CN108191671B - Method for preparing aliphatic amine by reducing aromatic amine compound - Google Patents
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Abstract
The invention provides a method for preparing aliphatic amine by reducing aromatic amine compound. The method takes aromatic amine compound as a reaction substrate, and the aromatic amine compound and a supported ruthenium catalyst and a deamination retarder are subjected to hydrogenation reaction in a solvent to prepare aliphatic amine compound; the deamination retarder is inorganic salt containing aluminum. The deamination retarder is added in the catalytic hydrogenation reduction process of the aromatic amine, so that the deamination side reaction of the target product is reduced, the yield of the target product is improved, and the production cost of the unit yield of the target product is reduced. Taking the preparation of PACM as an example, the yield of the target product PACM can reach more than 98%, and the preparation method has important application value in the industrial mass production.
Description
Technical Field
The invention belongs to the field of industrial chemical synthesis, and particularly relates to a method for preparing aliphatic amine by reducing aromatic amine compounds.
Background
Fatty amines are widely used in industrial and civil production and are also important raw materials for high molecular materials. The production of aliphatic amines by the hydrogenation reduction of aromatic amines is one of the methods for the production of aliphatic amines. In the preparation process, after the aromatic amine is subjected to hydrogenation reaction to produce the aliphatic amine, the aliphatic amine can continue to undergo deamination reaction to produce byproducts, so that the yield of the target product is reduced.
4,4' -diaminodicyclohexyl methane (PACM) is a very representative compound in aliphatic amine, contains two cyclohexyl groups in a molecule, belongs to a typical symmetric methane bridge type saturated aliphatic ring structure, is a very important intermediate in the polyurethane and polyamide industries, and can be used for preparing polyamide resin and aliphatic polyurethane. The PACM is usually prepared by using 4,4' -diaminodiphenylmethane (MDA) as a raw material, firstly generating intermediate hexahydro MDA under the action of a catalyst, and further hydrogenating. The generated PACM can generate deamination byproducts of 4-amino-dicyclohexylmethane and dicyclohexylmethane after continuous reaction, the deamination product of the PACM can be detected in the final product, and the content of the byproducts in the final product is particularly obvious in industrial production, so that the yield and the quality of the PACM are reduced, and the production cost of the PACM is increased.
Therefore, in the process of preparing the aliphatic amine by reducing the aromatic amine, the method is provided for avoiding the generated aliphatic amine from generating deamination side reaction so as to improve the yield of the target product and reduce the production cost, and has important application value.
Disclosure of Invention
The invention aims to provide a method for preparing aliphatic amine by reducing aromatic amine compound. The deamination retarder is added in the hydrogenation reduction process of the aromatic amine compound to reduce the occurrence of deamination side reaction of the generated target product, thereby improving the yield of the target product and reducing the production cost of the unit yield of the target product.
The above purpose of the invention is realized by the following technical scheme:
a method for preparing aliphatic amine by reducing aromatic amine compound, take aromatic amine compound as reaction substrate, carry on hydrogenation reaction with supported ruthenium catalyst and deamination retardant to get aliphatic amine compound; the deamination retarder is inorganic salt containing aluminum. The deamination retarder has the function of reducing the occurrence of deamination side reactions of target products.
The catalytic hydrogenation reaction of the present invention is carried out in a batch mode in a high pressure reactor.
Preferably, the aromatic amine compound has the structure shown in formula (I):
wherein R is1Is hydrogen or alkyl species with 1-4C atoms; r2Is hydrogen or an alkyl group having 1 to 4 carbon atoms.
More preferably, the aromatic amine compound has a structure represented by formula (IIa), formula (IIb) or formula (IIc):
wherein the formula (IIa) is 4,4 '-diaminodiphenylmethane (MDA) which is a raw material for preparing 4,4' -diaminodicyclohexylmethane (PACM); formula (IIb) is 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, which is the starting material for the preparation of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane (MACM); the compound of formula (IIc) is 3,3 '-diethyl-4, 4' -diaminodiphenylmethane, which is a starting material for the preparation of 3,3 '-diethyl-4, 4' -diaminodicyclohexylmethane.
