CN115487811A - Nitrogen-doped carbon film coated iron-based catalyst, preparation method and aromatic amine synthesis method - Google Patents
Nitrogen-doped carbon film coated iron-based catalyst, preparation method and aromatic amine synthesis method Download PDFInfo
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Abstract
The invention discloses an iron-based catalyst wrapped by a nitrogen-doped carbon film, a preparation method and an aromatic amine synthesis method. The composition of the iron-based catalyst wrapped by the nitrogen-doped carbon film comprises a nitrogen-doped carbon layer film structure and iron-based metal particles wrapped in the nitrogen-doped carbon film structure, and the preparation method comprises the following steps: uniformly mixing a carbon source, a nitrogen source, metal salt and ethylene glycol, fully stirring for 30min, carrying out hydrothermal carbonization under subcritical conditions, washing, filtering and freeze-drying a product to obtain the iron-based catalyst Fe coated with the nitrogen-doped carbon film x O y @ NC. The iron-based catalyst wrapped by the nitrogen-carbon film can selectively hydrogenate nitroaromatic compounds into corresponding aromatic amine, and 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 the preparation process is simple, the raw materials are easy to obtain, and the production cost is low.
Description
Technical Field
The invention relates to the field of nitroaromatic compounds, in particular to a nitrogen-doped carbon film coated iron-based catalyst, a preparation method and an arylamine synthesis method.
Background
The selective hydrogenation of nitroaromatic compounds to prepare aromatic amine is an important reaction in the synthesis process of fine chemicals, and is widely applied to the light industrial production of bioactive molecules, coloring agents, health-care foods and the like.
It is worth noting that nitroaromatics generally also contain other unsaturated or halogenated functional groups, such as C = C, C = O or C-X (halogenated elements), which tend to graze hydrogen atoms during hydrogenation to form saturated functional groups or to dehalogenate directly, thus forming by-products and reducing the selectivity of the reaction process, especially for noble metals with high activity. Therefore, it is critical to suppress side reactions while promoting hydrodeoxygenation of the aromatic nitro compound.
In recent years, some researches have selected transition metals as active phases and prepared heterogeneous catalysts for hydrogenation of nitroaromatic compounds, and the heterogeneous catalysts have the characteristics of high efficiency, low cost, simple recovery and the like.
However, such catalysts generally present two problems,
firstly, metal particles or oxides thereof are easy to agglomerate and leach out in the catalysis process, so that the cycle performance is weak;
secondly, the carbon source of the catalyst carrier is mostly derived from petrochemical derivatives, resulting in the unsustainability of the process.
In view of the above problems, there is a need to develop a method for preparing a catalyst which is efficient, stable and sustainable, and can be successfully applied to the selective hydrogenation of various nitroaromatic 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 provide a high-efficiency, stable and sustainable catalyst preparation method;
the invention also aims to provide a catalyst and a catalytic method which can be successfully applied to the selective hydrogenation of various nitroaromatic compounds.
The technical scheme of the invention is as follows: the invention discloses a preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film, which comprises the following steps:
s1: weighing and mixing reaction substrates and solvents: 40mL of ethylene glycol was prepared as a reaction solventMass concentration (unit g. L) -1 ) Ratio (0-10): 75:33.75 weighing a certain amount of carbon source, nitrogen source and inorganic iron salt, adding into the glycol solvent, and stirring until the carbon source, the nitrogen source and the inorganic iron salt are completely dissolved to obtain a transparent solution;
s2: alcohol-heat reaction: transferring the transparent solution to a moderate reaction kettle for alcohol-heat reaction to obtain a mixed solid-liquid product;
s3: and (3) product separation treatment: and centrifuging, filtering and separating the mixed solid-liquid product to obtain a solid product, rinsing the solid product with deionized water for multiple times until the solid product is neutral, and performing vacuum freeze drying, crushing and screening to obtain the nitrogen-doped carbon film coated iron-based catalyst.
Further, the nitrogen source is at least one of urea, melamine or ammonium citrate; the carbon source is at least one of glucose, sucrose or fructose; the inorganic ferric salt is at least one of ferric nitrate, ferric acetate or ferric chloride.
Further, the alcohol thermal reaction temperature is 180-210 ℃, and the retention time is 10-20hr.
