CN107857704B - Method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine and catalyst used in method - Google Patents
Method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine and catalyst used in method Download PDFInfo
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- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
Abstract
The invention discloses a method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine and a catalyst used in the method. The method comprises two steps of reaction, a) 3-cyano-3, 5, 5-trimethylcyclohexanone is reacted in the presence of hydrogenation catalyst in hydrogen atmosphere to generate 3-aminomethyl-3, 5, 5-trimethylcyclohexanol; b) 3-aminomethyl-3, 5, 5-trimethylcyclohexanol reacts with liquid ammonia in the presence of a hydroamination catalyst to produce 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine. The method breaks through the limitation of imidization yield of the traditional method and can prepare the 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine with high yield.
Description
Technical Field
The invention relates to a preparation method of aliphatic amine, in particular to a method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexanol by hydrogenating 3-cyano-3, 5, 5-trimethylcyclohexanone and then preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine by hydroamination and a catalyst used in the method.
Background
3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (also called isophorone diamine, abbreviated as IPDA) is a raw material for preparing 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (also called isophorone diisocyanate, abbreviated as IPDI), polyamide and the like, and can also be used as a curing agent of epoxy resin.
At present, in industrial scale, the mainstream preparation method of IPDA is to react 3-cyano-3, 5, 5-trimethylcyclohexanone (also called isophorone nitrile, abbreviated as IPN) with liquid ammonia to form 3-cyano-3, 5, 5-trimethylcyclohexylimine (also called isophorone nitrile imine, abbreviated as IPNI), and then the IPNI is subjected to reductive amination reaction with hydrogen in the presence of liquid ammonia in a catalytic manner. The reaction process is as follows:
in the Chinese patent publication CN101386579, IPDA is prepared by one-step method in which IPN, liquid ammonia, solvent, catalyst and cocatalyst are reacted in a reactor at 50-120 ℃ and 5-15MPa hydrogen pressure. This process inevitably leads to a large amount of amino alcohol (a) being formed, which leads to a limited yield of IPDA.
According to DE10142635, in the preparation of IPDA in a three-step process (one imidization step and two hydrogenation steps), the imidization step is carried out by reacting IPN with excess liquid ammonia at 20-150 ℃ and 50-300 bar pressure to form 3-cyano-3, 5, 5-trimethylcyclohexanone imine (IPNI), optionally over an acidic metal oxide catalyst. Although this method increases the yield of IPDA by increasing the imidization yield, the imidization is a reversible reaction, and a part of IPN is not reacted all the time, so that the amount of amino alcohol produced is still large.
The imidization reaction is a reversible exothermic reaction, and the imidization equilibrium yield can be changed by adjusting parameters such as reaction temperature, raw material proportion and the like. The imidization equilibrium yield can be improved within a certain range by means of reducing the reaction temperature and increasing the molar ratio of liquid ammonia to IPN, but the reduction of the reaction temperature can sacrifice the reaction rate, increase the size of the reactor and further increase the equipment investment, and the increase of the molar ratio of liquid ammonia to IPN can increase the energy consumption for separation and further increase the operation cost. It is difficult to achieve imidization equilibrium yields above 95 wt% for economic feasibility, which means that nearly 5 wt% IPN enters the hydrogenation reactor. Of course, the IPN entering the hydrogenation reactor will be further converted to imine with a reduction in imine, but still 1 wt% or more of the IPN will not achieve conversion to imine to amino alcohol directly.
In summary, because the nature of imidization determines that the conventional preparation process of IPDA cannot overcome the generation of amino alcohol, resulting in the limitation of IPDA yield, a new preparation process of IPDA is required to overcome the technical defects.
Disclosure of Invention
The invention aims to provide a method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (IPDA), which can break through the limitation of imidization yield of the traditional method and prepare the 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine with low amino alcohol and high IPDA yield.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a process for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (IPDA), the process comprising the steps of:
a) 3-cyano-3, 5, 5-trimethylcyclohexanone (IPN for short) is used for generating 3-aminomethyl-3, 5, 5-trimethylcyclohexanol (IPAA for short) in the presence of a hydrogenation catalyst under a hydrogen atmosphere;
b) 3-aminomethyl-3, 5, 5-trimethylcyclohexanol (IPAA) reacts with liquid ammonia in the presence of a hydroamination catalyst to produce 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (IPDA).
