CN114380699A - Method for synthesizing isophorone diamine, catalyst and preparation method thereof - Google Patents
Method for synthesizing isophorone diamine, catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for synthesizing isophorone diamine, a catalyst and a preparation method thereof. Reacting isophorone nitrile, liquid ammonia and hydrogen serving as raw materials in the presence of a catalyst to obtain isophorone diamine, wherein the catalyst is obtained by reduction reaction of a supported catalyst; the supported catalyst comprises a carrier, and metal oxide and ionic liquid which are supported on the carrier, wherein the metal oxide comprises cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or more of transition metal oxides, alkali metal oxides and alkaline earth metal oxides, the carrier is a silicon-based material, the ionic liquid is selected from one or two of quaternary phosphine ionic liquid and quaternary ammonium ionic liquid, and the boiling point of the ionic liquid is higher than the temperature of reduction reaction. The catalyst of the invention can realize high conversion rate and catalytic selectivity, and has good stability.
Description
Technical Field
The invention relates to a method for synthesizing isophorone diamine, a catalyst and a preparation method thereof.
Background
Isophoronediamine (IPDA) is an important alicyclic diamine, and is easy to modify, and the modified product of the isophorone diamine plays an indispensable role in magnetic tape adhesives, adhesives for flexible packaging composite films, ink industry, agricultural and pharmaceutical industries and the like. The isophorone diamine is mainly used as a curing agent of epoxy resin, a cross-linking agent of polyurethane and an amine component of polyamide, and has wide application prospect.
At present, isophorone diamine is generally synthesized by taking isophorone nitrile as a raw material through two steps of imidization and hydrogenation, and Raney-Co, a skeletal cobalt catalyst and a supported catalyst are mostly used as hydrogenation catalysts in the method.
The Raney-Co catalyst is already industrialized, but most of alloy in the catalyst is only used as a substrate of an active layer, so that the metal utilization rate is extremely low, the catalyst cost is high, a large amount of alkaline wastewater is generated in the activation process, and the treatment cost is high.
US6437186 discloses the preparation of hollow Raney-Co catalyst, which comprises mixing alloy powder, binder, auxiliary agent, etc. into suspension, coating on polystyrene spheres, or coating for the second time, wherein the coating can be the same or different from the previous suspension, calcining to remove organic substance to obtain stable hollow spheres, and activating with NaOH solution to obtain the catalyst, but the hollow catalyst has insufficient strength and is affected to use.
Chinese patent CN106111160A discloses a preparation method and application of a skeletal Co catalyst, the specific method is: the catalyst is prepared by smelting to prepare Co-Al alloy, then crushing the Co-Al alloy into alloy powder, adding an organic binder, a lubricant, a high-temperature binder and a special binder, and carrying out molding, drying, roasting, activating and post-treatment on the mixture to obtain the catalyst. Although the catalyst has high selectivity for the hydrogenation reaction of isophorone nitrile, the preparation process is complex, the introduced binder components are excessive, the stability of the catalyst is unknown, and the stable running time of the catalyst when used in a fixed bed reactor is unknown.
Chinese patent CN112538020A discloses a method for preparing amine compounds such as isophorone diamine by continuously hydrogenating energy-saving nitrile compounds such as isophorone nitrile, which adopts a modified supported nickel catalyst, and comprises the following components in percentage by mass: 30-60% of a magnesium-aluminum oxide composite carrier, 30-68% of an active component nickel, 2-9.5% of an auxiliary active component cobalt and/or molybdenum, and 0.1-0.5% of one or more of auxiliary agents vanadium, strontium and lanthanum; although the catalyst has high selectivity for the hydrogenation reaction of isophorone nitrile, the composite carrier is adopted, the cost of the carrier is high, the cost of the catalyst is further increased by the aid of rare earth metal, and the stable running time and the dispersion uniformity of the catalyst are unknown.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an improved method for synthesizing isophorone diamine, which uses a novel catalyst, and can accelerate the reaction rate and shorten the reaction period on the premise of ensuring high conversion rate and high catalytic selectivity of the reaction.
The invention also provides a novel catalyst for synthesizing isophorone diamine, which has good stability, can effectively prevent the aggregation of active metal components and obviously improve the dispersion degree of the active components, and when the catalyst is used in the synthesis method, the conversion rate and the catalytic selectivity are both high, and the catalyst has long stable operation time in a fixed bed reactor and has no obvious inactivation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for synthesizing isophorone diamine uses isophorone nitrile, liquid ammonia and hydrogen as raw materials, and comprises the steps of reacting in the presence of a catalyst to obtain isophorone diamine, wherein the catalyst is obtained by reduction reaction of a supported catalyst; the supported catalyst comprises a carrier, and a metal oxide and an ionic liquid which are supported on the carrier, wherein the metal oxide comprises cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or more of transition metal oxides, alkali metal oxides and alkaline earth metal oxides, the carrier is a silicon-based material, the ionic liquid is selected from one or two of quaternary phosphine ionic liquid and quaternary ammonium ionic liquid, and the boiling point of the ionic liquid is higher than the temperature of the reduction reaction.
