CN110746309A - Preparation method of aromatic amine compound - Google Patents
Preparation method of aromatic amine compound Download PDFInfo
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- CN110746309A CN110746309A CN201810816611.1A CN201810816611A CN110746309A CN 110746309 A CN110746309 A CN 110746309A CN 201810816611 A CN201810816611 A CN 201810816611A CN 110746309 A CN110746309 A CN 110746309A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention provides a preparation method of aromatic amine compounds, which comprises the step of carrying out catalytic hydrogenation on aromatic nitro compounds by using nano platinum encapsulated by a Y molecular sieve as a catalyst in a hydrogen atmosphere to prepare the aromatic amine compounds. According to the preparation method of the aromatic amine compound, the aromatic amine compound is prepared by hydrogenation of the aromatic nitro compound, and the reduction operation under mild reaction conditions can be realized by adopting the Y molecular sieve-encapsulated nano platinum as a catalyst.
Description
Technical Field
The invention relates to a preparation method of aromatic amine compounds, in particular to a method for preparing aromatic amine compounds by hydrogenation of nitro groups.
Background
The selective hydrogenation of aromatic nitro compounds to prepare aromatic amine compounds is a very important hydrogenation reaction in industry, because the generated amine compounds are important intermediates for synthesizing dyes, pesticides, medicaments, other fine chemicals and the like at present.
At present, in the industrial technical process aiming at the selective hydrogenation of nitro compounds, stoichiometric reducing agents are commonly used for selectively reducing nitro groups without influencing other reducible groups. These stoichiometric reducing agents include iron powder, hydrazine hydrate, triethylhydrosilane, and the like. However, the method has great environmental pollution, generates much waste water and waste residues, and has poor product quality (WO 91/00278, chem. Commun.2010,46,1769).
The supported transition metal is used for catalyzing the reaction, so that the method is more economical and more environment-friendly. Although the catalytic systems reported at present generally have higher activity and certain chemoselectivity, the problems still exist that the reaction conditions are harsh and/or the chemoselectivity cannot be maintained.
The topic group of Kempe reports that Co nano-particles loaded on SiCN carrier can realize directional conversion of aromatic amine compounds with high selectivity, but the catalyst needsThe reaction conditions are harsh, the hydrogen pressure is up to 5MPa, and the reaction temperature needs 110 ℃ (Angew. Professor Corma et al use TiO2Or Fe2O3The supported nano Au particles as a catalyst for the carrier also shows excellent catalytic selectivity in the nitro-selective reduction, but the reaction needs to be carried out at high temperature (140 ℃) and high pressure (2.5MPa) (Science,2006,313,332), and the high-temperature and high-pressure system limits the industrial application and production of the catalyst.
The conditions required by the supported platinum group catalyst in the catalysis of the reaction are quite mild, but the problem that the catalytic selectivity is difficult to control exists. Professor tevehei et al reported that the selectivity of ZSM-5 molecular sieve-encapsulated Pt particles in catalytic hydrogenation of p-ethylene nitrobenzene was 80% (ACS Catal,2015,5, 6893); the professor shochu reports that Beta molecular sieve encapsulated palladium particles exhibit near 100% selectivity when aromatic nitro compounds are selectively hydrogenated, but the selectivity of the desired amine product decreases rapidly when the reaction continues after the conversion of the reaction feedstock reaches 100% (angelw. chem. int. ed.2017,56,9749).
Disclosure of Invention
The invention mainly aims to provide a preparation method of an aromatic amine compound, which comprises the step of carrying out catalytic hydrogenation on an aromatic nitro compound by using nano platinum encapsulated by a Y molecular sieve as a catalyst (Pt @ Y) in a hydrogen atmosphere to prepare the aromatic amine compound.
According to an embodiment of the present invention, the mass of the nano platinum in the catalyst is 0.05% to 10% of the mass of the aromatic nitro compound.
According to an embodiment of the invention, in the Y molecular sieve encapsulated nano platinum catalyst, the mass of the nano platinum accounts for 0.1-5% of the mass of the whole catalyst.
According to an embodiment of the invention, in the Y molecular sieve encapsulated nano platinum catalyst, the mass of the nano platinum accounts for 0.5-2% of the mass of the whole catalyst.
According to an embodiment of the present invention, the aromatic nitro compound may further include one or more substituents selected from the group consisting of aldehyde, carbonyl, cyano, chlorine, bromine, and iodine on the aromatic ring.
According to an embodiment of the present invention, the aromatic nitro compound is one selected from p-bromonitrobenzene, m-chloronitrobenzene, p-nitrobenzaldehyde, p-nitrobenzonitrile, and p-chloronitrobenzene.