The reaction scheme is as follows:
the method of the invention firstly contacts the IPN as the raw material with the hydrogenation catalyst for hydrogenation to generate IPAA, and then carries out ammonolysis on the IPAA under the catalysis of the hydroamination catalyst to generate IPDA.
Preferably, the step a) is carried out at the temperature of 30-150 ℃ and the pressure of 5-30 MPa, preferably at the temperature of 80-120 ℃ and the pressure of 5-15MPa, and particularly, the temperature rise of the reaction liquid is ensured to be 20-30 ℃, namely, the outlet temperature of the hydrogenation reactor is 20-30 ℃ higher than the inlet temperature.
Preferably, step b) is carried out at a temperature of 100 to 260 ℃ and a pressure of 2 to 25MPa, preferably at a temperature of 140 to 200 ℃ and a pressure of 5 to 15 MPa.
Preferably, the molar ratio of the hydrogen to the IPN in the step a) is 3: 1 to 1000: 1, preferably 10: 1 to 500: 1, and particularly preferably 20: 1 to 100: 1.
Preferably, the molar ratio of the hydrogen to the IPAA in the step b) is 3: 1-1000: 1, preferably 10: 1-500: 1, and particularly preferably 20: 1-100: 1.
Preferably, according to the method of the present invention, the molar ratio of the liquid ammonia to the IPAA in step b) is 1:1 to 100: 1, preferably 10: 1 to 30: 1.
Preferably, the catalyst used in step a) may be of the supported or raney type, and may be a noble or non-noble metal catalyst, for example: copper, nickel, cobalt, Raney copper, Raney nickel, Raney cobalt or palladium, platinum, ruthenium, rhodium, iridium or noble metal chloride or nitrate, wherein the carrier of the supported catalyst can be any common catalyst carrier.
Preferably, the catalyst used in step a) is preferably Raney nickel, Raney cobalt, ruthenium/carbon, palladium/alumina, particularly preferably Raney nickel catalyst.
Preferably, the catalyst used in step b) comprises an active component, an auxiliary agent and a carrier, wherein the active component is nickel, cobalt, copper and ruthenium, the auxiliary agent is one or more of palladium, chromium, manganese, iron, molybdenum, zinc, vanadium, bismuth, iridium, lanthanum and cerium, preferably one or more of palladium, chromium, manganese, molybdenum and zinc, and the carrier is preferably any one of activated carbon, alumina, zirconia, titania and magnesia, preferably alumina.
The content of active components in the catalyst used in the step b) is as follows based on the total weight of the catalyst:
the content of nickel element is 5 wt% -30 wt%, preferably 7 wt% -25 wt%, particularly preferably 10 wt% -20 wt%;
the content of the cobalt element is 2 to 15 wt%, preferably 5 to 12 wt%, and particularly preferably 7 to 11 wt%;
the content of the copper element is 0.2 to 3 wt%, preferably 0.5 to 2 wt%, and particularly preferably 0.8 to 1.5 wt%;
the content of the ruthenium element is 5 to 25 wt%, preferably 7 to 20 wt%, and particularly preferably 8 to 15 wt%.
The auxiliary agent in the catalyst used in the step b) comprises one or more of the following components based on the total weight of the catalyst:
the content of palladium element is 0 wt% -0.5 wt%, preferably 0.1 wt% -0.3 wt%;
the content of the chromium element is 0 to 0.8 weight percent, preferably 0.1 to 0.6 weight percent;
the content of manganese element is 0 wt% -0.2 wt%, preferably 0.1 wt% -0.15 wt%;
the content of the molybdenum element is 0 to 0.4 weight percent, and preferably 0.1 to 0.2 weight percent;
the content of zinc element is 0 wt% -0.5 wt%, preferably 0.1 wt% -0.4 wt%.
The balance being the carrier.
According to the method of the invention, the space velocity of the raw material in the step a) is 0.04-1 g IPN/(g catalyst h), and preferably 0.1-0.3 g IPN/(g catalyst h).