Preferably, the mass ratio of the aromatic amine compound to the solvent, the supported ruthenium catalyst and the deamination retarder is 1: 0.5-10: 0.01-0.1: 0.005-0.1.
More preferably, the mass ratio of the aromatic amine compound to the solvent, the supported ruthenium catalyst and the deamination retarder in the method is 1: 1-8: 0.02-0.08: 0.01-0.05.
Preferably, the pressure of the hydrogenation reaction is 6-16 MPa, the temperature is 120-200 ℃, and the time is 2-10 h.
More preferably, the reaction pressure is 8-12 MPa, the reaction temperature is 140-180 ℃, and the reaction time is 3-8 h.
Preferably, the deamination retarder is one or more of potassium aluminum sulfate, ammonium aluminum sulfate, calcium sulfoaluminate, sodium metaaluminate, potassium metaaluminate and calcium aluminate; by adding the deamination retarder in the reaction process, the occurrence of deamination side reaction of the target product can be effectively reduced.
More preferably, the deamination retardant is aluminum potassium sulfate or aluminum ammonium sulfate.
Preferably, the carrier of the supported ruthenium catalyst is one or more of activated carbon, aluminum oxide, silicon dioxide, titanium dioxide, manganese dioxide, zinc chloride, zirconium oxide and molecular sieve. The supported ruthenium catalyst disclosed by the invention is directly used without activation, can be repeatedly used and still keeps higher catalytic activity, and the repeated use times are 30-36.
More preferably, the carrier of the supported ruthenium catalyst is activated carbon or alumina.
Preferably, the ruthenium in the supported ruthenium catalyst accounts for 1-10% of the mass of the carrier.
More preferably, the ruthenium in the supported ruthenium catalyst is 5% of the mass of the support.
Preferably, the solvent is one or more of cyclohexane, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexylamine, methanol, ethanol, isopropanol and n-butanol.
More preferably, the solvent is cyclohexane, dioxane, tetrahydrofuran, isopropanol.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the deamination retarder is added in the hydrogenation reduction process of the aromatic amine, so that the deamination side reaction of the target product can be obviously reduced or even inhibited, the content of the by-product in the final product is reduced, the yield and the content of the target product are improved, and the production cost of the unit yield of the target product is reduced. Taking the preparation of PACM as an example, the yield of the target product PACM can reach more than 98%, and the preparation method has important application value in actual large-batch industrial production.
Drawings
FIG. 1 is a total gas chromatogram of the product prepared in example 1. Wherein peaks at time points of 15.64 minutes and 15.73 minutes are two isomers of the by-product 4-amino-dicyclohexylmethane, respectively, and peaks at time points of 18.15 minutes, 18.24 minutes, and 18.31 minutes are three isomers of the target product PACM, respectively.
FIG. 2 is a total gas chromatogram of the product prepared in example 8. Among them, peaks at time points of 18.15 minutes, 18.24 minutes and 18.31 minutes were three isomers of the target product PACM, respectively, and the presence of the by-product was not detected.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. Unless otherwise indicated, the reagents and methods referred to in the examples are those commonly used in the art.
The method of the invention is adopted to carry out hydrogenation reduction reaction by using a formula (IIa), a formula (IIb) or a formula (IIc) as raw materials, and the reaction process and the result are shown in specific examples.
Example 1
Preparation of PACM from the formula (IIa)
An autoclave having a volume of 200L was charged with 15kg MDA and 45kg dioxane, followed by 450g of 5% Ru/Al2O3The catalyst and 300g of potassium metaaluminate are sealed, then the air in the autoclave is replaced by hydrogen, then 8MPa hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 10MPa, and the mixture is stirred vigorously for reaction for 4 hours. After cooling, sampling is carried out, and detection is carried out by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 98.8%, and the sum of the contents of by-products, namely 4-amino-dicyclohexyl methane and dicyclohexyl methane is 0.26%.
Example 2
Preparation of PACM from the formula (IIa)
5kg of MDA and 30kg of cyclohexane are added into an autoclave with the volume of 100L, then 450g of 5% Ru/C catalyst and 150g of aluminum potassium sulfate are added, the air in the autoclave is replaced by hydrogen after sealing, then 8MPa of hydrogen is introduced, the temperature of the autoclave is raised to 150 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 10MPa, and the autoclave is stirred vigorously for reaction for 4 hours. After cooling, sampling is carried out, and detection is carried out by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.0%, and the sum of the contents of by-products, namely 4-amino-dicyclohexyl methane and dicyclohexyl methane is 0.13%.