According to one embodiment of the present invention, the catalytic hydrogenation is performed at a reaction temperature of 55 to 80 ℃, and the pressure of hydrogen is 0.2 to 0.5 MPa.
According to an embodiment of the present invention, the catalytic hydrogenation is performed in an ethanol solvent, and the amount of ethanol is 10 to 50 times of the amount of the aromatic nitro compound by mass.
According to an embodiment of the present invention, the preparation method further comprises: after the catalytic hydrogenation is completed, collecting and processing the Y molecular sieve encapsulated nano platinum so as to be used as a catalyst for the catalytic hydrogenation again.
According to an embodiment of the present invention, the treating includes washing, drying and calcining the collected Y molecular sieve-encapsulated nano platinum.
According to the preparation method of the aromatic amine compound, the aromatic amine compound is prepared by hydrogenation of the aromatic nitro compound, and the reduction operation under mild reaction conditions can be realized by adopting the nano platinum particles encapsulated by the Y molecular sieve as the catalyst.
Drawings
FIG. 1 is an XRD pattern of Pt @ Y catalyst and Y molecular sieve alone of example 1 of the present invention;
FIG. 2 is a HADDF-STEM plot of Pt @ Y catalyst of example 1 of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
The invention provides a preparation method of an aromatic amine compound, which comprises the step of carrying out catalytic hydrogenation on an aromatic nitro compound by using nano platinum encapsulated by a Y molecular sieve as a catalyst to prepare the aromatic amine compound.
In one embodiment, the aromatic amine compound is prepared by hydrogenation of the aromatic nitro compound, and the reduction operation under mild reaction conditions can be realized by using nano platinum encapsulated by the Y molecular sieve as a catalyst.
The aromatic nitro compound refers to a compound in which a nitro group is bonded to a benzene ring. Preferably, the aromatic nitro compound also contains one or more other reducible groups, such as aldehyde groups, carbonyl groups, cyano groups, chlorine, bromine, iodine, and the like.
In one embodiment, under the condition that a plurality of reducible groups are connected to a benzene ring of the aromatic nitro compound, nano platinum encapsulated by a Y molecular sieve is used as a catalyst, and the aromatic amino compound is prepared by selective hydrogenation of nitro.
In one embodiment, the aromatic nitro compound may be: aromatic nitro compounds containing aldehyde groups, aromatic nitro compounds containing carbonyl groups, aromatic nitro compounds containing chlorine, aromatic nitro compounds containing bromine, and the like.
In one embodiment, the aromatic nitro compound comprises two reducible groups, the structure of which is shown below, and X can be an aldehyde group, a carbonyl group, a cyano group, chlorine, bromine, or iodine. For example, the aromatic nitro compound may be p-chloronitrobenzene, m-chloronitrobenzene, p-bromonitrobenzene, p-nitrobenzaldehyde, p-nitrobenzonitrile, etc.
In one embodiment, the use of a Pt @ Y catalyst allows for the targeted, highly selective reduction of nitro groups when other reducible groups such as aldehyde, carbonyl, cyano, chloro, bromo, iodo are also present on the phenyl ring. In addition, when the conversion of the reaction raw materials is complete, the reaction is continued to be prolonged, the selectivity of the catalytic reaction is well maintained, no side reaction occurs, and the method is very suitable for industrial production.
In the present invention, the Y molecular sieve encapsulation of the catalyst can force the aromatic nitro compound to adsorb on the surface of the platinum particles in an end-point adsorption conformation, rather than a lying adsorption conformation.
Without being bound by theory, it is speculated that during the reaction, reducible groups other than nitro groups are not reduced by the catalyst, mainly because the Y molecular sieve encapsulation limits the adsorption conformation of nitro compound raw materials on the platinum particle surface to end point adsorption rather than lying down adsorption. The end point adsorption conformation is beneficial to the adsorption of the nitro group on one hand, and inhibits the hydrogenation activity of other reducible groups on the other hand, the two factors cooperate to lead the hydrogenation reduction of the nitro group to have good chemical selectivity, even if the reaction raw materials are completely converted, the reaction time is continuously prolonged, the reaction selectivity is still well maintained, and the method is very suitable for practical production.
In one embodiment, the Y molecular sieve-encapsulated nano platinum particles are prepared by mixing a platinum-containing compound (platinum source), a silicon-containing compound (silicon source), an aluminum-containing compound (aluminum source), an alkali and water, aging, crystallizing and calcining.