According to the method, the space velocity of the raw material in the step b) is 0.1-10 g of IPAA/(g of catalyst.h), and preferably 0.6-3 g of IPAA/(g of catalyst.h).
According to the process of the invention, steps a) and b) may be carried out in the presence of a solvent, for example in a C3-C15 alkane or a C3-C10 ester, for example butane, cyclohexane, heptane, ethyl acetate, butyl propionate. Preferably without the addition of a solvent.
According to the process of the invention, steps a) and b) can be carried out in fixed-bed reactors, fluidized-bed reactors, moving-bed reactors, preferably in fixed-bed reactors, particularly preferably in trickle-bed reactors with parallel gas-liquid downflow.
The invention also aims to provide a hydroammonation catalyst for generating 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine by reacting 3-aminomethyl-3, 5, 5-trimethylcyclohexanol (IPAA for short) with liquid ammonia, which comprises an active component, an auxiliary agent and a carrier, wherein the active component is nickel, cobalt, copper and ruthenium, the auxiliary agent is one or more of palladium, chromium, manganese, iron, molybdenum, zinc, vanadium, bismuth, iridium, lanthanum and cerium, and preferably one or more of palladium, chromium, manganese, molybdenum and zinc.
Based on the total weight of the catalyst, the content of active components in the hydroammonation catalyst is as follows:
the content of nickel element is 5 wt% -30 wt%, preferably 7 wt% -25 wt%, particularly preferably 10 wt% -20 wt%;
the content of the cobalt element is 2 to 15 wt%, preferably 5 to 12 wt%, and particularly preferably 7 to 11 wt%;
the content of the copper element is 0.2 to 3 wt%, preferably 0.5 to 2 wt%, and particularly preferably 0.8 to 1.5 wt%;
the content of the ruthenium element is 5 wt% to 25 wt%, preferably 7 wt% to 20 wt%, and particularly preferably 8 wt% to 15 wt%;
the auxiliary agent in the hydroamination catalyst comprises one or more of the following components in percentage by weight of the total weight of the catalyst:
the content of palladium element is 0 wt% -0.5 wt%, preferably 0.1 wt% -0.3 wt%;
the content of the chromium element is 0 to 0.8 weight percent, preferably 0.1 to 0.6 weight percent;
the content of manganese element is 0 wt% -0.2 wt%, preferably 0.1 wt% -0.15 wt%;
the content of the molybdenum element is 0 to 0.4 weight percent, and preferably 0.1 to 0.2 weight percent;
the content of zinc element is 0 wt% -0.5 wt%, preferably 0.1 wt% -0.4 wt%.
The balance being the carrier. The carrier is preferably any one of activated carbon, alumina, zirconia, titania and magnesia, and is preferably alumina.
The hydroamination catalyst can be prepared by the following steps:
1) impregnating a support with an aqueous solution (concentration may be 1 to 40 wt%) of a metal salt and/or a molten metal salt of a metal to obtain a catalyst precursor, wherein the metal salt includes a halide, nitrate or organic acid salt of nickel, cobalt, copper, ruthenium, or the like and one or more selected from a halide, nitrate or organic acid salt of a metal such as palladium, chromium, manganese, molybdenum, zinc, or the like, preferably a nitrate, formate or oxalate of the metal, particularly preferably a nitrate of the metal;
2) drying the catalyst precursor obtained in the step 1) at the temperature of 100-150 ℃ for 2-48 hours, and roasting at the temperature of 350-600 ℃ for 1-24 hours, preferably drying at the temperature of 120 ℃ for 24 hours and roasting at the temperature of 400 ℃ for 8 hours to obtain the catalyst;
3) the catalyst is preferably reduced under a hydrogen atmosphere before use, under such conditions as: and (3) at 200 ℃ for 24h, wherein the reducing gas is a hydrogen-nitrogen mixed gas with the volume ratio of 1:1, the flow rate is 5-100 standard liters/(kg catalyst. h), and the catalyst is preferably reduced in situ in the reactor.
