CN119039149A - Method for preparing aromatic methylamine - Google Patents
Method for preparing aromatic methylamine Download PDFInfo
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- CN119039149A CN119039149A CN202411544968.0A CN202411544968A CN119039149A CN 119039149 A CN119039149 A CN 119039149A CN 202411544968 A CN202411544968 A CN 202411544968A CN 119039149 A CN119039149 A CN 119039149A
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/46—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acids or esters thereof in presence of ammonia or amines
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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Abstract
The invention belongs to the technical field of chemical industry, and discloses a method for preparing aromatic methylamine, which comprises the following steps of mixing aromatic carboxylic acid, ammonia gas and carrier gas, and preheating to a gaseous state to obtain mixed gas; and a second step, carrying out gas-solid phase catalytic reaction on the mixed gas at the reaction temperature of 380-560 ℃ and the reaction pressure of 0.05-0.25 MPa to obtain the aromatic methylamine. In the preparation process of the aromatic methylamine, the aromatic carboxylic acid is subjected to gas-phase reaction, so that the continuous preparation of the aromatic methylamine can be realized, and the production efficiency is improved. By controlling the reaction temperature and pressure ranges, the direct preparation of aromatic methylamine from aromatic carboxylic acid can be realized, and the reaction control steps are reduced. The catalyst doped with various elements can play a synergistic effect, shorten the duration time of the intermediate product of the transition state and realize the rapid conversion from aromatic carboxylic acid to aromatic methylamine.
Description
Technical Field
The present invention relates generally to the field of chemical technology. More particularly, the present invention relates to a process for preparing aromatic methylamines.
Background
Aromatic amine compounds are important organic raw materials and are widely used for the production of dyes, medicines, agrochemicals, additives, surfactants, textile assistants, chelating agents, polymers, flame retardants and the like.
The preparation of aromatic amines includes direct preparation from aromatic hydrocarbons, preparation from hydrogenation of nitrated aromatic hydrocarbons, preparation from hydrogenation of aromatic amides, and the like. Most aromatic amines are produced from aromatic nitro compounds by reduction. There are many methods for reducing nitro group into amino group, and the methods for reducing nitro group adopted in industry at present mainly include a reduction method of metal in an acidic, neutral and alkaline system, a chemical reduction method, a catalytic hydrogenation reduction method, an electrochemical reduction method and the like. The catalytic hydrogenation reduction method uses noble metals such as Pd, pt, ni and the like and alloys thereof as catalysts, and reduces nitro into amino under certain temperature and pressure.
The preparation of aromatic amine in the prior art has the problems of low production efficiency, low raw material conversion efficiency, complicated steps and the like, and a method capable of directly preparing aromatic amine through continuous reaction is still needed to improve the production efficiency and the raw material conversion rate.
Disclosure of Invention
In order to at least solve one or more of the technical problems mentioned above, the invention provides a method for preparing aromatic methylamine, which comprises the steps of mixing aromatic carboxylic acid, ammonia gas and carrier gas, preheating to a gaseous state to obtain mixed gas, and carrying out gas-solid phase catalytic reaction on the mixed gas at the reaction temperature of 380-560 ℃ and the reaction pressure of 0.05-0.25 MPa to obtain the aromatic methylamine.
According to one embodiment of the invention, ammonia is present in excess relative to the aromatic carboxylic acid in the mixed gas.
According to one embodiment of the invention, the molar ratio of the aromatic carboxylic acid to the ammonia gas in the mixed gas is 1:15-1:30.
According to one embodiment of the invention, the molar ratio of aromatic carboxylic acid to ammonia in the mixed gas is 1:20.
According to one embodiment of the invention, in the mixed gas, ammonia accounts for 10-100% of the total volume of the ammonia and the carrier gas.
According to one embodiment of the invention, in the mixed gas, ammonia accounts for 20-60% of the total volume of the ammonia and the carrier gas.
According to one embodiment of the invention, the aromatic carboxylic acid is selected from C (2+4n)H(2n+4-m)(COOH)m, wherein n is selected from 1,2 or 3, when n=1, m=1, 2 or 3, when n=2, m=1 or 2, when n=3, m=1.
According to one embodiment of the present invention, the aromatic carboxylic acid is selected from any one of benzoic acid, isophthalic acid, terephthalic acid, 1, 8-naphthalene dicarboxylic acid, 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 9-anthracene carboxylic acid, 3-phenanthrene carboxylic acid, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, 1, 3-naphthalene dicarboxylic acid, 1, 7-naphthalene dicarboxylic acid, 2-phenanthrene carboxylic acid, trimellitic acid.
According to one embodiment of the present invention, the carrier gas is selected from at least one of nitrogen, carbon dioxide, helium, argon, hydrogen and ammonia. Preferably, the carrier gas is selected from at least one of hydrogen and ammonia. More preferably, the carrier gas is selected from ammonia.
According to one embodiment of the present invention, the preheating temperature of the mixed gas is 200 ℃ to 500 ℃. Preferably, the preheating temperature of the mixed gas is 300 ℃ or 350 ℃.