In one embodiment, the platinum-containing compound is platinum tetraaminonitrate, the silicon-containing compound is Ludox HS-30, the aluminum-containing compound is aluminum hydroxide, and the base is sodium hydroxide or potassium hydroxide.
In one embodiment, the temperature of the crystallization is 90 to 110 ℃, such as 95 ℃, 100 ℃, 105 ℃, etc.
In one embodiment, the temperature of the baking is 340-360 deg.C, such as 350 deg.C.
In one embodiment, the product obtained by calcination is subjected to reduction treatment in a mixed gas of hydrogen and nitrogen, and the treatment temperature may be 280 to 320 ℃, for example, 300 ℃.
The Y molecular sieve encapsulated nano platinum used in the present invention may be prepared, for example, as described in j.am.chem.soc.2012,134, 17688; synthesized by the method disclosed in J.Am.chem.Soc.2014,136, 15280. For example, platinum tetraaminoplatinum nitrate is used as a platinum source, Ludox HS-30 is used as a silicon source for synthesizing a Y molecular sieve, aluminum hydroxide is used as an aluminum source for synthesizing the Y molecular sieve, and the platinum source, the silicon source, the aluminum source and the aluminum hydroxide are usedAnd sodium is fully and uniformly stirred in the water phase at room temperature, is aged for 24 hours at room temperature, is statically crystallized for 12 hours at the temperature of 100 ℃, and is subjected to suction filtration and drying to obtain the white material of the platinum precursor packaged by the Y molecular sieve. Roasting the dried material of the platinum precursor encapsulated by the Y molecular sieve for 3 hours at 350 ℃ in the air atmosphere, and then carrying out H treatment at 300 DEG C2/N2And treating for 2 hours in the mixed gas atmosphere to obtain the Y molecular sieve encapsulated nano platinum particles.
In one embodiment, the platinum nanoparticles have an average particle size of 1.5-2.5 nm, such as 1.9 nm.
In one embodiment, the nano platinum particles encapsulated by the Y molecular sieve consist of 0.1-5 wt% of nano platinum and the balance of the Y molecular sieve; preferably, the mass of the nano platinum particles accounts for 0.5-2 wt%, such as 1%, 1.5% and the like, of the total mass of Pt @ Y.
In one embodiment, the nano platinum particles encapsulated by the Y molecular sieve, the solvent and the aromatic nitro compound are added into a reaction kettle, and the reaction is carried out at a certain reaction temperature in a hydrogen atmosphere, so as to obtain the corresponding aromatic amine compound after the reaction is completed.
In one embodiment, the mass of the nano platinum in the Y molecular sieve encapsulated nano platinum catalyst is 0.05 to 10% of the mass of the aromatic nitro compound, for example, 1%, 5%, 8%, and the like.
In one embodiment, the temperature of the catalytic hydrogenation reaction of the aromatic nitro compound is 55 to 80 ℃, preferably 60 to 70 ℃, for example 65 ℃. The temperature range is easy to control, and the operation cost is low.
In one embodiment, the catalytic hydrogenation reaction time of the aromatic nitro compound is 30 to 240 minutes, and the reaction time can be properly adjusted according to different substrates.
In one embodiment, the pressure of hydrogen in the catalytic hydrogenation reaction of the aromatic nitro compound is 0.2-0.5 MPa, and the pressure condition is easy to control, convenient to implement, cost-saving and relatively safe; more preferably, the reaction is carried out under a hydrogen atmosphere of 0.2 MPa.
In the catalytic hydrogenation reaction of the aromatic nitro compound according to an embodiment of the present invention, ethanol is used as a reaction solvent, and the amount of ethanol may be 10 to 50 times of the amount of the aromatic nitro compound.
In the catalytic hydrogenation reaction of the aromatic nitro compound according to an embodiment of the present invention, after the reaction is completed, the corresponding aromatic amine compound can be obtained by centrifuging and then rotary evaporating the reaction solution.
In one embodiment, after the reaction is completed, the nano platinum particles encapsulated by the Y molecular sieve are washed by ethanol, dried at 80 ℃, and then roasted for 2 hours at 500 ℃ in the air atmosphere, so that the catalyst can be reused and is simple to operate.
In one embodiment, the aromatic nitro compound is selectively reduced by using a nano platinum particle catalyst encapsulated by a Y molecular sieve, and the selectivity and the conversion rate are close to 100 percent; meanwhile, even if the reaction time is continuously prolonged after the reaction raw materials are completely converted, the reaction selectivity can still be maintained to be more than 99 percent; in addition, the reaction condition is mild, the operability is strong, and the method has certain market prospect.