For many years, the research on the reaction of IPN to IPDA has been around the traditional process route, i.e. IPNI is prepared by imidizing IPN, and IPDA is prepared by hydrogenating IPNI. However, the imidization step is a reversible reaction, and the conversion rate of IPN is limited, so that the content of IPAA in the hydrogenated product is high, and the yield of IPDA is limited.
In order to overcome the defects of the traditional process route, the inventor adopts a brand new process route to prepare IPDA, namely IPN generates IPAA in the presence of a hydrogenation catalyst in a hydrogen atmosphere, and then the IPAA reacts with liquid ammonia in the presence of a hydroamination catalyst to generate IPDA. The method breaks through the limitation of imidization yield of the traditional method, can prepare the 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine with high yield, and has the IPAA content in the final reaction liquid lower than 0.2 wt% and the IPDA yield higher than 98.5 wt%.
The pressures referred to in the present invention are gauge pressures.
Drawings
FIG. 1 is a schematic flow diagram of one embodiment of the process of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
The quantitative analysis of each organic matter involved in the invention is carried out on an Agilent 7890B type gas chromatography, and the analysis conditions of the gas chromatography are as follows:
a chromatographic column: agilent HP-5 capillary chromatographic column (specification of 30m × 0.32mm × 0.25 μm)
Sample inlet temperature: 280 deg.C
The split ratio is as follows: 30: 1
Column flow rate: 1.5ml/min
Column temperature: 0.5min at 100 DEG C
Increasing the temperature to 260 ℃ at 15 ℃/min and keeping the temperature for 8min
Detector temperature: 280 ℃, hydrogen flow rate: 35ml/min
Air flow rate: 350ml/min
In the following examples, the hydrogenation catalyst used in step a) was a Raney nickel catalyst, available from Graies catalysts, USA under the trade name Raney 5886.
In the following examples, the hydroamination catalyst used in step b) is a self-made catalyst.
As shown in fig. 1, the process flow of the present invention is: IPN liquid enters an IPN hydrogenation trickle bed reactor which flows downwards and is in gas-liquid flow through a high-pressure pump to generate IPAA through hydrogenation reaction with hydrogen, IPAA and liquid ammonia are mixed and then enter the IPN hydrogenation trickle bed reactor which flows downwards and is in gas-liquid flow to generate IPDA through ammonolysis reaction, IPDA reaction liquid is subjected to gas-liquid separation, hydrogen is recycled, liquid phase is subjected to a deamination system, removed ammonia returns to the hydroammonia reactor for recycling, and deamination reaction liquid enters a refining process to be refined to obtain a product.
The invention is further illustrated by the following specific examples. The amounts stated in the examples are all wt.%.
Preparation of a hydroamination catalyst:
example 1:
30kg of activated alumina sphere-type carrier with a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 20kg of nickel, 22kg of cobalt, 3kg of copper, 16kg of ruthenium, 1.2kg of chromium, 0.3kg of manganese and 0.8kg of zinc, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to obtain 37.5kg of catalyst 1 containing 6.3% of nickel, 7.0% of cobalt, 0.9% of copper, 5.1% of ruthenium, 0.4% of chromium, 0.1% of manganese, and 0.3% of zinc.
Example 2:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 40kg of nickel, 14kg of cobalt, 1.6kg of copper, 24kg of ruthenium, 0.6kg of palladium and 0.4kg of molybdenum, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to obtain 39.0kg of catalyst 2 containing 11.5% of nickel, 4.0% of cobalt, 0.5% of copper, 6.9% of ruthenium, 0.2% of palladium, and 0.1% of molybdenum.
Example 3:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 24kg of nickel, 16kg of cobalt, 2.4kg of copper, 30kg of ruthenium, 0.4kg of palladium, 0.6kg of chromium, 0.2kg of manganese, 0.2kg of molybdenum and 0.4kg of zinc, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and then cooled to obtain 42.0kg of catalyst 3 containing 9.2% of nickel, 6.2% of cobalt, 0.9% of copper, 11.6% of ruthenium, 0.2% of palladium, 0.3% of chromium, 0.1% of manganese, 0.1% of molybdenum, and 0.2% of zinc.