According to one embodiment of the invention, the reaction temperature of the gas-solid phase catalytic reaction is 400-500 ℃, the reaction pressure is 0.07-0.10 MPa, and the reaction time is 10-60 s.
According to one embodiment of the invention, the catalyst for the gas-solid phase catalytic reaction is a supported catalyst, wherein the active component of the supported catalyst is selected from at least three elements of transition metals, alkali metals, alkaline earth metals and noble metals. Preferably, the active component of the supported catalyst is selected from at least three elements of Au, P, ti, mo, ru, ni, pt, pd, rh, ag, co. More preferably, the active component of the supported catalyst comprises at least Au and Ag.
According to one embodiment of the invention, the active component accounts for 1-10% of the weight of the supported catalyst.
According to one embodiment of the invention, the active component accounts for 5-8% of the weight of the supported catalyst.
According to one embodiment of the invention, the support of the supported catalyst is selected from the group consisting of SiO 2、Al2O3、TiO2.
According to one embodiment of the invention, the support of the supported catalyst is Al 2O3.
According to one embodiment of the invention, the active component of the supported catalyst comprises 1 part by weight of Ag, 0-0.5 part by weight of P, 0-0.3 part by weight of Ti, 0-0.3 part by weight of Mo, 0-0.4 part by weight of Ru, 0-0.5 part by weight of Ni, 0-0.2 part by weight of Pt, 0-0.3 part by weight of Pd, 0-0.3 part by weight of Rh, 0-0.5 part by weight of Au and 0-0.3 part by weight of Co.
In the preparation process of the aromatic methylamine, aromatic carboxylic acid is used as a starting point, and gas-phase reaction is carried out in the presence of ammonia gas and a catalyst to directly and continuously generate the aromatic methylamine and byproducts. In the invention, the aromatic carboxylic acid which is in a gaseous state is formed by preheating, and the mixed gas is formed by ammonia gas and carrier gas, so that continuous gas phase reaction can be realized, and the production efficiency can be improved. By controlling the reaction temperature and pressure ranges, the direct preparation of aromatic methylamine from aromatic carboxylic acid can be realized, and the reaction control steps are reduced. By selecting the reaction temperature and the reaction pressure, the intermediate products of the transition states such as aromatic amide and the like are quickly converted into aromatic methylamine after being temporarily stored. The catalyst doped with various elements can play a synergistic effect, and the duration time of the intermediate product in the transition state is shortened, so that the reaction efficiency is improved, and the rapid conversion from aromatic carboxylic acid to aromatic methylamine is realized.
Drawings
The above, as well as additional purposes, features, and advantages of exemplary embodiments of the present invention will become readily apparent from the following detailed description when read in conjunction with the accompanying drawings. In the drawings, embodiments of the invention are illustrated by way of example and not by way of limitation, and like reference numerals refer to similar or corresponding parts and in which:
FIG. 1 shows a schematic step diagram of a process for preparing aromatic methylamines;
FIG. 2 shows a block diagram of a reaction system suitable for use in embodiments of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and in the claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification and claims, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should be further understood that the term "and/or" as used in the present specification and claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Figure 1 shows a schematic step diagram of a process for preparing aromatic methylamines.
As shown in fig. 1, the invention provides a method for preparing aromatic methylamine, which comprises the steps of mixing aromatic carboxylic acid, ammonia gas and carrier gas, preheating to a gaseous state to obtain mixed gas, and carrying out gas-solid phase catalytic reaction on the mixed gas at the reaction temperature of 380-560 ℃ and the reaction pressure of 0.05-0.25 MPa in the second step S2 to obtain the aromatic methylamine.
In the preparation process of the aromatic methylamine, aromatic carboxylic acid is used as a starting point, gas phase reaction is carried out in the presence of ammonia gas and a catalyst, continuous reaction can be carried out, and the aromatic methylamine and byproducts are directly generated.
The reactor suitable for use in the present invention comprises at least one of a fixed bed, a fluidized bed, an ebullated bed, preferably a fluidized bed or a fixed bed. Wherein, the reactor is preloaded with a solid-phase catalyst, the aromatic carboxylic acid is preheated to be in a gaseous state, and the aromatic carboxylic acid and ammonia gas are conveyed into the reactor together by carrier gas to carry out gas-solid phase catalytic reaction.
In the invention, the aromatic carboxylic acid which is in a gaseous state is formed by preheating, and the mixed gas is formed by ammonia gas and carrier gas, so that continuous gas phase reaction can be realized, and the production efficiency can be improved. By controlling the reaction temperature and pressure range, the aromatic methylamine can be directly prepared from the aromatic carboxylic acid, the reaction control steps are reduced, and the reaction efficiency is improved.
In an embodiment of the invention the aromatic carboxylic acid is selected from C (2+4n)H(2n+4-m)(COOH)m, wherein n is selected from 1,2 or 3, when n=1, m=1, 2 or 3, when n=2, m=1 or 2, when n=3, m=1.