Further, the temperature of the reduction reaction is 100-400 ℃.
Further preferably, the temperature of the reduction reaction is 150-250 ℃.
Further, the cation of the ionic liquid is
Wherein X is selected from N or P, R1Selected from ethyl or butyl, R2Selected from linear, branched or cyclic alkyl of C1-C8.
Further preferably, R2Selected from methyl, ethyl, butyl, hexyl or octyl.
Further, the anion of the ionic liquid is selected from a bis (trifluoromethanesulfonyl) imide anion, a tetrafluoroborate anion or a hexafluorophosphate anion.
Further preferably, the quaternary phosphine-based ionic liquid is selected from the group consisting of alkyl triethylphosphine bis (trifluoromethanesulfonyl) imide salt, alkyl tributylphosphine bis (trifluoromethanesulfonyl) imide salt, alkyl triethylphosphine tetrafluoroborate, alkyl tributylphosphine tetrafluoroborate, alkyl triethylphosphine hexafluorophosphate and alkyl tributylphosphine hexafluorophosphate in combination of one or more thereof.
Further preferably, the quaternary ammonium-based ionic liquid is selected from one or more combinations of alkyl hydroxyethylammonium bis (trifluoromethanesulfonyl) imide salts, alkyl triethylammonium bis (trifluoromethanesulfonyl) imide salts, alkyl tributylammonium bis (trifluoromethanesulfonyl) imide salts, alkyl triethylammonium tetrafluoroborate, alkyl tributylammonium tetrafluoroborate, alkyl triethylammonium hexafluorophosphate and alkyl tributylammonium hexafluorophosphate.
The alkyl is selected from linear chain, branched chain or cyclic alkyl of C1-C8.
The alkyl group is preferably a methyl, ethyl, butyl, hexyl or octyl group.
Further, the silicon-based material is selected from spherical molecular sieves.
In some embodiments of the invention, the silicon-based material is selected from the group consisting of 3A, 4A and 5A molecular sieves in combination with one or more.
In some embodiments of the present invention, the silicon-based material has a specific surface area of 200 to 800m2/g。
In some embodiments of the present invention, the diameter of the silicon-based material is 2 to 3 mm.
In some embodiments of the invention, the silicon-based material is a hierarchical pore molecular sieve, wherein the thickness of large pores in the outer layer is 0.5-1 mm, and the thickness of small pores in the inner layer is 1-2.5 mm.
In some preferred embodiments of the invention, the silica-based material is a hierarchical pore ZSM-5.
The ionic liquid with the boiling point higher than the temperature of the reduction reaction of the supported catalyst is adopted, so that the gasification loss of the ionic liquid in the reduction preparation of the hydrogenation catalyst by the supported catalyst can be avoided, and the content and the function of the ionic liquid in the final hydrogenation catalyst can be ensured to be exerted.
Further, the other metal oxide includes a transition metal oxide.
Further, the alkali metal oxide is selected from one or two of sodium oxide and potassium oxide.
Further, the alkaline earth metal is selected from one or two of magnesium oxide and calcium oxide.
Further, the transition metal oxide is selected from one or more of titanium dioxide, chromium trioxide, ferric oxide, nickel oxide, copper oxide, zinc oxide, molybdenum trioxide and palladium oxide.
In some embodiments of the present invention, the supported catalyst comprises 50 to 80 wt% of the silicon-based material, 5 to 30 wt% of the ionic liquid, and 15 to 40 wt% of the metal oxide.
In some embodiments of the present invention, the metal oxide comprises, by mass%, 25 to 65 wt% of cobalt oxide, 3 to 25 wt% of manganese dioxide, 3 to 25 wt% of transition metal oxide, 1 to 20 wt% of alkali metal oxide, and 1 to 20 wt% of alkaline earth metal oxide.
In some embodiments of the present invention, the process for synthesizing isophorone diamine comprises the steps of:
1) charging the catalyst into a fixed bed reactor;
2) mixing the isophorone nitrile and liquid ammonia to obtain a mixture, and adding the mixture into the fixed bed reactor;
3) and introducing hydrogen to react to obtain the isophorone diamine.
Further, the molar ratio of the isophorone nitrile to the liquid ammonia is 1: 10-100.
Further, the pressure of the hydrogen is 10-50 MPa, the reaction temperature is 80-160 ℃, and the reaction time is 0.5-6 h.
Further, the mass space velocity of the mixture is 0.1-5 h-1。
The invention further provides the catalyst.
The invention still further provides a preparation method of the catalyst, which comprises the following steps:
1) preparing metal salt into first impregnation liquid, preheating the carrier, and impregnating the preheated carrier in the first impregnation liquid to obtain a supported catalyst precursor;
2) calcining the supported catalyst precursor to obtain a calcined supported catalyst precursor;
3) preparing ionic liquid into second impregnation liquid, and impregnating the calcined supported catalyst precursor into the second impregnation liquid to obtain the supported catalyst;
4) and reducing the supported catalyst under hydrogen to obtain the catalyst.