Example 4:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 32kg of nickel, 18kg of cobalt, 2kg of copper, 20kg of ruthenium, 0.2kg of palladium, 0.2kg of chromium and 0.2kg of zinc, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and then cooled to obtain 37.5kg of catalyst 4 containing 8.8% of nickel, 5.0% of cobalt, 0.6% of copper, 5.5% of ruthenium, 0.1% of palladium, 0.1% of chromium, and 0.1% of zinc.
Example 5:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, and then poured into a nitrate-impregnated solution containing 40kg of nickel, 20kg of cobalt, 2kg of copper, 16kg of ruthenium and 0.6kg of palladium, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and then cooled to obtain 36.0kg of catalyst 5 containing 8.4% of nickel, 4.2% of cobalt, 0.4% of copper, 3.4% of ruthenium, and 0.1% of palladium.
Example 6:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 36kg of nickel, 20kg of cobalt, 1.6kg of copper, 18kg of ruthenium and 1.2kg of chromium, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to give 39.0kg of catalyst 6 containing 10.8% nickel, 6.0% cobalt, 0.5% copper, 5.4% ruthenium, and 0.4% chromium.
Example 7:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 24kg of nickel, 16kg of cobalt, 2.4kg of copper, 30kg of ruthenium and 0.3kg of manganese, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to obtain 40.0kg of catalyst 7 containing 8.3% of nickel, 4.7% of cobalt, 0.8% of copper, 8.8% of ruthenium, and 0.1% of manganese.
Example 8:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, poured into a nitrate-impregnated solution containing 28kg of nickel, 22kg of cobalt, 2kg of copper, 26kg of ruthenium and 0.4kg of molybdenum, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to obtain 38.5kg of catalyst 8 containing 7.9% nickel, 6.2% cobalt, 0.6% copper, 7.3% ruthenium, and 0.1% molybdenum.
Example 9:
30kg of an activated alumina sphere-type carrier having a diameter of 3mm was dried at 120 ℃ for 12 hours, and then poured into a nitrate-impregnated solution containing 36kg of nickel, 14kg of cobalt, 1.6kg of copper, 22kg of ruthenium and 0.8kg of zinc, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 24 hours, calcined at 400 ℃ for 8 hours, and cooled to obtain 41.8kg of catalyst 9 containing 13.7% of nickel, 5.3% of cobalt, 0.6% of copper, 8.3% of ruthenium, and 0.3% of zinc.
IPN hydrogenation and IPAA ammonolysis reaction:
example 10:
180kg Graies Raney5886 catalyst is filled in an IPN hydrogenation reactor, 30kg of self-made catalyst 1 is filled in an IPAA hydroamination reactor, the catalyst 1 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of the activated gas is 1500 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to be below 100 ℃ after the activation is finished. Pressurizing the reaction system to 12MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 80 ℃, preheating an IPAA hydroamination reactor to 140 ℃, feeding amount of the IPN to 18kg/h and hydrogen to 7.33Nm3The outlet temperature of the IPN hydrogenation reactor is 110 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 55.6kg/h, the pressure of the reaction system is maintained at 15MPa, and the circulating hydrogen of the reaction system is 245Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.8％ | 0.08％ |
| IPDA content | 2.5％ | 99.2％ |
Example 11:
180kg Graies Raney5886 catalyst is filled in the IPN hydrogenation reactor, 27kg self-made catalyst 2 is filled in the IPAA hydroamination reactor, the catalyst 2 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of activated gas is 1350 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to be below 100 ℃ after the activation is finished. Pressurizing the reaction system to 8MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 90 ℃, preheating an IPAA hydroamination reactor to 160 ℃, feeding amount of the IPN to 27kg/h and hydrogen to 11Nm3The outlet temperature of the IPN hydrogenation reactor is 115 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 55.6kg/h, the pressure of the reaction system is maintained at 10MPa, and the circulating hydrogen of the reaction system is 256Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.3％ | 0.12％ |
| IPDA content | 1.8％ | 98.6％ |
Example 12:
180kg Graies Raney5886 catalyst is filled in the IPN hydrogenation reactor, 25.7kg self-made catalyst 3 is filled in the IPAA hydroamination reactor, the catalyst 3 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the activated gas flow rate is 1300 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 4MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 100 ℃, preheating an IPAA hydroamination reactor to 180 ℃, feeding amount of the IPN to 36kg/h and hydrogen to 14.7Nm3The outlet temperature of the IPN hydrogenation reactor is 120 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 37kg/h, the pressure of the reaction system is maintained at 5MPa, and the circulating hydrogen of the reaction system is 200Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.5％ | 0.1％ |
| IPDA content | 3.2％ | 98.8％ |
Example 13:
180kg Graies Raney5886 catalyst is filled in an IPN hydrogenation reactor, 22.5kg self-made catalyst 4 is filled in an IPAA hydroamination reactor, the catalyst 4 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of activated gas is 1150 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 4MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 100 ℃, preheating an IPAA hydroamination reactor to 200 ℃, feeding amount of the IPN is 45kg/h, and hydrogen is 18.33Nm3The outlet temperature of the IPN hydrogenation reactor is 120 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 46.3kg/h, the pressure of a reaction system is maintained at 5MPa, and the circulating hydrogen of the reaction system is 122Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.9％ | 0.23％ |
| IPDA content | 1.9％ | 98.5％ |
Example 14:
180kg Graies Raney5886 catalyst is filled in the IPN hydrogenation reactor, 21.7kg self-made catalyst 5 is filled in the IPAA hydroamination reactor, the catalyst 5 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the activated gas flow is 1100 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 8MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 90 ℃, preheating an IPAA hydroamination reactor to 200 ℃, feeding amount of the IPN to 54kg/h and 22Nm of hydrogen3The outlet temperature of the IPN hydrogenation reactor is 115 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 111kg/h, the pressure of a reaction system is maintained at 10MPa,circulating hydrogen 3675Nm in reaction system3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.8％ | 0.09％ |
| IPDA content | 2.1％ | 99.1％ |
Example 15:
180kg Graies Raney5886 catalyst is filled in the IPN hydrogenation reactor, 6kg self-made catalyst 6 is filled in the IPAA hydroamination reactor, the catalyst 6 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of activated gas is 600 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 12MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 80 ℃, and hydrogenating IPAAThe ammoniation reactor is preheated to 180 ℃, the IPN feeding amount is 18kg/h, and the hydrogen is 7.33Nm3The outlet temperature of the IPN hydrogenation reactor is 110 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 55.6kg/h, the pressure of the reaction system is maintained at 15MPa, and the circulating hydrogen of the reaction system is 245Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.8％ | 0.38％ |
| IPDA content | 0.91％ | 98.5％ |
Example 16:
180kg Graies Raney5886 catalyst is filled in the IPN hydrogenation reactor, 13.5kg self-made catalyst 7 is filled in the IPAA hydroamination reactor, the catalyst 7 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, and the flow rate of the activated gas is 1350 standard liter/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to be below 100 ℃ after the activation. Pressurizing the reaction system to 8MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 100 ℃, preheating an IPAA hydroamination reactor to 160 ℃, feeding amount of the IPN to 27kg/h and hydrogen to 11Nm3The outlet temperature of the IPN hydrogenation reactor is 120 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 83.4kg/h, the pressure of the reaction system is maintained at 10MPa, and the circulating hydrogen of the reaction system is 256Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.6％ | 0.14％ |
| IPDA content | 2.2％ | 98.9％ |
Example 17:
IPN hydrogenation180kg Graies Raney5886 catalyst is filled in the reactor, 25.7kg self-made catalyst 8 is filled in the IPAA hydroamination reactor, the catalyst 8 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of the activated gas is 1300 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 10MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 90 ℃, preheating an IPAA hydroamination reactor to 140 ℃, feeding amount of the IPN to 36kg/h and hydrogen to 14.7Nm3The outlet temperature of the IPN hydrogenation reactor is 115 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 74kg/h, the pressure of a reaction system is maintained at 12MPa, and the circulating hydrogen of the reaction system is 195Nm3/h。
After the device runs for 200 hours, sampling is respectively carried out at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, wherein the results are as follows:
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.7％ | 0.04％ |
| IPDA content | 2.9％ | 99.4％ |
Example 18:
180kg Graies Raney5886 catalyst is filled in an IPN hydrogenation reactor, 22.5kg self-made catalyst 9 is filled in an IPAA hydroamination reactor, the catalyst 9 is activated in situ in the reactor by using hydrogen and nitrogen mixed gas with the volume ratio of 1:1, the flow rate of activated gas is 1150 standard liters/h, the activation temperature is 200 ℃, the activation time is 24h, and the temperature is reduced to below 100 ℃ after the activation is finished. Pressurizing the reaction system to 10MPa by using hydrogen, preheating the system by using the hydrogen, preheating the temperature of an IPN hydrogenation reactor to 90 ℃, preheating an IPAA hydroamination reactor to 180 ℃, feeding amount of the IPN to 45kg/h and hydrogen to 18.33Nm3The outlet temperature of the IPN hydrogenation reactor is 115 ℃, the liquid ammonia dosage of the IPAA hydroamination reactor is 92.7kg/h, the pressure of a reaction system is maintained at 12MPa, and the circulating hydrogen of the reaction system is 123Nm3/h。
After the device runs for 200 hours, samples are respectively taken at the outlet of the IPN hydrogenation reactor and the outlet of the IPAA hydroamination reactor, and gas chromatography analysis is carried out, and the results are as follows.