Example 3
Preparation of PACM from the formula (IIa)
20kg of MDA and 40kg of tetrahydrofuran are added into an autoclave with the volume of 100L, 2000 g of 5% Ru/C catalyst and 1000 g of aluminum ammonium sulfate are added, the autoclave is sealed and the air in the autoclave is replaced by hydrogen, then 8MPa of hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 10MPa, and the autoclave is stirred vigorously for reaction for 4 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.6%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 4
Preparation of PACM from the formula (IIa)
10kg of MDA and 30kg of cyclohexane were charged in an autoclave having a volume of 100LAlkane, then 300g of 5% Ru/Al are added2O3The catalyst and 300g of a mixture of aluminum potassium sulfate and sodium metaaluminate are sealed, the air in the autoclave is replaced by hydrogen, then 6MPa of hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 8MPa, and the mixture is stirred vigorously for reaction for 3.5 hours. After cooling, sampling is carried out, and detection is carried out by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 98.8%, and the sum of the contents of by-products 4-amino-dicyclohexylmethane and dicyclohexylmethane is 0.23%.
Example 5
Preparation of PACM from the formula (IIa)
10kg of MDA and 30kg of isopropanol are added into an autoclave with the volume of 100L, then 500 g of 5% Ru/C catalyst and 400 g of a mixture of aluminum ammonium sulfate and calcium aluminate are added, the autoclave is sealed, the air in the autoclave is replaced by hydrogen, then 10MPa of hydrogen is introduced, the autoclave is heated to 135 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 12MPa, and the autoclave is intensively stirred and reacts for 3.5 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.2%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 6
Preparation of PACM from the formula (IIa)
An autoclave having a volume of 200L was charged with 15kg MDA and 60kg tetrahydrofuran, followed by 450g of 5% Ru/Al2O3The catalyst and 450g of aluminum potassium sulfate are sealed, then the air in the autoclave is replaced by hydrogen, then 8MPa hydrogen is introduced, the autoclave is heated to 140 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 10MPa, and the mixture is stirred vigorously for reaction for 4 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.6%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 7
Preparation of PACM from the formula (IIa)
10kg of MDA and 50kg of cyclohexylamine are added into an autoclave with the volume of 200L, then 500 g of 5% Ru/C catalyst and 300g of aluminum ammonium sulfate are added, the autoclave is sealed and the air in the autoclave is replaced by hydrogen, then 8MPa of hydrogen is introduced, the autoclave is heated to 140 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 10MPa, and the autoclave is stirred vigorously for reaction for 4 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.3%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 8
Preparation of PACM from the formula (IIa)
600Kg of MDA and 1200Kg of tetrahydrofuran are added into a 3000L high pressure autoclave, then 60Kg of 5% Ru/C catalyst and 30Kg of aluminum ammonium sulfate are added, the air in the high pressure autoclave is replaced by hydrogen after sealing, then 8MPa of hydrogen is introduced, the high pressure autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the high pressure autoclave at 10MPa, and the high pressure autoclave is stirred vigorously for reaction for 4 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.5%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 9
Preparation of PACM from the formula (IIa)
2000Kg MDA and 2000Kg tetrahydrofuran were charged into an autoclave having a volume of 6000L, and then 100Kg of 5% Ru/Al was charged2O3The catalyst and 100Kg of ammonium aluminum sulfate are sealed, then the air in the autoclave is replaced by hydrogen, then 6MPa of hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 8MPa, and the mixture is stirred vigorously for reaction for 4 hours. And (3) cooling, sampling, and detecting by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of MDA is 100%, the yield of PACM is 99.6%, and byproducts 4-amino-dicyclohexylmethane and dicyclohexylmethane are not detected.