Further, the nitrogen source is urea, the carbon source is glucose, and the inorganic ferric salt is ferric chloride hexahydrate.
Further, the alcohol thermal reaction temperature is 200 ℃, and the retention time is 12hr.
Furthermore, the grain diameter of the iron-based catalyst wrapped by the nitrogen-doped carbon film is less than or equal to 80 meshes.
The invention also discloses a nitrogen-doped carbon film coated iron-based catalyst, which is prepared by the preparation method of the nitrogen-doped carbon film coated iron-based catalyst and comprises a nitrogen-doped carbon layer film structure and iron-based metal particles coated in the nitrogen-doped carbon film structure.
The invention also discloses an aromatic amine synthesis method, which comprises the step of wrapping the iron-based catalyst with the nitrogen-doped carbon film and is used for catalyzing the selective hydrogenation of the nitroaromatic compound to prepare the aromatic amine compound;
the catalytic reaction is carried out in a closed reaction kettle in a methanol solvent environment, the dosage of the nitroaromatic compound is 0.5mmol, the dosage of the iron-based catalyst wrapped by the nitrogen-doped carbon film is 5-10mg, the volume of the methanol is 5mL, the reaction temperature is 60-80 ℃, the reaction time is 1-2hr, the stirring speed is 300rpm, the reaction hydrogen source is at least one of hydrogen, formic acid and hydrazine hydrate, and the target product is obtained by filtering and rotary steaming the mixture after the reaction.
Further, the reaction hydrogen source is at least one of 1-2MPa hydrogen, 2.0mmol formic acid and 2.0mol hydrazine hydrate (50%).
Further, the nitroaromatic compound is: nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-fluoronitrobenzene, p-bromonitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrobenzyl alcohol, p-nitrobenzonitrile, p-nitrophenol, p-nitroanisole, p-nitrobenzaldehyde, 4-nitropyrazole, 4-nitropyridine and 5-nitroindole.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the nitrogen-doped carbon film coated iron-based catalyst comprises the steps of uniformly mixing a carbon source, a nitrogen source, a metal salt and ethylene glycol, fully stirring for 30min, carrying out hydrothermal carbonization under subcritical conditions, then washing, filtering and freeze-drying a product to obtain the nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y @ NC), compared with the prior art, the invention has the advantages of simple preparation process, easily obtained raw materials and low production cost
2. The nitrogen-doped carbon film coated iron-based catalyst can selectively hydrogenate nitroaromatic compounds into corresponding aromatic amine, and has the advantages of high catalytic activity, wide substrate application range, easy recovery and reuse, mild reaction conditions, green and environment-friendly reaction solvent and the like.
Drawings
FIG. 1 shows the iron-based catalyst (Fe) coated with the nitrogen-doped carbon thin film in example 1 x O y @ NC-0.2 g) SEM, TEM, and EDS images.
FIG. 2 is a schematic view of the example 1 in which the iron-based catalyst (Fe) is coated with the nitrogen-doped carbon thin film x O y XRD pattern of @ NC-0.2 g).
FIG. 3 is a schematic view of an embodimentExample 2 Nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y @ NC-0.1 g).
FIG. 4 shows the iron-based catalyst (Fe) coated with the nitrogen-doped carbon thin film in example 3 x O y @ NC-0.4 g).
Detailed Description
For the understanding of the present invention, the following detailed description will be given with reference to the accompanying drawings, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, and a target product mainly comprises aromatic amine, and specifically comprises the following steps:
s1, mixing 0.2g of glucose, 3.0g of urea and 0.125 mol.L -1 The ferric chloride and 40mL of glycol are mixed evenly, transferred into a hydrothermal kettle, sealed, and blown with nitrogen to repeatedly purge to provide an inert atmosphere, and then the temperature is raised to 200 ℃ and carbonization is continued for 12 hours. After the reaction is finished, separating the solid-liquid product, washing the solid-phase product for many times until the solid-phase product is neutral, carrying out vacuum freeze drying, crushing and sieving with a 80-mesh sieve to obtain the nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y @NC-0.2g)。
S2, 0.5mmol of nitrobenzene, 5mL of methanol solution and 10mg of catalyst (Fe) x O y @ NC-0.2 g) is mixed and added into a high-pressure reaction kettle, hydrogen is filled, the pressure of the system is controlled to be 2MPa, the other operation conditions such as stirring speed of 300rpm, temperature of 80 ℃ and time of 2 hours are adopted, and finally aniline with the yield of 94.6 percent can be obtained.
Nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y @ NC-0.2 g) are shown in FIG. 1.
As can be seen from FIG. 1, fe x O y The catalyst @ NC-0.2g is in the shape of a particle sphere, the surface of the catalyst is concave-convex, a proper number of pore structures are formed, and iron-based nano particles are uniformly dispersed in the carbon layer.
Nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y XRD results of @ NC-0.2 g) are shown in FIG. 2.
As can be seen from FIG. 2, fe x O y The metal particles of @ NC-0.2g catalyst are mainly in an oxidation state, and exhibit characteristic crystal planes of (2 0), (3 1) and (4 0) of ferroferric oxide.
Example 2
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, a target product is mainly aromatic amine, except that 0.2g of glucose in the step S1 in the embodiment 1 is replaced by 0.1g of glucose, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 5.4% can be obtained.
Nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y The SEM results of @ NC-0.1 g) are shown in FIG. 3.
As can be seen from FIG. 3, fe x O y The catalyst @ NC-0.1g cannot form a good carbon layer outer membrane due to insufficient carbon source, so that the loss of metallic iron loaded on the catalyst is serious, and the catalytic activity is reduced.
Example 3
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, a target product is mainly aromatic amine, except that 0.2g of glucose in the step S1 in the embodiment 1 is replaced by 0.4g of glucose, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 29.5% can be obtained.
Nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y The SEM results of @ NC-0.4 g) are shown in FIG. 4.
As can be seen from FIG. 4, fe x O y The catalyst of @ NC-0.4g completely wraps the iron-based nanoparticles due to excessive carbon sources, so that the contact area of the iron-based nanoparticles and reactants is blocked, and the catalytic activity is reduced.
Example 4
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that the step S1 in the embodiment 1, namely heating to 200 ℃ and continuously carbonizing for 12h, is replaced by the step S1, namely heating to 180 ℃ and continuously carbonizing for 16h, the steps are completely consistent with those in the embodiment 1, and finally aniline with the yield of 88.2% can be obtained.
Example 5
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that a catalyst of 10mg in the step S2 in the embodiment 1 is replaced by a catalyst of 5mg, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 50.0% can be obtained.
Example 6
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitro-aromatic compounds, a target product is aromatic amine, except that hydrogen is filled and the system pressure is controlled to be 2MPa in the step S2 in the embodiment 1 is replaced by hydrogen is filled and the system pressure is controlled to be 1MPa, the method is completely consistent with the embodiment 1, and aniline with the yield of 46.2% can be finally obtained.
Example 7
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that the temperature of 80 ℃ in the step S2 in the embodiment 1 is replaced by the temperature of 60 ℃, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 1.0% can be obtained.
Example 8
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that the temperature of 80 ℃ in the step S2 in the embodiment 1 is replaced by the temperature of 70 ℃, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 37.0% can be obtained.
Example 9
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that the time of 2h in the step S2 in the embodiment 1 is replaced by the time of 1h, the method is completely consistent with the embodiment 1, and finally aniline with the yield of 54.9% can be obtained.
Example 10
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product takes aromatic amine as a main component, except that the steps S2 in the step 1 are replaced by the steps of charging hydrogen and controlling the system pressure to be 2MPa, adding 2.0mmol of formic acid serving as a hydrogen source, replacing the steps S2 with the steps S90 ℃ and S12 h, and the steps S1 and S2 are completely consistent with those in the step 1, so that aniline with the yield of 67.3% can be finally obtained.
Example 11
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product takes aromatic amine as a main component, except that the steps S2 in the step 1 are replaced by adding 2.0mmol of hydrazine hydrate (50%) serving as a hydrogen source, replacing the steps S2 with hydrogen filling and controlling the system pressure to be 2MPa, and replacing the steps S2 with hydrazine hydrate at the temperature of 80 ℃ and the time of 2h by replacing the steps S120 ℃ and the time of 10h, the method is completely consistent with the step 1, and finally aniline with the yield of 52.5% can be obtained.