| IPN hydrogenation reactor outlet | IPAA hydroammonation reactor outlet | |
| Conversion of IPN | ＞99.9％ | —— |
| IPAA content | 99.7％ | 0.16％ |
| IPDA content | 2.3％ | 98.9％ |
Claims (14)
1. A process for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, the process comprising the steps of:
a) 3-cyano-3, 5, 5-trimethylcyclohexanone is used for generating 3-aminomethyl-3, 5, 5-trimethylcyclohexanol in the presence of a hydrogenation catalyst under a hydrogen atmosphere;
b) 3-aminomethyl-3, 5, 5-trimethylcyclohexanol reacts with liquid ammonia in the presence of a hydroamination catalyst to generate 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine;
the catalyst used in the step a) is a supported or Raney-type noble metal catalyst or a non-noble metal catalyst; the hydroammonation catalyst used in the step b) comprises an active component, an auxiliary agent and a carrier, wherein the active component is nickel, cobalt, copper and ruthenium, the auxiliary agent is one or more selected from palladium, chromium, manganese, iron, molybdenum, zinc, vanadium, bismuth, iridium, lanthanum and cerium,
the step a) is carried out at the temperature of 30-150 ℃ and under the pressure of 5-30 MPa;
the step b) is carried out at the temperature of 100-260 ℃ and under the pressure of 2-25 MPa.
2. The method according to claim 1, wherein step a) is carried out at a temperature of 80 to 120 ℃ and a pressure of 5 to 15 MPa;
the step b) is carried out at a temperature of 140-200 ℃ and a pressure of 5-15 MPa.
3. The process according to claim 2, characterized in that the reaction temperature and pressure of step a) are such that the hydrogenation reactor outlet is 20-30 ℃ higher than the inlet temperature.
4. The process according to any one of claims 1 to 3, wherein the molar ratio of hydrogen to 3-cyano-3, 5, 5-trimethylcyclohexanone in step a) is from 3: 1 to 1000: 1; the molar ratio of the hydrogen to the 3-aminomethyl-3, 5, 5-trimethylcyclohexanol in step b) is 3: 1 to 1000: 1.
5. The process according to any one of claims 1 to 3, wherein the molar ratio of hydrogen to 3-cyano-3, 5, 5-trimethylcyclohexanone in step a) is from 10: 1 to 500: 1; the molar ratio of the hydrogen to the 3-aminomethyl-3, 5, 5-trimethylcyclohexanol in the step b) is 10: 1-500: 1.
6. The process according to any one of claims 1 to 3, wherein the molar ratio of hydrogen to 3-cyano-3, 5, 5-trimethylcyclohexanone in step a) is from 20: 1 to 100: 1; the molar ratio of the hydrogen to the 3-aminomethyl-3, 5, 5-trimethylcyclohexanol in the step b) is 20: 1-100: 1.