Example 10
Preparation of MACM starting from formula (IIb)
2000kg of 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane and 2000kg of tetrahydrofuran were charged in an autoclave having a volume of 6000L,then 100Kg of 5% Ru/Al was added2O3The catalyst and 100Kg of ammonium aluminum sulfate are sealed, then the air in the autoclave is replaced by hydrogen, then 6MPa of hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 8MPa, and the mixture is stirred vigorously for reaction for 4 hours. After cooling, sampling is carried out, and detection is carried out by a gas chromatography-mass spectrometer, wherein the detection result is that the conversion rate of the 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane is 100 percent, and the MACM yield is 99.4 percent.
Example 11
Preparation of 3,3 '-diethyl-4, 4' -diaminodicyclohexylmethane from the formula (IIc)
2000Kg of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane and 2000Kg of tetrahydrofuran were charged in an autoclave having a volume of 6000L, and then 100Kg of 5% Ru/Al was charged2O3The catalyst and 100Kg of ammonium aluminum sulfate are sealed, then the air in the autoclave is replaced by hydrogen, then 6MPa of hydrogen is introduced, the autoclave is heated to 160 ℃, a hydrogen valve is adjusted to maintain the pressure in the autoclave at 8MPa, and the mixture is stirred vigorously for reaction for 4 hours. After cooling, sampling was performed, and the conversion of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane was 100% and the yield of 3,3 '-diethyl-4, 4' -diaminodicyclohexylmethane was 99.2% as detected by a gas chromatography-mass spectrometer.
Comparative example 1
Preparation of PACM from the formula (IIa)
This comparative example is the same as the preparation of example 3, except that no deamination retarder aluminum ammonium sulfate was added, and the results were 99% conversion of MDA, 91.8% yield of PACM, and 5.1% sum of contents of by-product 4-amino-dicyclohexylmethane and dicyclohexylmethane.
Comparative example 2
Preparation of PACM from the formula (IIa)
This comparative example was the same as example 4 except that aluminum sulfate A as a deamination retarder was not added, and the results of the test showed that the conversion of MDA was 100%, the yield of PACM was 91.5%, and the sum of the contents of by-product 4-amino-dicyclohexylmethane and dicyclohexylmethane was 5.3%.
Comparative example 3
Preparation of MACM starting from formula (IIb)
This comparative example was the same as example 10 except that no deamination retarder aluminum ammonium sulfate was added and the conversion of 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane was 100% and the MACM yield was 91.4%.
Comparative example 4
Preparation of 3,3 '-diethyl-4, 4' -diaminodicyclohexylmethane from the formula (IIc)
This comparative example was the same as example 11 except that aluminum ammonium sulfate, which is a deamination retarder, was not added, and the conversion of 3,3 '-diethyl-4, 4' -diaminodiphenylmethane was 100%, and the yield of 3,3 '-diethyl-4, 4' -diaminodicyclohexylmethane was 90.4%.
The yield results of the target products and by-products in examples 1 to 11 and comparative examples 1 to 4 are shown in Table 1. Examples 1 to 7 are pilot experiments, and examples 8 to 11 are main production processes.
TABLE 1 yield results for target products and byproducts in examples 1-11 and comparative examples 1-4
| Serial number | Conversion ratio of raw material% | Yield of the target product% | Content of by-products% |
| Example 1 | 100 | 98.8 | 0.26 |
| Example 2 | 100 | 99.0 | 0.13 |
| Example 3 | 100 | 99.6 | 0 |
| Example 4 | 100 | 98.8 | 0.23 |
| Example 5 | 100 | 99.2 | 0 |
| Example 6 | 100 | 99.6 | 0 |
| Example 7 | 100 | 99.3 | 0 |
| Example 8 | 100 | 99.5 | 0 |
| Example 9 | 100 | 99.6 | 0 |
| Example 10 | 100 | 99.4 | - |
| Example 11 | 100 | 99.2 | - |
| Comparative example 1 | 99 | 91.8 | 5.1 |
| Comparative example 2 | 100 | 91.5 | 5.3 |
| Comparative example 3 | 100 | 91.4 | - |
| Comparative example 4 | 100 | 90.4 | - |
As can be seen from table 1, the yields of the objective products were all improved to some extent by the preparation method of the present invention, wherein the yields of PACM prepared in examples 3, 6, and 9 were the highest up to 99.6%, which was improved by at least 7.8% compared to the comparative example, and no by-product was detected; in all examples, the minimum yield of PACM was 98.8%, which is at least a 7% increase over the comparative example; the content of the by-products is up to 0.26%, which is reduced by 4.84% compared with the comparative example, and the by-products are not detected in 6 examples in 9 examples using the formula (a) as the raw material, so that the deamination retarder can obviously reduce or even inhibit the target product from generating deamination side reaction. In examples 10 and 11 and comparative examples 3 and 4, the aliphatic amine is prepared by using the formula (b) or the formula (c) as a raw material, and a standard sample of a side reaction product of the reaction cannot be obtained, so that the content of a by-product cannot be detected, but the yield of a target product is obviously increased, and the addition of a deamination retarder is helpful for improving the yield of the target product of the aliphatic amine.