Further, the metal salt includes cobalt salt, manganese salt, and other metal salt selected from a combination of one or more of transition metal salt, alkali metal salt, and alkaline earth metal salt.
In some embodiments of the invention, the cobalt salt is cobalt nitrate and the manganese salt is manganese nitrate.
In some embodiments of the invention, the transition metal salt is a transition metal nitrate, preferably the transition metal salt is selected from the group consisting of titanium nitrate, chromium nitrate, iron nitrate, nickel nitrate, copper nitrate, zinc nitrate, molybdenum nitrate and palladium nitrate in combination with one or more of them.
In some embodiments of the invention, the alkali metal salt is an alkali metal nitrate salt, preferably the alkali metal salt is selected from one or both of sodium nitrate and potassium nitrate.
In some embodiments of the invention, the alkaline earth metal salt is an alkaline earth metal nitrate salt, preferably the alkaline earth metal salt is selected from one or both of calcium nitrate and magnesium nitrate.
In some embodiments of the invention, the metal salts are dissolved in water and mixed to form the first impregnation solution.
In some embodiments of the present invention, the ionic liquid is dissolved in ethanol to prepare a second impregnation solution.
In some embodiments of the present invention, in step 1), the carrier is preheated and then fully contacted with the first impregnation solution, and the impregnated carrier is filtered, evaporated and dried to obtain a supported catalyst precursor. The preheating temperature of the carrier preheating is 50-400 ℃, and preferably, the preheating temperature of the carrier preheating is 60-200 ℃. The drying temperature is 30-200 ℃, and preferably 60-150 ℃.
In other embodiments of the present invention, the carrier preheating and impregnation process is repeated 2 to 6 times in step 1), and the repeated impregnation can increase the loading amount of the metal active component on the carrier, and can make the metal salt distributed on the carrier more uniformly, thereby reducing the agglomeration of the metal active component in the final hydrogenation catalyst. After the first impregnation liquid is impregnated for each time, carrier filtration, evaporation and drying processes are carried out to obtain a supported catalyst precursor, or after the first impregnation liquid is impregnated for each time, the carrier is not filtered and is directly evaporated and dried together with the residual impregnation liquid to obtain the supported catalyst precursor, and the supported catalyst precursor can completely load the first impregnation liquid of the metal salt on the carrier.
In other embodiments of the present invention, the calcination temperature in the step 2) is 100 to 600 ℃ and the calcination time is 1 to 12 hours. Preferably, the calcining temperature is 150-450 ℃, and the time is 4-10 h.
In some embodiments of the invention, the calcined supported catalyst precursor is impregnated in the second impregnation solution in the step 3), and is dried to obtain the supported catalyst, wherein the impregnation temperature is 50 to 100 ℃, preferably, the impregnation temperature is 40 to 80 ℃, and the drying temperature is 80 to 150 ℃, preferably, the drying temperature is 90 to 130 ℃.
In some embodiments of the invention, the reduction temperature in the step 4) is 100 to 400 ℃ and the reduction time is 4 to 48 hours, preferably, the reduction temperature is 150 to 250 ℃ and the reduction time is 20 to 36 hours.
In some embodiments of the invention, the mass ratio of the ionic liquid to the calcined supported catalyst precursor in the step 3) is 0.05-0.5: 1.
In some embodiments of the present invention, the amount of the hydrogen in the step 4) is 0.01 to 1Nm based on 1Kg of the supported catalyst3Preferably, the amount of hydrogen is 0.05 to 0.5Nm based on 1Kg of the supported catalyst3/h。
Compared with the prior art, the invention has the following advantages:
the synthesis method of isophorone diamine has the advantages of extremely high conversion rate and catalytic selectivity, high reaction rate, short reaction period and low cost.
The catalyst is prepared by a hot dipping method, the loading capacity of an active component can be improved by multiple times of hot dipping and evaporation drying, an active metal oxide is obtained after metal salt calcination, then the loading of ionic liquid is carried out, then the supported catalyst is reduced, anions in the ionic liquid can be subjected to coordination and complexation with the metal active component in the reduction process, further the aggregation of metal component particles in the catalyst can be prevented, the dispersion degree of the metal component in the catalyst is obviously improved, in addition, the supported ionic liquid is stably distributed on the surface of the catalyst, a layer of liquid film is formed on the surface of the catalyst, the hydrogen absorption capacity of the catalyst is increased, when the catalyst is applied to an isophorone diamine synthesis method, the hydrogenation of C ═ N and C ≡ N is promoted, the reaction rate is accelerated, and the selectivity of hydrogenation reaction is improved.
The boiling point of the ionic liquid is higher than the reaction temperature of the supported catalyst for reduction preparation of the catalyst, so that the loss of the ionic liquid in the process of preparing the catalyst can be avoided, and the improvement of the ionic liquid loading in the catalyst is facilitated.