7. A process according to any one of claims 1 to 3, characterised in that the catalyst used in step a) is selected from one or more of supported copper, supported nickel, supported cobalt, raney copper, raney nickel, raney cobalt or supported palladium, platinum, ruthenium, rhodium, iridium or chlorides or nitrates of precious metals.
8. The process of claim 7, wherein the catalyst used in step a) is Raney nickel, Raney cobalt, ruthenium on carbon, or palladium on alumina.
9. A method according to any one of claims 1-3, characterised in that the auxiliary agent used in step b) is one or more of palladium, chromium, manganese, molybdenum, zinc.
10. A process according to any one of claims 1 to 3, characterised in that the hydroamination catalyst used in step b) has the following active component content, based on the total weight of the catalyst:
the content of nickel element is 5 wt% -30 wt%;
the content of the cobalt element is 2-15 wt%;
the content of copper element is 0.2 wt% -3 wt%;
the content of the ruthenium element is 5 to 25 weight percent;
the content of the auxiliary agent in the hydroammonation catalyst used in the step b) is as follows based on the total weight of the catalyst:
the content of palladium element is 0 wt% -0.5 wt%;
the content of the chromium element is 0 to 0.8 weight percent;
the content of manganese element is 0 wt% -0.2 wt%;
the content of the molybdenum element is 0 wt% -0.4 wt%;
the content of zinc element is 0 wt% -0.5 wt%;
the carrier is preferably any one of activated carbon, alumina, zirconia, titania and magnesia.
11. The process according to claim 10, wherein the hydroamination catalyst used in step b) has the following active component content, based on the total weight of the catalyst:
the content of nickel element is 7 wt% -25 wt%;
the content of the cobalt element is 5-12 wt%;
the content of copper element is 0.5 wt% -2 wt%;
the content of the ruthenium element is 7 to 20 weight percent;
the content of the auxiliary agent in the hydroammonation catalyst used in the step b) is as follows based on the total weight of the catalyst:
the content of palladium element is 0.1 wt% -0.3 wt%;
the content of the chromium element is 0.1 to 0.6 weight percent;
the content of manganese element is 0.1 wt% -0.15 wt%;
the content of the molybdenum element is 0.1 to 0.2 weight percent;
the content of zinc element is 0.1 wt% -0.4 wt%.
12. The process according to claim 11, wherein the hydroamination catalyst used in step b) has the following active component content, based on the total weight of the catalyst:
the content of nickel element is 10 wt% -20 wt%;
the content of the cobalt element is 7-11 wt%;
the content of copper element is 0.8 wt% -1.5 wt%;
the content of the ruthenium element is 8 wt% -15 wt%.
13. The process according to any one of claims 1 to 3, wherein the space velocity of the feedstock in step a) is from 0.04 to 1 gram IPN per gram catalyst per hour; the space velocity of the raw material in the step b) is 0.1-10 g of IPAA/g of catalyst per hour.
14. The process according to any one of claims 1 to 3, wherein the space velocity of the feedstock in step a) is from 0.1 to 0.3 g IPN per g catalyst per hour; the space velocity of the raw material in the step b) is 0.6-3 g of IPAA/g of catalyst per hour.
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| JPH04300852A (en) * | 1991-03-29 | 1992-10-23 | Mitsubishi Kasei Corp | Production of 3-aminomethyl-3,5,5-trialkylcyclohexylamine |
| JPH05301847A (en) * | 1992-04-22 | 1993-11-16 | Showa Denko Kk | Production of isophoronediamine |
| JPH0625111A (en) * | 1992-07-13 | 1994-02-01 | Mitsubishi Kasei Corp | Production of 3-aminomethyl-3,5,5-trialkylcyclohexylamine |
| JPH06321870A (en) * | 1992-08-10 | 1994-11-22 | Asahi Chem Ind Co Ltd | Production of isophoronediamine |
| JPH06116213A (en) * | 1992-10-05 | 1994-04-26 | Sumitomo Chem Co Ltd | Production-of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine |
| EP0611137A1 (en) * | 1993-02-08 | 1994-08-17 | Sumitomo Chemical Company, Limited | Process for producing amines starting from cyclic ketones |
| DE4426472A1 (en) * | 1993-07-27 | 1995-02-02 | Du Pont | Preparation of isophoronediamine |
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