vacuum freeze drying, crushing, sieving with a 80-mesh sieve, and then reducing for 4 hours at 700 ℃ in a nitrogen atmosphere to obtain the reduced hydrothermal carbon catalyst.
S2, adding 0.5mmol of benzaldehyde into 5mL of solution with the concentration of 7 mol.L -1 The methanolic ammonia solution and 10mg of reduced hydrothermal carbon catalyst are mixed and added into a high-pressure reaction kettle, hydrogen is filled, the system pressure is controlled to be 2MPa, and the benzylamine can be obtained under the other operation conditions such as stirring speed of 300rpm, temperature of 90 ℃ and time of 4 hours. Wherein, benzylamine is corresponding primary amine of benzaldehyde, and the yield is 81.1%.
Combining example 1 and example 23, the following conclusions can be drawn:
the SEM, TEM and EDS results of the hydrothermal carbon catalyst are shown in fig. 1, and it can be seen from fig. 1 that the hydrothermal carbon catalyst prepared by the preparation method of the hydrothermal carbon catalyst of the present invention has a smooth and full surface, is embedded with metal crystals with a large size, and is well dispersed and uniformly mixed.
The SEM, TEM, and EDS results of the reduced hydrothermal carbon catalyst are shown in fig. 3, and it can be seen from fig. 3 that the surface of the reduced hydrothermal carbon catalyst prepared by the method of preparing the hydrothermal carbon catalyst of the present invention is uneven and porous, and the metal crystals are also cracked by high temperature and uniformly distributed on the surface of the carbon microspheres, exposing more catalytic sites.
The XRD results of the hydrothermal carbon catalyst are shown in fig. 2, and it can be seen from fig. 2 that the metal particles of the hydrothermal carbon catalyst are mainly in an oxidized state and are bonded to the graphene carbon matrix.
Fig. 4 shows XRD results of the reduced hydrothermal carbon catalyst, and it can be seen from fig. 4 that the metal particles of the reduced hydrothermal carbon catalyst are mainly in a simple substance state, and exhibit a simple substance iron diffraction peak, a 110 crystal plane at 44.7 ° and a 200 crystal plane at 65.1 °.
Examples 24 to 25
A hydrothermal carbon catalyst preparing method is mainly applied to aldehyde compound reductive amination process, a target product is mainly primary amine, except that ' 700 ℃ is replaced by ' 600 ℃ or ' 800 ℃ in step S1 of example 23, the yield of benzylamine is 68.7% or 78.6% as in example 23.
The optimal condition for preparing the reduced hydrothermal carbon catalyst under the nitrogen atmosphere is shown in 700 ℃ when the primary amine compound is taken as the target product.
Example 26
A hydrothermal carbon catalyst preparation method is mainly applied to aldehyde compound reductive amination, a target product is mainly primary amine, except that the 'reduction at 700 ℃ for 4h under a nitrogen atmosphere' in the step S1 of the embodiment 23 is replaced by the 'reduction at 400 ℃ for 12h under a hydrogen atmosphere', the method is completely the same as the embodiment 23, and the yield of benzylamine is 79.5%. Therefore, the reduction state hydrothermal carbon catalyst prepared by reducing for 4h at 700 ℃ in a nitrogen atmosphere and reducing for 12h at 400 ℃ in a hydrogen atmosphere has excellent effects on the preparation of primary amine.
Comparative examples 1 to 11
A comparative catalyst was selected for the reductive amination of benzaldehyde under the same conditions as in step S2 of example 23 except that the type of the catalyst was changed, and the yield of the objective benzylamine or azenobutylamine was as shown in the following Table.
TABLE 3 catalyst type and target product yield
The comparative experiment shows that the hydrothermal carbon catalyst is used for the reductive amination reaction of benzaldehyde, the yield of the target product of the N-benzylbutylamine is higher than that of the existing commercial catalyst, and the N-benzylbutylamine has excellent effect in imine preparation; the reduction state hydrothermal carbon catalyst is used for carrying out reductive amination reaction on benzaldehyde, and the target product benzylamine is higher than the existing commercial catalyst, namely, the catalyst has excellent effect on primary amine preparation.
The surface acid-base levels of the hydrothermal carbon catalysts analyzed by chemical titration are shown in the following table.
TABLE 4 surface acid-base degree of hydrothermal carbon catalyst
By combining the above characterization and analysis, it can be inferred that the control mechanism of the hydrothermal carbon catalyst in the amination process under different processes is mainly reflected in three differences of particle size, crystalline phase valence state, surface acidic functional group and the like.