The catalyst of the invention is loaded with specific quaternary phosphine ionic liquid or specific quaternary ammonium ionic liquid, the cation of the catalyst is electron-deficient, and the catalyst is easy to form electron interaction with lone pair electrons on silicon hydroxyl of a carrier, so that the ionic liquid is stably distributed on the surface of the catalyst, thereby realizing the cyclic application of the catalyst, being capable of stably running for a long time, having extremely low desorption rate of the ionic liquid in the application or continuous running process, having the service life of more than 500h, keeping good activity of the catalyst and having no obvious inactivation.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50 wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of ZSM-5 molecular sieve carrier with the specific surface area of 410m is weighed2The diameter of the ZSM-5 molecular sieve is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the ZSM-5 molecular sieve is preheated to 240 ℃ in a muffle furnace, taken out, poured into the impregnation liquid A, fully contacted for 0.5h for first heat impregnation, filtered out, stirred, evaporated and dried at 80 ℃ for 2h, and then dried at 110 ℃ for 4 h; preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out second heat impregnation, stirring the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnation liquid A at 80 ℃, evaporating and drying for 2h, and then drying for 4h at 110 ℃. And calcining for 6h at 280 ℃ in an air atmosphere after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
Dissolving 20g of tributylhexylphosphine bis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid B is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, the weight percentage of the molecular sieve is 65.42%, the weight percentage of the ionic liquid is 14.54%, and the weight percentage of the active component is 20.05%. Active groupWherein the oxides are respectively CoO55.84 percent and MnO by weight2 16.42％，MgO 8.27％，Fe2O3 8.59％，NiO 10.88％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid materials is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 99.45% under the condition.
Example 2
1) Preparation of Supported catalyst precursor, same as example 1
2) Preparation of Supported catalysts
Dissolving 10g of tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, by weight, the molecular sieve accounts for 70.68%, the ionic liquid accounts for 7.85%, and the active component accounts for 21.46%. The active components comprise, by weight, CoO 56.28% and MnO respectively2 16.83％，MgO 8.49％，Fe2O3 8.16％，NiO 10.25％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 97.73% under the conditions.
Example 3
1) Preparation of Supported catalyst precursor, same as example 1
2) Preparation of Supported catalysts
Dissolving 20g of trimethyl hydroxyethyl ammonium bis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, by weight, the molecular sieve accounts for 65.58%, the ionic liquid accounts for 14.57%, and the active component accounts for 19.84%. The active components comprise, by weight, CoO56.56% and MnO respectively2 16.71％，MgO 8.15％，Fe2O3 8.37％，NiO 10.21％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.61% under the conditions.
Example 4
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of calcium nitrate hexahydrate, 20g of 50 wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of ZSM-5 molecular sieve carrier with the specific surface area of 410m is weighed2The diameter of the ZSM-5 molecular sieve is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the ZSM-5 molecular sieve is preheated to 240 ℃ in a muffle furnace, then poured into the impregnation liquid A, fully contacted for 0.5h for first heat impregnation, filtered out, stirred, evaporated and dried at 80 ℃ for 2h, and then dried at 110 ℃ for 4 h; preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out second heat impregnation, stirring the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnation liquid A at 80 ℃, evaporating and drying for 2h, and then drying for 4h at 110 ℃. And calcining for 6h at 280 ℃ in an air atmosphere after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
Dissolving 20g of tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, the weight percentage of the molecular sieve is 64.28%, the weight percentage of the ionic liquid is 14.28%, and the weight percentage of the active component is 21.44%. In the active component, by weight, the oxides are respectively CoO 51.23% and MnO2 15.52％，CaO16.19％，Fe2O3 7.73％，NiO 9.33％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia in a molar ratio of 1:50 to obtain a mass liquidThe space velocity of the material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.36% under the conditions.
Example 5
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of a 50 wt% aqueous solution of manganese nitrate, 12g of palladium nitrate dihydrate and 3.1g of potassium nitrate are dissolved in 100ml of water, and the components are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of ZSM-5 molecular sieve carrier with the specific surface area of 410m is weighed2The diameter of the ZSM-5 molecular sieve is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the ZSM-5 molecular sieve is preheated to 240 ℃ in a muffle furnace, then poured into the impregnation liquid A, fully contacted for 0.5h for first heat impregnation, filtered out, stirred, evaporated and dried at 80 ℃ for 2h, and then dried at 110 ℃ for 4 h; preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out second heat impregnation, stirring the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnation liquid A at 80 ℃, evaporating and drying for 2h, and then drying for 4h at 110 ℃. And calcining for 6h at 280 ℃ in an air atmosphere after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
Dissolving 20g of methyltributylammonium tetrafluoroborate in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, by weight, the molecular sieve accounts for 63.74%, the ionic liquid accounts for 14.17%, and the active component accounts for 22.09%. In the active component, by weight, the oxides are respectively CoO 49.37% and MnO214.94％，MgO 7.21％，KO 8.34％，PdO 20.13％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.61% under the conditions.