Preferably, the aromatic carboxylic acid is selected from the group consisting of benzoic acid, isophthalic acid, terephthalic acid, 1, 8-naphthalene dicarboxylic acid, 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 9-anthracene carboxylic acid, 3-phenanthrene carboxylic acid, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, 1, 3-naphthalene dicarboxylic acid, 1, 7-naphthalene dicarboxylic acid, 2-phenanthrene carboxylic acid, trimellitic acid.
In the invention, by preferably selecting the aromatic carboxylic acid shown in the expression and the listed aromatic carboxylic acid, the rapid preheating gasification can be realized, the temperature requirement is low, the fluidity is strong, and the method is suitable for large-flow production in industrial scenes.
According to one embodiment of the present invention, the carrier gas is selected from at least one of nitrogen, carbon dioxide, helium, argon, hydrogen, ammonia. Preferably, the carrier gas is selected from at least one of hydrogen and ammonia. More preferably, the carrier gas is selected from ammonia.
In the present invention, the carrier gas may be nitrogen, carbon dioxide, helium or argon which are relatively inert to the hydrogenation reaction, or may be hydrogen and/or ammonia which have a promoting effect on the hydrogenation reaction. When ammonia gas is selected as the carrier gas, the ammonia gas can properly release hydrogen at the temperature and pressure defined in the present invention, thereby promoting the forward progress of the catalytic hydrogenation reaction.
According to one embodiment of the invention, ammonia is present in excess relative to the aromatic carboxylic acid in the mixed gas. That is, the molar amount of ammonia is greater than the molar amount of aromatic carboxylic acid. The excessive ammonia can promote the catalytic hydrogenation reaction of the aromatic carboxylic acid and improve the conversion rate of the aromatic carboxylic acid. Preferably, in the mixed gas, the molar ratio of the aromatic carboxylic acid to the ammonia gas is 1:15-1:30. More preferably, the molar ratio of aromatic carboxylic acid to ammonia is 1:20. The molar amount of ammonia is 15 to 30 times that of the aromatic carboxylic acid, so that on one hand, the conversion rate of the aromatic carboxylic acid can be improved, and on the other hand, the excessive ammonia can provide hydrogen in the reaction process so as to promote the catalytic hydrogenation reaction.
According to one embodiment of the invention, in the mixed gas, ammonia accounts for 10-100% of the total volume of the ammonia and the carrier gas. Preferably, the ammonia accounts for 20-60% of the total volume of the ammonia and the carrier gas. The total volume of ammonia and carrier gas is the sum of the volume of ammonia and the volume of carrier gas. When the carrier gas is other than ammonia, the ammonia accounts for at least 10% to ensure that the ammonia concentration is not lower than the reaction concentration with the aromatic carboxylic acid. When the carrier gas is ammonia, the ammonia ratio is 100%. Preferably, when the carrier gas is not ammonia, the ammonia accounts for 20-60% of the total volume of the ammonia and the carrier gas, so that the concentration of the ammonia is optimal, and the ammonia reacting with the aromatic carboxylic acid and the ammonia providing hydrogen can be provided simultaneously.
According to one embodiment of the present invention, the preheating temperature of the mixed gas is 200 ℃ to 500 ℃. Preferably, the preheating temperature of the mixed gas is 300 ℃ or 350 ℃. In the present invention, the selection of the lowest preheating temperature is set differently depending on the kind of aromatic carboxylic acid. The maximum preheating temperature may be set to be slightly lower than the reaction temperature of the gas-solid phase catalytic reaction, and early decomposition of the aromatic carboxylic acid during gasification of the aromatic carboxylic acid may be reduced.
According to one embodiment of the invention, the reaction temperature of the gas-solid phase catalytic reaction is 400-500 ℃, the reaction pressure is 0.07-0.10 MPa, and the reaction time is 10-60 s. Wherein, the reaction time is adjusted according to different reaction temperatures and reaction pressures and the catalytic capability of the catalyst. Under the conditions of the reaction temperature, the reaction pressure and the like, the aromatic carboxylic acid and ammonia gas form aromatic amide or a transition intermediate product thereof, and the aromatic amide or other transition intermediate products are hydrogenated under the catalysis of a gas-solid phase catalyst to form aromatic methylamine, so that the aromatic amide or other transition intermediate products are directly converted into the aromatic methylamine after being subjected to transient duration due to the selection of the reaction temperature and the reaction pressure.
According to one embodiment of the invention, the catalyst for the gas-solid phase catalytic reaction is a supported catalyst, wherein the active component of the supported catalyst is selected from at least three elements of transition metals, alkali metals, alkaline earth metals and noble metals. Preferably, the active component of the supported catalyst is at least three elements selected from Au (gold), P (phosphorus), ti (titanium), mo (molybdenum), ru (ruthenium), ni (nickel), pt (platinum), pd (palladium), rh (rhodium), ag (silver), co (cobalt). More preferably, the active components of the supported catalyst include at least Au (gold) and Ag (silver).
Transition metals refer primarily to IIIB, IVB, VB, VIB, VIIB, and all elements of group VIII, IB, IIB.
Noble metals are mainly gold, silver and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum).
Alkaline earth metals mainly refer to beryllium, magnesium, calcium, strontium, barium and radium.