Examples 12 to 27
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product is mainly aromatic amine, except that nitrobenzene in a step S2 in an example 1 is replaced by other nitroaromatic compounds, the method is completely the same as that in the example 1, and the specific nitroaromatic compounds and the corresponding aromatic amine yield are shown in the following table.
TABLE 1 yield of nitroaromatics and corresponding aromatic amines
Example 28 Scale-up test for Selective hydrogenation of an aromatic Compound
A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to the selective hydrogenation process of nitroaromatic compounds, and a target product mainly comprises aromatic amine, and specifically comprises the following steps:
sb1 was prepared in the same manner as in step S1 of example 1, except that 0.2g of glucose, 3.0g of urea and 0.125 mol. L -1 The ferric chloride and 40mL of glycol are mixed uniformly, transferred into a hydrothermal kettle, sealed, and repeatedly purged by introducing nitrogen to provide an inert atmosphere, and then the temperature is raised to 200 ℃ and carbonization is continued for 12 hours. After the reaction is finished, separating a solid-liquid product, washing the solid-phase product for many times until the solid-phase product is neutral, carrying out vacuum freeze drying, crushing and sieving by a 80-mesh sieve to obtain the nitrogen-doped carbon film coated iron-based catalyst (Fe) x O y @ NC-0.2 g); sb2. 5mmol of nitrobenzene, 50mL of methanol solution and 100mg of catalyst (Fe) x O y @ NC-0.2 g) is mixed and added into a high-pressure reaction kettle, hydrogen is filled, the pressure of the system is controlled to be 2MPa, the other operation conditions such as stirring speed of 300rpm, temperature of 80 ℃ and time of 2 hours are adopted, and finally aniline with the yield of 95.4% can be obtained.
Examples 29 to 30
A method for preparing an iron-based catalyst wrapped by a nitrogen-doped carbon film is mainly applied to a selective hydrogenation process of nitroaromatic compounds, a target product is aromatic amine, except that nitrobenzene in step Sb 2) of example 28 is replaced by p-nitrotoluene or p-nitroanisole, the method is completely the same as example 28, and corresponding aromatic amine with the yield of 96.8% and 93.7% can be finally obtained.
Example 31 recycle test for Selective hydrogenation of nitroaromatics
The nitrogen-doped carbon film in the example 1 is wrapped by the iron-based catalyst Fe x O y @ NC-0.2 g) was separated from the reaction mixture and continued to be used for repetition of the same conditionsThe results of the sexual tests are shown in the following table:
TABLE 2 results of the repeatability tests
Comparative examples 1 to 7
A comparative catalyst was selected for selective hydrogenation of nitrobenzene, and the reaction conditions were identical to those in step S2) of example 1 except for the type of catalyst, and the yields of the target product (aniline) were as shown in the following table.
TABLE 3 catalyst types and target product yields
| Comparative example | Catalyst type | Conversion (%) | Selectivity (%) | Product yield (%) |
| 1 | Fe x O y @NC-0g | 2.8 | 8.5 | 0.2 |
| 2 | Iron powder | 22.2 | 3.7 | 0.8 |
| 3 | Ferroferric oxide | >99 | 91.3 | 91.3 |
| 4 | Ruthenium noble metal catalyst | >99 | 21.8 | 21.8 |
| 5 | Platinum noble metal catalyst | >99 | 94.1 | 94.1 |
| 6 | Rhodium noble metal catalyst | >99 | 0.8 | 0.8 |
| 7 | Palladium noble metal catalyst | >99 | 80.1 | 80.1 |
Comparative examples 8 to 9 (Cyclic test for Selective hydrogenation of nitroaromatics)
The catalyst (ferroferric oxide or platinum noble metal catalyst) in the comparative example 3 or 5 was separated from the reaction solution and then continuously used for the repeatability test under the same conditions, and the results are shown in the following table:
TABLE 4 results of the repeatability tests
By combining the above experiments, fe can be obtained x O y The catalyst @ NC-0.2g can convert nitro aromatic compounds into corresponding aromatic amines, and is mainly benefited from a porous carbon layer film structure constructed by proper carbon source proportion. The porous carbon layer film structure can prevent the sintering and loss of metal nano particles and promote the full reaction between reactants and a metal active phase.