Example 6
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50 wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of 3A molecular sieve carrier is weighed, and the specific surface area is 196m2The diameter of the dipping solution is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the dipping solution is preheated to 240 ℃ in a muffle furnace and then poured into the dipping solution A, the dipping solution A is fully contacted for 0.5h for carrying out first hot dipping, a 3A molecular sieve after the hot dipping is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then the dipping solution is dried for 4h at 110 ℃; preheating the 3A molecular sieve subjected to the first heat soaking to 240 ℃, pouring the preheated 3A molecular sieve into the soaking liquid A, fully contacting for 0.5h, carrying out second heat soaking, stirring the 3A molecular sieve subjected to heat soaking and the residual soaking liquid A at 80 ℃, evaporating and drying for 2h, and then drying for 4h at 110 ℃. And calcining for 6h at 280 ℃ in an air atmosphere after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
Dissolving 20g of tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, by weight, is divided intoThe ratio of the sub-sieve to the ionic liquid is 65.35 percent, the ratio of the ionic liquid to the ionic liquid is 14.52 percent, and the ratio of the active component to the active component is 20.13 percent. In the active component, the weight percentage of each oxide is respectively CoO 55.39 percent and MnO2 17.24％，MgO 8.29％，Fe2O3 8.44％，NiO 10.64％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.17% under the condition.
Example 7
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50 wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of ZSM-5 molecular sieve carrier with the specific surface area of 410m is weighed2The diameter of the ZSM-5 molecular sieve is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the ZSM-5 molecular sieve is preheated to 240 ℃ in a muffle furnace, then poured into the impregnation liquid A, fully contacted for 0.5h for first heat impregnation, filtered out, stirred, evaporated and dried at 80 ℃ for 2h, and then dried at 110 ℃ for 4 h; preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out second heat impregnation, filtering the ZSM-5 molecular sieve subjected to the heat impregnation, and drying the ZSM-5 molecular sieve at 110 ℃ for 4 h. At the moment, 70% of the total mass of the metal nitrate is loaded on the molecular sieve, and the metal nitrate is calcined for 6 hours at the temperature of 280 ℃ in the air atmosphere after being dried, so that the supported catalyst precursor is obtained.
2) Preparation of Supported catalysts
Dissolving 20g of tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, the weight percentage of the molecular sieve is 69.59%, the weight percentage of the ionic liquid is 14.47%, and the weight percentage of the active component is 14.94%. In the active component, the weight percentage of each oxide is respectively CoO 55.43 percent and MnO2 16.88％，MgO 8.19％，Fe2O3 8.62％，NiO 10.87％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.22% under the conditions.
Example 8
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50 wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and are uniformly mixed to form liquid containing active components, namely impregnation liquid A. Then 90g of ZSM-5 molecular sieve carrier with the specific surface area of 410m is weighed2The diameter of the ZSM-5 molecular sieve is about 4mm, the thickness of a large hole on the outer layer is about 1mm, the thickness of a small hole in the inner layer is about 1mm, the ZSM-5 molecular sieve is preheated to 240 ℃ in a muffle furnace, poured into the impregnation liquid A, fully contacted for 0.5h for first heat impregnation, and the ZSM-5 molecular sieve after heat impregnation is filtered outStirring at 80 deg.C, evaporating and drying for 2 hr, and drying at 110 deg.C for 4 hr; preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out second heat impregnation, stirring the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnation liquid A at 80 ℃, evaporating and drying for 2h, and then drying for 4h at 110 ℃. Preheating the ZSM-5 molecular sieve subjected to the second heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out the third heat impregnation, filtering the ZSM-5 molecular sieve subjected to the heat impregnation, stirring at 80 ℃, evaporating and drying for 2h, and then drying at 110 ℃ for 4 h. Preheating the ZSM-5 molecular sieve subjected to the third heat impregnation to 240 ℃, then pouring the ZSM-5 molecular sieve into the impregnation liquid A to fully contact for 0.5h for carrying out the fourth heat impregnation, filtering the ZSM-5 molecular sieve subjected to the heat impregnation, stirring at 80 ℃, evaporating and drying for 2h, and then drying at 110 ℃ for 4 h. And calcining for 6h at 280 ℃ in an air atmosphere after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
Dissolving 20g of tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt in 20ml of ethanol to prepare impregnation liquid B, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, the weight percentage of the molecular sieve is 65.41%, the weight percentage of the ionic liquid is 14.53%, and the weight percentage of the active component is 20.06%. In the active component, the weight percentage of each oxide is respectively CoO 55.54 percent and MnO2 17.03％，MgO 8.12％，Fe2O38.59％，NiO 10.72％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding into the fixed bed reactor filled with the catalyst, and feeding under the hydrogen pressure of 26MPa and at the temperature of 100 DEG CAfter the reaction, a sample was taken and filtered to obtain an isophorone diamine reaction solution, and the result shows that the conversion rate of IPN under the conditions is 100% and the selectivity of isophorone diamine IPDA is 99.29%.