Alkali metal mainly refers to lithium, sodium, potassium, rubidium, cesium, francium.
The active component may be selected randomly among the above metals. Preferably, the active component must be present in Ag and/or Au.
In the invention, the synergistic effect of the catalyst doped with various elements can be exerted, the duration of the intermediate product of the transition state of the aromatic methylamine is shortened, and the intermediate product is quickly converted into the aromatic methylamine, so that the reaction efficiency is improved, and the quick conversion from the aromatic carboxylic acid to the aromatic methylamine is realized.
Catalytic hydrogenation reactions are not only related to adsorption and dissociation of hydrogen, but also to adsorption of substrate molecules and desorption of product molecules. By selecting at least three of the above catalysts, the hydrogenation activity of the single-type atomic catalyst can be broken through, thereby realizing efficient hydrogenation reaction. The inventors have studied that Au (gold) and Ag (silver) have strong synergistic effects with the other catalysts described above, and therefore, it is preferable that the active component is a mixture of gold and silver with the other catalysts. In addition, the use of the above-mentioned various catalysts plays an important role in improving the stability of the catalyst.
In the present invention, the absolute amount of the catalyst may be adjusted according to the amount of the reactants such as aromatic carboxylic acid and ammonia gas in the reactor, the size of the reactor, and the like.
According to one embodiment of the invention, the support of the supported catalyst is selected from the group consisting of SiO 2、Al2O3、TiO2. Preferably, the support is Al 2O3. The above support can provide multiple pore sizes, a large specific surface area, and high dispersibility.
According to one embodiment of the invention, the active component accounts for 1-10% of the weight of the supported catalyst. For example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and the like may be used, and 5 to 8% is preferable. By adopting the proportion, a larger specific surface area can be provided for the catalytic hydrogenation reaction.
According to one embodiment of the invention, the active component of the supported catalyst comprises 1 part by weight of Ag, 0-0.5 part by weight of P, 0-0.3 part by weight of Ti, 0-0.3 part by weight of Mo, 0-0.4 part by weight of Ru, 0-0.5 part by weight of Ni, 0-0.2 part by weight of Pt, 0-0.3 part by weight of Pd, 0-0.3 part by weight of Rh, 0-0.5 part by weight of Au and 0-0.3 part by weight of Co.
For example, the formulation may be 1 part by weight of Ag, 0.5 part by weight of P, 0.3 part by weight of Ti, 0.3 part by weight of Mo, 0.4 part by weight of Ru, 0.5 part by weight of Ni, 0.2 part by weight of Pt, 0.3 part by weight of Pd, 0.3 part by weight of Rh, 0.5 part by weight of Au, 0.3 part by weight of Co, or a formulation in which one or more of the other components except silver are reduced based on the above formulation.
Preferably, the active component consists of Ag-P-Ni-Pt-Rh according to the weight ratio of 1:0.40:0.30:0.09:0.15.
Preferably, the active component consists of Ag-Ni-Pt-Au-P-Rh according to the weight ratio of 1:0.30:0.09:0.10:0.40:0.15.
Preferably, the active component consists of Ag-Ni-Pt-Mo-Ti-Ru according to the weight ratio of 1:0.30:0.09:0.15:0.10:0.25.
Preferably, the active component consists of Ag-Ni-Pt-Au-Mo-Ru according to the weight ratio of 1:0.30:0.09:0.10:0.05:0.25.
Preferably, the active component consists of Ag-Ni-Pt-Au-Co according to the weight ratio of 1:0.30:0.09:0.40:0.20.
Preferably, the active component consists of Ag-Ni-Pt-Au-P-Rh-Ru-Mo according to the weight ratio of 1:0.30:0.09:0.40:0.40:0.15:0.25:0.05.
Preferably, the active component consists of Ag-Ni-Pt-Au-P-Rh-Ru in a weight ratio of 1:0.30:0.09:0.40:0.40:0.15:0.25.
Preferably, the active component consists of Ag-P-Ni-Pt-Rh-Mo according to the weight ratio of 1:0.40:0.30:0.09:0.15:0.05.
Preferably, the active component consists of Ag-P-Ni-Pt-Rh according to the weight ratio of 1:0.10:0.30:0.09:0.15.
Preferably, the active component consists of Ag-Au-Mo-Ni-Pt-Ru according to the weight ratio of 1:0.10:0.05:0.30:0.09:0.25.
In the formula, silver is used as a main catalyst, and other components are used as auxiliary components. When the amounts of the other elements than silver are all 0, pure silver is used as the catalyst. In the present invention, it is preferable that at least two other elements other than silver are contained as the auxiliary catalyst. By setting the weight proportion, the catalytic activity of silver on the catalytic hydrogenation reaction of the aromatic carboxylic acid can be improved.
The catalytic hydrogenation reaction of the aromatic carboxylic acid can be continuously performed by preloading the above-mentioned supported gas-solid phase catalyst in the reactor.
FIG. 2 shows a block diagram of a reaction system suitable for use in embodiments of the present invention.