The hydrothermal carbon catalyst can mainly catalyze aldehyde compounds to synthesize corresponding imine, and the reduced hydrothermal carbon catalyst tends to catalyze the aldehyde compounds to synthesize corresponding primary amine.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a hydrothermal carbon catalyst is characterized by comprising the following steps: mixing a carbon source, metal salt and absolute ethyl alcohol, and fully and uniformly stirring until the solution is transparent; then carrying out hydrothermal carbonization under subcritical conditions; finally, washing, filtering and freeze-drying the hydrothermal carbonized product to obtain the hydrothermal carbon catalyst.
2. The method of preparing a hydrothermal carbon catalyst according to claim 1, wherein: comprises the following steps of (a) carrying out,
s1, adding 100 g.L of carbon source and iron salt -1 :72g·L -1 Adding the concentration ratio into 30mL of absolute ethyl alcohol;
s2, transferring the solution into a closed reaction kettle, and carrying out carbonization reaction in a nitrogen atmosphere; carbonizing at 150-210 deg.C for 2-24hr;
and S3, after the reaction is finished, sequentially carrying out centrifugal filtration separation, washing to be neutral, vacuum freeze drying, crushing and screening on a solid product serving as a target to obtain the hydrothermal carbon catalyst.
3. The method of preparing a hydrothermal carbon catalyst according to claim 2, characterized in that: and carrying out high-temperature reduction reaction on the hydrothermal carbon catalyst, and cooling to obtain the reduced hydrothermal carbon catalyst.
4. The method of claim 3, wherein: in the high-temperature reduction reaction, the reducing atmosphere is nitrogen or hydrogen, the reducing temperature is 400-800 ℃, and the reducing time is 4-12hr.
5. The method of claim 3, wherein: the carbon source is glucose, the nitrogen source is ferric nitrate, the hydrothermal carbonization reaction temperature is 180 ℃, and the carbonization time is 16hr;
when the high-temperature reduction reaction adopts a nitrogen atmosphere, the reduction temperature is 700 ℃, and the reduction time is 4hr;
when the high-temperature reduction reaction adopts a hydrogen atmosphere, the reduction temperature is 400 ℃, and the reduction time is 12hr.
6. A hydrothermal carbon catalyst, characterized by: comprises hydrothermal carbon microspheres and transition metal loaded on the carbon microspheres; the carbon microspheres are obtained by carrying out hydrothermal carbonization on glucose, sucrose or fructose; the transition metal is iron element, cobalt element or nickel element.
7. The hydrothermal carbon catalyst of claim 6, wherein: prepared on the basis of the process as claimed in any of claims 1 to 5.
8. A method for preparing a primary imine compound, characterized by: comprises a primary amine compound preparation method and an imine compound preparation method;
the imine compound preparation method comprises the steps of adding the hydrothermal carbon catalyst prepared by the hydrothermal carbon catalyst preparation method according to claim 2 into a high-pressure reaction kettle by taking an aldehyde compound as a raw material and taking an ammonia-containing methanol solution as a solvent, and carrying out reductive amination reaction on the raw material in a hydrogen environment to generate an imine compound;
the preparation method of the primary amine compound comprises the steps of adding the hydrothermal carbon catalyst prepared by the preparation method of the hydrothermal carbon catalyst according to claim 3 into a high-pressure reaction kettle by using an aldehyde compound as a raw material and an ammonia-containing methanol solution as a solvent, and carrying out reductive amination reaction on the raw material in a hydrogen environment to generate the primary amine compound.
9. The method of preparing a primary imine compound according to claim 8, characterized in that: the temperature of the reductive amination reaction is 90-110 ℃; the reaction time is 4hr, and the hydrogen pressure of the reaction system is 2MPa; the reaction concentration ratio of the aldehyde compound raw material, the hydrothermal carbon catalyst and the ammonia methanol is 0.5mmol:10mg:7mol.
10. The method of preparing a primary imine compound according to claim 9, characterized in that: in the preparation of primary amine compounds, the reductive amination reaction temperature is 110 ℃; in the preparation of the imine compound, the reaction temperature is 90 ℃.
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CN104741122A (en) * | 2015-03-11 | 2015-07-01 | 常州大学 | Preparation method of catalyst used for oxidative desulfurization |
CN106881059A (en) * | 2017-02-04 | 2017-06-23 | 中国科学技术大学苏州研究院 | A kind of preparation method of iron/carbon composite |
CN111097421A (en) * | 2018-10-29 | 2020-05-05 | 中国科学院大连化学物理研究所 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
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CN104741122A (en) * | 2015-03-11 | 2015-07-01 | 常州大学 | Preparation method of catalyst used for oxidative desulfurization |
CN106881059A (en) * | 2017-02-04 | 2017-06-23 | 中国科学技术大学苏州研究院 | A kind of preparation method of iron/carbon composite |
CN111097421A (en) * | 2018-10-29 | 2020-05-05 | 中国科学院大连化学物理研究所 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
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