Comparative example 1
The catalyst in this comparative example did not carry an ionic liquid
1) A supported catalyst precursor was prepared, and in the supported catalyst precursor obtained in example 7, the molecular sieve accounted for 76.55% and the active component accounted for 23.45% by weight. The active components comprise, by weight, CoO55.79% of oxides and MnO2 17.12％，MgO 8.16％，Fe2O3 8.45％，NiO10.48％。
2) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
3) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.25h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 87.1% under the conditions.
It can be seen that when no ionic liquid is supported in the catalyst, the selectivity of the reaction for synthesizing isophorone diamine from isophorone nitrile is significantly reduced. The reason is that when the catalyst does not load ionic liquid, the catalyst has no hydrogen absorption effect and no metal component agglomeration prevention effect, the space velocity of the comparative example 1 is reduced, the residence time of the reaction liquid on the surface of the catalyst is prolonged, namely the reaction time is prolonged, and the selectivity is obviously reduced.
Comparative example 2
The kind of ionic liquid supported by the catalyst in this comparative example is outside the scope of the present invention
1) Preparation of Supported catalyst precursor, same as example 6
2) Preparation of Supported catalysts
Preparing 20g of pyridine hydrochloride (with the boiling point of 222-224 ℃) into impregnation liquid B in 20ml of ethanol, fully contacting the supported catalyst precursor with the impregnation liquid B at 60 ℃ until the impregnation liquid is completely supported on the supported catalyst precursor, and drying at 90 ℃ for 2h to obtain the supported catalyst. In the supported catalyst, the weight percentage of the molecular sieve is 65.38%, the weight percentage of the ionic liquid is 14.53%, and the weight percentage of the active component is 20.09%. In the active component, the weight percentage of each oxide is respectively CoO 55.55 percent and MnO2 16.96％，MgO 8.14％，Fe2O3 8.5％，NiO 10.85％。
3) Preparation of the catalyst
100g of the prepared supported catalyst is loaded into a fixed bed reactor, and then the supported catalyst is subjected to online reduction treatment in a pure hydrogen atmosphere, wherein the reduction treatment temperature is 250 ℃, and the reduction treatment time is 48 hours, so that the catalyst is obtained.
4) Preparation of isophoronediamine
Mixing isophorone nitrile IPN and liquid ammonia at a molar ratio of 1:50, wherein the space velocity of mass liquid material is 0.5h-1Adding the mixture into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and at the temperature of 100 ℃, then sampling and filtering to obtain an isophorone diamine reaction solution, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 89.8% under the conditions.
It can be seen that when the boiling point of the supported ionic liquid in the catalyst is lower than the temperature at which the supported catalyst is reduced to a catalyst, the ionic liquid is lost during the catalyst preparation process, resulting in a decrease in the selectivity of the reaction for synthesizing isophoronediamine from isophoronenitrile.
Example 9
The process for the preparation of isophorone diamine of step 4) shown in example 1 was run continuously under the same reaction conditions, and the data are shown in table 1 below. Therefore, the catalyst can stably and continuously operate for more than 500 hours, and the catalytic activity is not obviously reduced.
TABLE 1
| Duration of operation/h | Conversion rate | Selectivity is |
| 10 | 100％ | 99.52％ |
| 50 | 100％ | 99.45％ |
| 100 | 100％ | 99.37％ |
| 200 | 100％ | 99.28％ |
| 500 | 100％ | 99.31％ |
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (14)
1. A method for synthesizing isophorone diamine takes isophorone nitrile, liquid ammonia and hydrogen as raw materials, and reacts in the presence of a catalyst to obtain isophorone diamine, and is characterized in that: the catalyst is obtained by reduction reaction of a supported catalyst; the supported catalyst comprises a carrier, and a metal oxide and an ionic liquid which are supported on the carrier, wherein the metal oxide comprises cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or more of transition metal oxides, alkali metal oxides and alkaline earth metal oxides, the carrier is a silicon-based material, the ionic liquid is selected from one or two of quaternary phosphine ionic liquid and quaternary ammonium ionic liquid, and the boiling point of the ionic liquid is higher than the temperature of the reduction reaction.
2. The method of synthesizing isophorone diamine of claim 1, wherein: the temperature of the reduction reaction is 100-400 ℃, and preferably 150-250 ℃; and/or the cation of the ionic liquid is
Wherein X is selected from N or P, R1Selected from ethyl or butyl, R2Selected from linear, branched or cyclic alkyl of C1-C8, preferably R2Selected from methyl, ethyl, butyl, hexyl or octyl; the anion of the ionic liquid is selected from bis (trifluoromethanesulfonyl) imide anion, tetrafluoroborate anion or hexafluorophosphate anion.