As shown in fig. 2, the aromatic carboxylic acid, ammonia gas and carrier gas are input into the mixer 1 for mixing and preheating, when the mixing and preheating are completed, the preheated mixed gas is input into the reactor 2 from the mixer 1, the temperature and pressure are controlled in the reactor 2, the mixed gas is subjected to gas-phase continuous reaction under the catalysis of the supported gas-solid phase catalyst preloaded in the reactor 2, and the obtained product comprises aromatic methylamine, amide, nitrile and other byproducts, and the product is collected by the catcher 3.
The following examples are provided to illustrate the reaction process of the present invention.
Example 1.
The active component is loaded in the fluidized bed and is a supported catalyst with Al 2O3 as a carrier, wherein the weight ratio of the active component to the supported catalyst is 1:0.40:0.30:0.09:0.15.
Benzoic acid, ammonia and nitrogen were mixed in a mixer in a molar ratio of 1:15:40, and heated to 200 ℃ during the mixing process to obtain a mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 420 ℃, the reaction pressure was 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.8%, and the molar yield of benzylamine reaches 50.1%.
Example 2.
Based on example 1, the molar ratio of benzoic acid, ammonia and nitrogen was adjusted to 1:20:40, the reaction temperature was controlled to 560 ℃, the reaction pressure was 0.25MPa, and the residence time of the mixed gas in the fluidized bed was 28s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.9%, and the molar yield of benzylamine reaches 56.3%.
Example 3.
Based on example 1, the molar ratio of benzoic acid, ammonia and nitrogen was adjusted to 1:15:12.5, the reaction temperature was controlled to 380 ℃, the reaction pressure was 0.05MPa, and the residence time of the mixed gas in the fluidized bed was 60s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.9%, and the molar yield of benzylamine reaches 39.2%.
Example 4.
The active component is loaded in the fluidized bed and is a supported catalyst with Al 2O3 as a carrier, wherein the weight ratio of the active component to the supported catalyst is 1:0.40:0.30:0.09:0.15.
Mixing benzoic acid and ammonia gas in a mixer according to a molar ratio of 1:160, and heating to 200 ℃ in the mixing process to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 560 ℃, the reaction pressure was 0.25MPa, and the residence time of the mixed gas in the fluidized bed was 10s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.8%, and the molar yield of benzylamine reaches 54.9%. Therefore, ammonia is used as carrier gas, and the conversion rate and the yield are high.
Example 5.
The active component is loaded in the fluidized bed and is a supported catalyst with Al 2O3 as a carrier, wherein the weight ratio of the active component to the supported catalyst is 1:0.40:0.30:0.09:0.15.
Mixing benzoic acid, ammonia and hydrogen in a mixer according to a molar ratio of 1:100:40, and heating to 200 ℃ in the mixing process to obtain mixed gas. The mixed gas is introduced into the fluidized bed from the mixer, the reaction temperature is controlled to be 420 ℃, the reaction pressure is controlled to be 0.10MPa, and the residence time of the mixed gas in the fluidized bed is controlled to be 10s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.8%, and the molar yield of benzylamine reaches 57.6%. It can be seen that when hydrogen is used as a carrier gas, both the conversion of benzoic acid and the molar yield of benzylamine are high.
Example 6.
The active component is loaded in the fluidized bed and is a supported catalyst with Al 2O3 as a carrier, wherein the weight ratio of the active component to the supported catalyst is 1:0.40:0.30:0.09:0.15.
Benzoic acid, ammonia and nitrogen were mixed in a mixer in a molar ratio of 1:15:135, and heated to 200 ℃ during the mixing process to obtain a mixed gas. The mixed gas is introduced into the fluidized bed from the mixer, the reaction temperature is controlled to be 420 ℃, the reaction pressure is controlled to be 0.08MPa, and the residence time of the mixed gas in the fluidized bed is controlled to be 10s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzyl amine, benzonitrile and benzamide, wherein the conversion rate of benzoic acid is 79.1%, and the molar yield of the benzyl amine reaches 13.7%.
Example 7.
The active component is loaded in the fluidized bed and is a supported catalyst with Al 2O3 as a carrier, wherein the weight ratio of the active component to the supported catalyst is 1:0.30:0.09:0.10:0.40:0.15.
Benzoic acid, ammonia and nitrogen were mixed in a mixer in a molar ratio of 1:20:40, and heated to 200 ℃ during the mixing process to obtain a mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 380 ℃, the reaction pressure was 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 27.5s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains benzylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of benzoic acid is 99.2%, and the molar yield of benzylamine reaches 42.1%.
Example 8.
Based on example 7, the reaction temperature was adjusted from 380 ℃ to 560 ℃ at 20 ℃ intervals, and the benzoic acid conversion and the molar yield of benzylamine at different reaction temperatures were obtained by detecting the products respectively as shown in table 1.
TABLE 1
| Sequence number | Reaction temperature/°c | Benzoic acid conversion/% | Molar yield of benzylamine/% |
| 1 | 400 | 99.6 | 47.8 |
| 2 | 420 | 99.8 | 50.4 |
| 3 | 440 | 99.8 | 51.3 |
| 4 | 460 | 99.0 | 44.5 |
| 5 | 480 | 98.7 | 41.2 |
| 6 | 500 | 98.2 | 40.4 |
| 7 | 540 | 98.4 | 34.6 |
| 8 | 560 | 98.1 | 30.8 |
Example 9.