The preparation of the aromatic amine compound according to one embodiment of the present invention will be further described below with reference to specific examples. The physical and chemical structure characterization of the prepared packaged Pt @ Y catalyst adopts XRD and HADDF-STEM, the load content of Pt particles in a Y molecular sieve is characterized by ICP-MS, and the reactant conversion rate and the product selectivity in the hydrogenation reaction are analyzed by GC-MS.
Example 1
4.44g of sodium hydroxide, 1.04g of aluminum hydroxide and 12.0g of Ludox-HS 30 are dissolved in 40.0g of water together, 0.1g of tetraaminoplatinum nitrate is added and stirred uniformly, the mixed solution is aged for 24 hours at room temperature, then is statically crystallized for 12 hours at 100 ℃, and finally is filtered and dried to obtain a white material. The white material is roasted for 3 hours at 350 ℃ in air atmosphere at the heating rate of 0.0114 ℃/s, and then is roasted at 9% H at the heating rate of 0.0187 ℃/s2/N2And treating for 2 hours in a mixed gas atmosphere to obtain the required Pt @ Y catalyst.
XRD analysis in figure 1 shows that the self-structure of the Y molecular sieve is not influenced by the introduction of the platinum particles, and simultaneously, no characteristic peak of the platinum particles is observed in XRD, which shows that the particle size of the encapsulated platinum particles is small and the phenomenon of large-range agglomeration does not occur. An electron microscope picture shows that the platinum particles are uniformly distributed in the Y molecular sieve, the particle size of the synthesized platinum particles is uniform, the average particle size is about 1.9nm, and the mass percentage of the nano metal platinum in the catalyst is 1.23 wt%.
32.5mg of Pt @ Y catalyst was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was added to the autoclave, air in the autoclave was replaced with hydrogen three times, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, the conversion rate and the selectivity are both 100%, and no by-product is detected according to GC-MS analysis.
Example 2
28mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-bromonitrobenzene as a substrate was taken and added to the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. At the moment, taking out part of reaction liquid from the reaction system, centrifuging, carrying out rotary evaporation, washing the catalyst with ethanol for three times, wherein gas chromatography-mass spectrometry analysis shows that p-bromonitrobenzene is completely converted into p-bromoaniline, the conversion rate and the selectivity are both 100%, then continuing to react for 1 hour aiming at the rest reaction liquid, stopping the reaction, carrying out centrifugation, carrying out rotary evaporation, washing the catalyst with ethanol for three times, wherein the gas chromatography-mass spectrometry analysis shows that the conversion rate of the p-bromonitrobenzene is still 100%, the selectivity of the p-bromoaniline is kept at 100%, and no by-product is detected in GC-MS analysis.
Example 3
28mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-bromonitrobenzene as a substrate was taken and added to the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, rotary steaming, washing the catalyst with ethanol for three times, and gas chromatography-mass spectrometry analysis shows that p-bromonitrobenzene is completely converted into p-bromoaniline, and the conversion rate and the selectivity are both 100%.
Example 4
20mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of m-chloronitrobenzene as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of the hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that m-chloronitrobenzene is completely converted into m-chloroaniline, and the conversion rate and the selectivity are both 100%.
Example 5
40mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-nitrobenzaldehyde as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of the hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing gas chromatography-mass spectrometry to show that the p-nitrobenzaldehyde is completely converted into the p-aminobenzaldehyde, and the conversion rate and the selectivity are both 100 percent.
Example 6
40mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-nitrobenzonitrile as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that the p-nitrobenzonitrile is completely converted into the p-aminobenzonitrile, and the conversion rate and the selectivity are both 100 percent.
Example 7
40mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 180 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, and the conversion rate and the selectivity are both 100%.
Example 8
40mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of the hydrogen was increased to 0.5MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, and the conversion rate and the selectivity are both 100%.
Example 9
40mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of the hydrogen was increased to 0.2MPa, and the reaction was carried out at 80 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, and the conversion rate and the selectivity are both 100%.
Example 10
80mg of the Pt @ Y catalyst prepared in example 1 was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was charged in the autoclave, the air in the autoclave was replaced three times with hydrogen, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, and the conversion rate and the selectivity are both 100%.