3. The process for synthesizing isophorone diamine of claim 2, wherein: the quaternary phosphine ionic liquid is selected from one or more of alkyl triethyl phosphine bis (trifluoromethanesulfonyl) imide salt, alkyl tributylphosphine bis (trifluoromethanesulfonyl) imide salt, alkyl triethyl phosphine tetrafluoroborate, alkyl tributylphosphine tetrafluoroborate, alkyl triethyl phosphine hexafluorophosphate and alkyl tributylphosphine hexafluorophosphate; the quaternary ammonium ionic liquid is selected from one or more of alkyl triethyl ammonium bis (trifluoromethanesulfonyl) imide salt, alkyl tributyl ammonium bis (trifluoromethanesulfonyl) imide salt, alkyl triethyl ammonium tetrafluoroborate, alkyl tributyl ammonium tetrafluoroborate, alkyl triethyl ammonium hexafluorophosphate and alkyl tributyl ammonium hexafluorophosphate.
4. The process for synthesizing isophorone diamine of claim 1, wherein: the silicon-based material is selected from one or more of 3A, 4A and 5A molecular sieves; and/or the silica-based material is a hierarchical pore molecular sieve, wherein the thickness of a large pore on the outer layer is 0.5-1 mm, the thickness of a small pore on the inner layer is 1-2.5 mm, and preferably, the silica-based material is ZSM-5 of a hierarchical pore.
5. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: the other metal oxide includes a transition metal oxide; and/or, the alkali metal oxide is selected from one or two of sodium oxide and potassium oxide; and/or, the alkaline earth metal is selected from one or two of magnesium oxide and calcium oxide; and/or the transition metal oxide is selected from one or more of titanium dioxide, chromium trioxide, ferric oxide, nickel oxide, copper oxide, zinc oxide, molybdenum trioxide and palladium oxide.
6. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: in the supported catalyst, the content of the silicon-based material is 50-80 wt%, the content of the ionic liquid is 5-30 wt%, and the content of the metal oxide is 15-40 wt%.
7. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: in the metal oxide, by mass, cobalt oxide is 25-65 wt%, manganese dioxide is 3-25 wt%, transition metal oxide is 3-25 wt%, alkali metal oxide is 1-20 wt%, and alkaline earth metal oxide is 1-20 wt%.
8. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: the method comprises the following steps:
1) charging the catalyst into a fixed bed reactor;
2) mixing the isophorone nitrile and liquid ammonia to obtain a mixture, and adding the mixture into the fixed bed reactor;
3) and introducing hydrogen to react to obtain the isophorone diamine.
9. The process for synthesizing isophorone diamine of claim 9, wherein: the molar ratio of the isophorone nitrile to the liquid ammonia is 1: 10-100; and/or the pressure of the hydrogen is 10-50 MPa, the reaction temperature is 80-160 ℃, and the reaction time is 0.5-6 h; and/or the mass space velocity of the mixture is 0.1-5 h-1。
10. A catalyst as claimed in any one of claims 1 to 9.
11. A method of preparing the catalyst of claim 10, wherein: the preparation method comprises the following steps:
1) preparing metal salt into first impregnation liquid, preheating the carrier, and impregnating the preheated carrier in the first impregnation liquid to obtain a supported catalyst precursor;
2) calcining the supported catalyst precursor to obtain a calcined supported catalyst precursor;
3) preparing ionic liquid into second impregnation liquid, and impregnating the calcined supported catalyst precursor into the second impregnation liquid to obtain the supported catalyst;
4) and reducing the supported catalyst under hydrogen to obtain the catalyst.
12. The method for preparing a catalyst according to claim 11, characterized in that: the metal salt comprises cobalt salt, manganese salt and other metal salt, and the other metal salt is selected from one or more of transition metal salt, alkali metal salt and alkaline earth metal salt.
13. The method for preparing a catalyst according to claim 11, characterized in that: preheating the carrier in the step 1), fully contacting the preheated carrier with the first impregnation liquid, filtering, evaporating and drying the impregnated carrier to obtain a supported catalyst precursor, wherein the preheating temperature of the preheated carrier is 50-400 ℃; and/or, in the step 2), the calcining temperature is 100-600 ℃, and the time is 1-12 h; and/or, in the step 3), impregnating the calcined supported catalyst precursor into the second impregnation liquid, and drying to obtain the supported catalyst, wherein the calcination temperature is 100-600 ℃, the time is 1-12 h, and the drying temperature is 80-150 ℃; and/or in the step 4), the reduction temperature is 100-400 ℃, and the reduction time is 4-48 h.