Based on example 7, the reaction temperature was set at 420℃and the reaction pressures were adjusted to 0.07 and 0.10MPa, and the products were examined to obtain the benzoic acid conversion and the molar yield of benzylamine at different reaction pressures as shown in Table 2.
TABLE 2
| Sequence number | Reaction temperature/°c | Reaction pressure/MPa | Benzoic acid conversion/% | Molar yield of benzylamine/% |
| 1 | 420 | 0.07 | 99.5 | 49.2 |
| 2 | 420 | 0.10 | 99.8 | 49.9 |
Example 10.
On the basis of example 7, the reaction temperature was set at 420 ℃ in place of the different supported catalyst active components. The results of the respective tests are shown in Table 3 to obtain the conversion of benzoic acid and the molar yield of benzylamine in the presence of different supported catalysts.
TABLE 3 Table 3
| Sequence number | Supported catalyst active component | Benzoic acid conversion/% | Molar yield of benzylamine/% |
| 1 | Ag-Ni-Pt-Mo-Ti-Ru1:0.30:0.09:0.15:0.10:0.25 | 99.7 | 50.0 |
| 2 | Ag-Ni-Pt-Au-Mo-Ru1:0.30:0.09:0.10:0.05:0.25 | 99.2 | 48.9 |
| 3 | Ag-Ni-Pt-Au-Co1:0.30:0.09:0.40:0.20 | 99.8 | 49.3 |
| 4 | Ag-Ni-Pt-Au-P-Rh-Ru-Mo1:0.30:0.09:0.40:0.40:0.15:0.25:0.05 | 99.9 | 51.7 |
| 5 | Ag-Ni-Pt-Au-P-Rh-Ru1:0.30:0.09:0.40:0.40:0.15:0.25 | 99.8 | 51.5 |
Example 11.
The active component is filled in the fluidized bed and consists of Ag-P-Ni-Pt-Rh according to the weight ratio of 1:0.40:0.30:0.09:0.15, and the carrier is a supported catalyst of TiO 2.
1, 3-Phthalic acid, ammonia and nitrogen are mixed in a mixer according to a molar ratio of 1:15:40, and are heated to 350 ℃ in the mixing process, so as to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 460℃and the reaction pressure at 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The product contains 1, 3-xylylenediamine, isophthalonitrile and a small amount of 3-cyanobenzamide, wherein the conversion rate of 1, 3-phthalic acid is 99.6%, and the molar yield of 1, 3-xylylenediamine reaches 44.5%.
Example 12.
On the basis of example 11, the reaction temperature was set at 420 ℃ in place of the different supported catalyst active components. The products were separately examined to obtain the conversion of 1, 3-phthalic acid and the molar yield of 1, 3-xylylenediamine in the presence of different supported catalysts as shown in Table 4.
TABLE 4 Table 4
| Sequence number | Supported catalyst active component | 1, 3-Phthalic acid conversion/% | Molar yield/%of 1, 3-xylylenediamine |
| 1 | Ag-Ni-Pt-Au-P-Rh1:0.30:0.09:0.10:0.40:0.15 | 99.4 | 45.3 |
| 2 | Ag-Ni-Pt-Mo-Ti-Ru1:0.30:0.09:0.15:0.10:0.25 | 99.2 | 44.8 |
Example 13.
The active component is filled in the fluidized bed and consists of Ag-P-Ni-Pt-Rh according to the weight ratio of 1:0.40:0.30:0.09:0.15, and the carrier is a supported catalyst of SiO 2.
1, 4-Phthalic acid, ammonia and nitrogen are mixed in a mixer according to a molar ratio of 1:20:40, and are heated to 350 ℃ in the mixing process, so as to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 440 ℃, the reaction pressure was 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The product was found to contain 1, 4-xylylenediamine, terephthalonitrile and a small amount of 4-cyanobenzamide, wherein the conversion of 1, 4-phthalic acid was 99.8%, and the molar yield of 1, 4-xylylenediamine was 42.3%.
Example 14.
On the basis of example 13, the reaction temperature was set at 420 ℃ in place of the different supported catalyst active components. The results of the respective measurements are shown in Table 5 to obtain the conversion of 1, 4-phthalic acid and the molar yield of 1, 4-xylylenediamine in the presence of the different supported catalysts.
TABLE 5
| Sequence number | Supported catalyst active component | 1, 4-Phthalic acid conversion/% | Molar yield/%of 1, 4-xylylenediamine |
| 1 | Ag-Ni-Pt-Au-P-Rh1:0.30:0.09:0.10:0.40:0.15 | 99.5 | 43.9 |
| 2 | Ag-Ni-Pt-Mo-Ti-Ru1:0.30:0.09:0.15:0.10:0.25 | 99.0 | 42.6 |
Example 15.
The active component is filled in the fluidized bed and consists of Ag-P-Ni-Pt-Rh-Mo according to the weight ratio of 1:0.40:0.30:0.09:0.15:0.05, and the carrier is a supported catalyst of Al 2O3.