In addition, compared to the existing iron-based catalyst (ferroferric oxide) and platinum noble metal catalyst, fe x O y The circulation stability of the catalyst of @ NC-0.2g is better and the economic benefit is high.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, and equivalents which do not depart from the spirit and principle of the present invention may be made within the scope of the present invention. The invention also contemplates various changes and modifications that fall within the scope of the invention as claimed. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A preparation method of an iron-based catalyst wrapped by a nitrogen-doped carbon film is characterized by comprising the following steps:
s1: weighing of reaction substrate and solventQuantity and mixing: 40mL of ethylene glycol as a reaction solvent was prepared, and the reaction solvent was adjusted to the mass concentration (unit g. L) -1 ) Ratio (0-10): 75:33.75 certain carbon source, nitrogen source and inorganic iron salt are weighed, added into the glycol solvent and stirred until being completely dissolved, so as to obtain a transparent solution;
s2: alcohol heat reaction: transferring the transparent solution to a moderate reaction kettle for alcohol-heat reaction to obtain a mixed solid-liquid product;
s3: and (3) product separation treatment: and centrifuging, filtering and separating the mixed solid-liquid product to obtain a solid product, rinsing the solid product with deionized water for multiple times until the solid product is neutral, and performing vacuum freeze drying, crushing and screening to obtain the nitrogen-doped carbon film coated iron-based catalyst.
2. The method for preparing the iron-based catalyst wrapped with the nitrogen-doped carbon film according to claim 1, wherein the nitrogen source is at least one of urea, melamine or ammonium citrate; the carbon source is at least one of glucose, sucrose or fructose; the inorganic ferric salt is at least one of ferric nitrate, ferric acetate or ferric chloride.
3. The method of claim 2, wherein the alcohol thermal reaction temperature is 180-210 ℃ and the residence time is 10-20hr.
4. The method for preparing the iron-based catalyst wrapped with the nitrogen-doped carbon film according to claim 2, wherein: the nitrogen source is urea, the carbon source is glucose, and the inorganic ferric salt is ferric chloride hexahydrate.
5. The method for preparing the iron-based catalyst wrapped with the nitrogen-doped carbon film according to claim 3, wherein the method comprises the following steps: the alcohol heating reaction temperature is 200 deg.C, and the residence time is 12hr.
6. The method for preparing the iron-based catalyst wrapped with the nitrogen-doped carbon thin film according to any one of claims 1 to 5, wherein: the grain diameter of the iron-based catalyst wrapped by the nitrogen-doped carbon film is less than or equal to 80 meshes.
7. An iron-based catalyst wrapped by a nitrogen-doped carbon film is characterized in that: the nitrogen-doped carbon film coated iron-based catalyst is prepared by the preparation method of the nitrogen-doped carbon film coated iron-based catalyst as described in any one of claims 1 to 6, and comprises a nitrogen-doped carbon film structure and iron-based metal particles coated in the nitrogen-doped carbon film structure.
8. A method for synthesizing aromatic amine is characterized in that: the method is characterized in that the iron-based catalyst is wrapped by the nitrogen-doped carbon film in the claim 7 and is used for catalyzing selective hydrogenation of nitroaromatic compounds to prepare aromatic amine compounds;
the catalytic reaction is carried out in a closed reaction kettle in a methanol solvent environment, the dosage of the nitroaromatic compound is 0.5mmol, the dosage of the iron-based catalyst wrapped by the nitrogen-doped carbon film is 5-10mg, the volume of the methanol is 5mL, the reaction temperature is 60-80 ℃, the reaction time is 1-2hr, the stirring speed is 300rpm, the reaction hydrogen source is at least one of hydrogen, formic acid and hydrazine hydrate, and the target product is obtained by filtering and rotary steaming the mixture after the reaction.
9. The aromatic amine synthesis method according to claim 8, characterized in that: the reaction hydrogen source is at least one of 1-2MPa hydrogen, 2.0mmol formic acid and 2.0mol hydrazine hydrate (50%).
10. Use of a catalyst according to claim 8, characterized in that: the nitroaromatic compound is as follows: nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-fluoronitrobenzene, p-bromonitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrobenzyl alcohol, p-nitrobenzonitrile, p-nitrophenol, p-nitroanisole, p-nitrobenzaldehyde, 4-nitropyrazole, 4-nitropyridine and 5-nitroindole.
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