14. The method for preparing a catalyst according to claim 11, characterized in that: in the step 1), carrier preheating and dipping are repeated for 2-6 times; and/or the mass ratio of the ionic liquid to the calcined supported catalyst precursor in the step 3) is 0.05-0.5: 1; and/or, in the step 4), the amount of the hydrogen is 0.01-1 Nm based on 1Kg of the supported catalyst3/h。
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047856A (en) * | 1989-04-25 | 1990-12-19 | 联合碳化化学品及塑料有限公司 | The reduction amination of carbonyl nitrile and similar compound |
| US5696048A (en) * | 1995-05-09 | 1997-12-09 | Basf Aktiengesellschaft | Cobalt catalysts |
| US6437186B1 (en) * | 2000-12-23 | 2002-08-20 | Degussa Ag | Process for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN1561260A (en) * | 2001-08-31 | 2005-01-05 | 巴斯福股份公司 | Method for the production of isophorondiamine (IPDA,3-aminomethyl-3,5,5-trimethylcyclohexylamine) |
| CN1906150A (en) * | 2003-12-22 | 2007-01-31 | 巴斯福股份公司 | Nitrile hydrogenation method on heterogeneous catalysts in the presence of ionic liquids |
| CN101386579A (en) * | 2008-11-05 | 2009-03-18 | 烟台万华聚氨酯股份有限公司 | Method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN102307661A (en) * | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | Hydrogenation catalysts, the production and the use thereof |
| CN103429563A (en) * | 2011-03-22 | 2013-12-04 | 巴斯夫欧洲公司 | Method for hydrogenating nitriles |
| CN105032430A (en) * | 2015-08-05 | 2015-11-11 | 万华化学集团股份有限公司 | Method for preparing eggshell type Co-Ni-Fe@SiO2 catalyst, prepared catalyst and application thereof |
| CN107857704A (en) * | 2017-11-21 | 2018-03-30 | 万华化学集团股份有限公司 | A kind of method for preparing the trimethyl cyclohexylamine of 3 aminomethyl 3,5,5 and the catalyst for this method |
| CN108686660A (en) * | 2018-04-24 | 2018-10-23 | 浙江大学 | A kind of catalyst and its preparation method and application for cyan-3,5,5-trimethyl cyclohexanone reduction amination synthesis of isophorone diamines |
| CN110496645A (en) * | 2019-08-28 | 2019-11-26 | 浙江工业大学 | A kind of support type amine alkyl ionic liquid-metallic catalyst and its preparation and application |
| CN110606806A (en) * | 2019-10-04 | 2019-12-24 | 重庆工商大学 | Method for synthesizing primary amine under catalysis of nano ruthenium |
| CN111250158A (en) * | 2019-11-29 | 2020-06-09 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst and preparation and application thereof |
| CN112191269A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Alumina-supported ionic liquid-copper catalyst, preparation thereof and application thereof in acetylene hydrogenation reaction |
-
2022
- 2022-01-26 CN CN202210094732.6A patent/CN114380699B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047856A (en) * | 1989-04-25 | 1990-12-19 | 联合碳化化学品及塑料有限公司 | The reduction amination of carbonyl nitrile and similar compound |
| US5696048A (en) * | 1995-05-09 | 1997-12-09 | Basf Aktiengesellschaft | Cobalt catalysts |
| US6437186B1 (en) * | 2000-12-23 | 2002-08-20 | Degussa Ag | Process for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN1561260A (en) * | 2001-08-31 | 2005-01-05 | 巴斯福股份公司 | Method for the production of isophorondiamine (IPDA,3-aminomethyl-3,5,5-trimethylcyclohexylamine) |
| CN1906150A (en) * | 2003-12-22 | 2007-01-31 | 巴斯福股份公司 | Nitrile hydrogenation method on heterogeneous catalysts in the presence of ionic liquids |
| CN101386579A (en) * | 2008-11-05 | 2009-03-18 | 烟台万华聚氨酯股份有限公司 | Method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN102307661A (en) * | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | Hydrogenation catalysts, the production and the use thereof |
| CN103429563A (en) * | 2011-03-22 | 2013-12-04 | 巴斯夫欧洲公司 | Method for hydrogenating nitriles |
| CN105032430A (en) * | 2015-08-05 | 2015-11-11 | 万华化学集团股份有限公司 | Method for preparing eggshell type Co-Ni-Fe@SiO2 catalyst, prepared catalyst and application thereof |
| CN107857704A (en) * | 2017-11-21 | 2018-03-30 | 万华化学集团股份有限公司 | A kind of method for preparing the trimethyl cyclohexylamine of 3 aminomethyl 3,5,5 and the catalyst for this method |
| CN108686660A (en) * | 2018-04-24 | 2018-10-23 | 浙江大学 | A kind of catalyst and its preparation method and application for cyan-3,5,5-trimethyl cyclohexanone reduction amination synthesis of isophorone diamines |
| CN110496645A (en) * | 2019-08-28 | 2019-11-26 | 浙江工业大学 | A kind of support type amine alkyl ionic liquid-metallic catalyst and its preparation and application |
| CN110606806A (en) * | 2019-10-04 | 2019-12-24 | 重庆工商大学 | Method for synthesizing primary amine under catalysis of nano ruthenium |
| CN111250158A (en) * | 2019-11-29 | 2020-06-09 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst and preparation and application thereof |
| CN112191269A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Alumina-supported ionic liquid-copper catalyst, preparation thereof and application thereof in acetylene hydrogenation reaction |
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