2-Naphthoic acid, ammonia and nitrogen are mixed in a mixer according to a molar ratio of 1:20:40, and heated to 300 ℃ in the mixing process to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 480 ℃, the reaction pressure was 0.01MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains 2-naphthylmethylamine, 2-naphthylcarbonitrile and a small amount of 2-naphthylformamide, wherein the conversion rate of 2-naphthoic acid is 98.9%, and the molar yield of 2-naphthylmethylamine reaches 38.7%.
Example 16.
On the basis of example 15, the reaction temperature was set at 420℃and the reaction pressure was set at 0.08 MPa instead of the different supported catalyst active components. The products were separately examined to obtain the conversion of 2-naphthoic acid and the molar yield of 2-naphthylmethylamine in the presence of different supported catalysts as shown in Table 6.
TABLE 6
| Sequence number | Supported catalyst active component | Conversion of 2-naphthoic acid/% | Molar yield of 2-naphthylmethylamine/% |
| 1 | Ag-Ni-Pt-Au-P-Rh1:0.30:0.09:0.10:0.40:0.15 | 99.1 | 39.1 |
| 2 | Ag-Ni-Pt-Mo-Ti-Ru1:0.30:0.09:0.15:0.10:0.25 | 99.1 | 38.0 |
Example 17.
The active component is filled in the fluidized bed and consists of Ag-Ni-Pt-Au-P-Rh according to the weight ratio of 1:0.30:0.09:0.40:0.40:0.15, and the carrier is a supported catalyst of Al 2O3.
1, 8-Naphthalene dicarboxylic acid, ammonia gas and nitrogen gas are mixed in a mixer according to a molar ratio of 1:20:40, and are heated to 300 ℃ in the mixing process, so that mixed gas is obtained. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 420 ℃, the reaction pressure was 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains 1, 8-naphthalene dimethylamine, 1, 8-naphthalene dinitrile and a small amount of 1, 8-naphthalene dimethylamine, wherein the conversion rate of the 1, 8-naphthalene dicarboxylic acid is 99.4%, and the molar yield of the 1, 8-naphthalene dimethylamine reaches 32.8%.
Example 18.
Based on example 17, the different aromatic carboxylic acids were replaced, with the other conditions unchanged. The results of the respective measurements are shown in Table 7 for different aromatic carboxylic acid conversion and aromatic methylamine molar yields.
TABLE 7
| Sequence number | Aromatic carboxylic acid | Aromatic acid conversion/% | Aromatic methylamine molar yield/% |
| 1 | 1-Naphthoic acid | 99.0 | 37.6 |
| 2 | 1-Anthracene carboxylic acid | 98.9 | 34.6 |
| 3 | 2-Anthracene carboxylic acid | 98.3 | 34.2 |
| 4 | 1, 3-Naphthalenedicarboxylic acid | 99.2 | 31.3 |
Example 19.
Based on example 17, the alternative supported catalyst active component consisted of Ag-Ni-Pt-Au-P-Rh in a weight ratio of 1:0.30:0.09:0.10:0.40:0.15. Different aromatic carboxylic acids are replaced, different preheating temperatures are set, and other conditions are unchanged. The results of the respective tests are shown in Table 8 for different aromatic carboxylic acid conversion and aromatic methylamine molar yields.
TABLE 8
| Sequence number | Aromatic carboxylic acid | Preheating temperature/°c | Aromatic acid conversion/% | Aromatic methylamine molar yield/% |
| 1 | 1, 7-Naphthalenedicarboxylic acid | 300 | 99.1 | 30.8 |
| 2 | 2-Phenanthronic acid | 400 | 98.7 | 31.3 |
| 3 | Trimellitic acid | 350 | 98.2 | 25.4 |
Example 20.
The active component is filled in the fluidized bed and consists of Ag-Au-P-Ni-Pt-Rh according to the weight ratio of 1:0.10:0.40:0.30:0.09:0.15, and the carrier is a supported catalyst of Al 2O3.
1, 3-Phthalic acid, ammonia and hydrogen are mixed in a mixer according to the mol ratio of 1:20:40, and are heated to 350 ℃ in the mixing process, so as to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 420 ℃, the reaction pressure was 0.10MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The product contains 1, 3-xylylenediamine, isophthalonitrile and a small amount of 3-cyanobenzamide, wherein the conversion rate of 1, 3-phthalic acid is 99.8%, and the molar yield of 1, 3-xylylenediamine reaches 40.6%.
Example 21.
The active component is filled in the fluidized bed and consists of Ag-P-Ni-Pt-Rh according to the weight ratio of 1:0.10:0.30:0.09:0.15, and the carrier is a supported catalyst of Al 2O3.
1, 3-Phthalic acid, ammonia and argon are mixed in a mixer according to the mol ratio of 1:20:40, and are heated to 350 ℃ in the mixing process, so as to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 460℃and the reaction pressure at 0.08MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains 1, 3-xylylenediamine, isophthalonitrile, a small amount of 3-cyanobenzamide, benzonitrile and xylylenediamine, wherein the conversion rate of 1, 3-phthalic acid is 99.2%, and the molar yield of 1, 3-xylylenediamine reaches 45.7%.