Example 11
4.44g of sodium hydroxide, 1.04g of aluminum hydroxide and 12.0g of Ludox-HS 30 are dissolved in 40.0g of water together, 0.08g of tetraaminoplatinum nitrate is added and stirred uniformly, the mixed solution is aged for 24 hours at room temperature, then is statically crystallized for 12 hours at 100 ℃, and finally is filtered and dried to obtain a white material. The white material is roasted for 3 hours at 350 ℃ in air atmosphere at the heating rate of 0.0114 ℃/s, and then is roasted at 9% H at the heating rate of 0.0187 ℃/s2/N2And treating for 2 hours in a mixed gas atmosphere to obtain the required Pt @ Y catalyst.
Wherein, in the Pt @ Y catalyst, the average particle diameter of platinum particles is about 1.9nm, and the mass percent of nano metal platinum in the catalyst is 1.17 wt%.
42mg of Pt @ Y catalyst was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was added to the autoclave, the air in the autoclave was replaced with hydrogen three times, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, and analyzing by gas chromatography-mass spectrometry to show that p-chloronitrobenzene is completely converted into p-chloroaniline, the conversion rate and the selectivity are 100%, and no by-product is detected according to GC-MS analysis.
Comparative example
0.1g of tetraammineplatinum nitrate is loaded on a 2.4g Y molecular sieve by an impregnation method, the loaded catalyst is calcined for 3 hours at the temperature rising rate of 0.0114 ℃/s and in the air atmosphere of 350 ℃, and then at the temperature rising rate of 0.0187 ℃/s and in 9% H2/N2And treating for 2 hours in a mixed gas atmosphere to obtain the required Pt/Y catalyst.
32.5mg of Pt/Y catalyst was charged in a small autoclave, 10ml of ethanol was added, 0.1mmol of p-chloronitrobenzene as a substrate was added to the autoclave, the air in the autoclave was replaced with hydrogen three times, the pressure of hydrogen was increased to 0.2MPa, and the reaction was carried out at 65 ℃ for 40 minutes. After the reaction is completed, centrifuging, carrying out rotary evaporation, washing the catalyst for three times by using ethanol, wherein the gas chromatography-mass spectrometry analysis shows that the conversion rate of the p-chloronitrobenzene is 100 percent, but the selectivity is 41 percent, and the byproducts are aniline and nitrobenzene by GC-MS analysis.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (10)
1. A preparation method of aromatic amine compounds comprises the step of carrying out catalytic hydrogenation on aromatic nitro compounds by using nano platinum packaged by a Y molecular sieve as a catalyst in a hydrogen atmosphere to prepare the aromatic amine compounds.
2. The method according to claim 1, wherein the mass of the nano platinum in the catalyst is 0.05-10% of the mass of the aromatic nitro compound.
3. The method of claim 1, wherein in the Y molecular sieve encapsulated nano platinum catalyst, the mass of the nano platinum accounts for 0.1-5% of the total catalyst mass.
4. The method of claim 3, wherein in the Y molecular sieve encapsulated nano platinum catalyst, the mass of the nano platinum accounts for 0.5-2% of the total catalyst mass.
5. The method according to claim 1, wherein the aromatic nitro compound may further comprise one or more substituents selected from the group consisting of aldehyde group, carbonyl group, cyano group, chlorine, bromine and iodine on the aromatic ring.
6. The method according to claim 5, wherein the aromatic nitro compound is one selected from p-bromonitrobenzene, m-chloronitrobenzene, p-nitrobenzaldehyde, p-nitrobenzonitrile, p-chloronitrobenzene.
7. The process according to claim 1, wherein the catalytic hydrogenation is carried out at a reaction temperature of 55 to 80 ℃ and a hydrogen pressure of 0.2 to 0.5 MPa.
8. The method according to claim 7, wherein the catalytic hydrogenation is carried out in an ethanol solvent, and the amount of ethanol used is 10 to 50 times the amount of the aromatic nitro compound by mass.
9. The method of any of claims 1 to 8, further comprising: after the catalytic hydrogenation is completed, collecting and processing the Y molecular sieve encapsulated nano platinum so as to be used as a catalyst for the catalytic hydrogenation again.
10. The method of claim 9, wherein the processing comprises washing, oven drying, and calcining the collected Y molecular sieve encapsulated nanoplatinum.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112108175A (en) * | 2020-08-17 | 2020-12-22 | 西安交通大学 | Preparation method of aromatic olefin |
| CN115286515A (en) * | 2022-08-19 | 2022-11-04 | 中山大学 | Method for preparing parachloroaniline |
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| CN115286515A (en) * | 2022-08-19 | 2022-11-04 | 中山大学 | Method for preparing parachloroaniline |
| CN115286515B (en) * | 2022-08-19 | 2023-10-27 | 中山大学 | Method for preparing p-chloroaniline |
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