In summary, it can be seen from the results of the above examples and comparative examples that the addition of deamination retarder in the process of preparing aliphatic amine by hydrogenation reduction of aromatic amine can significantly improve the yield of the target product, reduce or even completely inhibit the occurrence of deamination side reaction of the target product, reduce the content of by-products in the final product, improve the yield of the target product, and reduce the production cost per unit yield.
Claims (8)
1. A method for preparing aliphatic amine by reducing aromatic amine compound is characterized in that aromatic amine compound is used as reaction substrate, and hydrogenation reaction is carried out on the aromatic amine compound, a supported ruthenium catalyst and a deamination retarder in a solvent to prepare aliphatic amine compound; the deamination retarder is one or more of potassium aluminum sulfate, ammonium aluminum sulfate, calcium sulphoaluminate, sodium metaaluminate, potassium metaaluminate and calcium aluminate;
the aromatic amine compound has a general formula shown in formula (I):
wherein R is1One or more of hydrogen or C1-4 alkyl; r2Is one or more of hydrogen or alkyl with 1-4C atoms.
2. According to claim 1The method is characterized in that the aromatic amine compound has a structure shown as a formula (IIa), a formula (IIb) or a formula (IIc):
3. the method according to claim 1, wherein the aromatic amine compound is mixed with the solvent, the supported ruthenium catalyst and the deamination retarder at a mass ratio of 1: 0.5-10: 0.01-0.1: 0.005-0.1.
4. The method according to claim 1, wherein the pressure of the hydrogenation reaction is 6-16 MPa, the temperature is 120-200 ℃, and the time is 2-10 h.
5. The method of claim 1, wherein the deamination retardant is aluminum potassium sulfate or aluminum ammonium sulfate.
6. The method of claim 1, wherein the carrier of the supported ruthenium catalyst is one or more of activated carbon, alumina, silica, titania, manganese dioxide, zinc chloride, zirconia, and molecular sieves.
7. The method according to claim 3, wherein the aromatic amine compound is mixed with the solvent, the supported ruthenium catalyst and the deamination retarder at a mass ratio of 1: 1 to 8: 0.02 to 0.08: 0.01 to 0.05.
8. The method according to claim 4, wherein the reaction pressure in the method is 8-12 MPa, the reaction temperature is 140-180 ℃, and the reaction time is 3-8 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6075167A (en) * | 1997-10-07 | 2000-06-13 | Korea Institute Of Science And Technology | Method for preparing cycloaliphatic diamines from aromatic diamines |
| CN101910108A (en) * | 2008-01-18 | 2010-12-08 | 巴斯夫欧洲公司 | Method for the production of cycloaliphatic amines |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6075167A (en) * | 1997-10-07 | 2000-06-13 | Korea Institute Of Science And Technology | Method for preparing cycloaliphatic diamines from aromatic diamines |
| CN101910108A (en) * | 2008-01-18 | 2010-12-08 | 巴斯夫欧洲公司 | Method for the production of cycloaliphatic amines |
Non-Patent Citations (1)
| Title |
|---|
| Ru-catalyzed hydrogenation of aromatic diamines: The effect of alkali metal salts;Kim H S，etc.;《Journal of Molecular Catalysis A: Chemical》;19981231;第132卷(第2-3期);第271页表4第2行、表格下方备注、第267页摘要 * |
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