Example 22.
The active component is filled in the fluidized bed and consists of Ag-Au-Mo-Ni-Pt-Ru according to the weight ratio of 1:0.10:0.05:0.30:0.09:0.25, and the carrier is a supported catalyst of Al 2O3.
9-Anthranilic acid, ammonia and nitrogen are mixed in a mixer according to a molar ratio of 1:30:40, and are heated to 350 ℃ in the mixing process, so as to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 480 ℃, the reaction pressure was 0.01MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The product contains 9-anthracenemethylamine, 9-anthracenecarbonitrile and a small amount of 9-anthracenecarboxamide, wherein the conversion rate of 9-anthracenecarboxylic acid is 99.1%, and the molar yield of 9-anthracenemethylamine reaches 33.9%.
Example 23.
The active component is filled in the fluidized bed and consists of Ag-Au-Mo-Ni-Pt-Ru according to the weight ratio of 1:0.10:0.05:0.30:0.09:0.25, and the carrier is a supported catalyst of Al 2O3.
3-Phenanthrene formic acid, ammonia and nitrogen are mixed in a mixer according to the mol ratio of 1:20:40, and are heated to 500 ℃ in the mixing process, so that mixed gas is obtained. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 500 ℃, the reaction pressure was 0.10MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains 3-phenanthrenemethylamine, 3-phenanthrenecarbonitrile and a small amount of 3-phenanthreneformamide, wherein the conversion rate of 3-phenanthrenecarboxylic acid is 99.3%, and the molar yield of 3-phenanthrenemethylamine reaches 32.6%.
Example 24.
The active component is filled in the fluidized bed and consists of Ag-Au-Mo-Ni-Pt-Ru according to the weight ratio of 1:0.10:0.05:0.30:0.09:0.25, and the carrier is a supported catalyst of Al 2O3.
Mixing 1,3, 5-benzene tricarboxylic acid, ammonia and nitrogen in a molar ratio of 1:30:40 in a mixer, and heating to 350 ℃ in the mixing process to obtain mixed gas. The mixed gas was introduced from the mixer into the fluidized bed, the reaction temperature was controlled at 460℃and the reaction pressure at 0.10MPa, and the residence time of the mixed gas in the fluidized bed was 30s. The product in the fluidized bed is collected in a trap to be detected.
The detection shows that the product contains 1,3, 5-benzene trimethylamine, benzonitrile and a small amount of benzamide, wherein the conversion rate of the 1,3, 5-benzene trimethylamine is 98.1%, and the molar yield of the 1,3, 5-benzene trimethylamine reaches 21.8%.
While various embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous modifications, changes, and substitutions will occur to those skilled in the art without departing from the spirit and scope of the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. The appended claims are intended to define the scope of the invention and are therefore to cover all equivalents or alternatives falling within the scope of these claims.
Claims (10)
1. A process for preparing aromatic methylamines comprising:
the method comprises the steps of firstly, mixing aromatic carboxylic acid, ammonia gas and carrier gas, and preheating to a gaseous state to obtain mixed gas;
and a second step, carrying out gas-solid phase catalytic reaction on the mixed gas at the reaction temperature of 380-560 ℃ and the reaction pressure of 0.05-0.25 MPa to obtain the aromatic methylamine.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
In the mixed gas, ammonia is excessive relative to aromatic carboxylic acid, and the ammonia accounts for 10-100% of the total volume of the ammonia and carrier gas.
3. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The aromatic carboxylic acid is selected from C (2+4n)H(2n+4-m)(COOH)m, wherein n is selected from 1,2 or 3;
When n=1, m=1, 2 or 3;
when n=2, m=1 or 2;
when n=3, m=1.
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The carrier gas is selected from at least one of nitrogen, carbon dioxide, helium, argon, hydrogen and ammonia.
5. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The carrier gas is at least one selected from hydrogen and ammonia.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The catalyst for the gas-solid phase catalytic reaction is a supported catalyst, wherein the active component of the supported catalyst is at least three elements selected from transition metal, alkali metal, alkaline earth metal and noble metal.
7. The method of claim 6, wherein the step of providing the first layer comprises,
The carrier of the supported catalyst is selected from any one of SiO 2、Al2O3、TiO2.
8. The method of claim 6, wherein the step of providing the first layer comprises,
The active component of the supported catalyst is selected from at least three elements of Au, P, ti, mo, ru, ni, pt, pd, rh, ag, co.
9. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
The active components of the supported catalyst at least comprise Au and Ag.
10. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
The active component of the supported catalyst comprises 1 part by weight of Ag, 0-0.5 part by weight of P, 0-0.3 part by weight of Ti, 0-0.3 part by weight of Mo, 0-0.4 part by weight of Ru, 0-0.5 part by weight of Ni, 0-0.2 part by weight of Pt, 0-0.3 part by weight of Pd, 0-0.3 part by weight of Rh, 0-0.5 part by weight of Au and 0-0.3 part by weight of Co.
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