CN114380699B - 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. Isophorone nitrile, liquid ammonia and hydrogen are used as raw materials to react in the presence of a catalyst to obtain isophorone diamine, and the catalyst is obtained by a reduction reaction of a supported catalyst; the supported catalyst comprises a carrier, and metal oxides and ionic liquid supported on the carrier, wherein the metal oxides comprise cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or a combination of a plurality 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. The catalyst of the invention can realize high conversion rate and catalytic selectivity, and has good catalyst stability.
Description
Technical Field
The invention relates to a method for synthesizing isophorone diamine, a catalyst and a preparation method thereof.
Background
Isophorone diamine (IPDA) is an important cycloaliphatic diamine, isophorone diamine is easy to modify, and the modified product of isophorone diamine plays an indispensable role in tape adhesives, adhesives for flexible packaging composite films, ink industry, and pesticide industry and pharmaceutical industry. 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 nitrile is generally used as a raw material to synthesize isophorone diamine through imidization and hydrogenation in two steps, and Raney-Co, a framework cobalt catalyst and a supported catalyst are mostly used as hydrogenation catalysts in the method.
Wherein, raney-Co catalyst has been industrialized, but most of alloy in the catalyst is only used as a matrix of an active layer, 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.
U.S. patent No. 6437186 discloses the preparation of hollow Raney-Co catalysts by uniformly mixing alloy powder, binder, auxiliary agent, etc. to form a suspension, then coating the suspension on polystyrene spheres, or performing secondary coating, wherein the coating can have the same or different composition with the previous suspension, then removing organic matters by roasting to obtain stable hollow spheres, and then activating the hollow spheres by a NaOH solution with a certain concentration to obtain the catalyst, but the strength of the hollow catalyst particles is not high enough to influence the use.
Chinese patent CN106111160a discloses a preparation method and application of skeleton Co catalyst, the specific method is: the Co-Al alloy is prepared by smelting, then crushed into alloy powder, and then added with an organic binder, a lubricant, a high-temperature binder and a special binder, and the catalyst is obtained by molding, drying, roasting, activating and post-treatment. Although the catalyst has high selectivity on the hydrogenation reaction of isophorone nitrile, the preparation process is complex, the introduced binder component is excessive, the stability of the catalyst is unknown, and the stable operation time of the catalyst when the catalyst is 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 magnesium aluminum oxide composite carrier, 30-68% of active component nickel, 2-9.5% of auxiliary active component cobalt and/or molybdenum, and 0.1-0.5% of one or more of auxiliary vanadium, strontium and lanthanum; the catalyst has high selectivity on the hydrogenation reaction of isophorone nitrile, but adopts a composite carrier, so that the carrier cost is high, the catalyst cost is further increased by the aid of rare earth metal, and the stable operation 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, 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 particles of active metal components from gathering, obviously improves the dispersion degree of the active components, has high conversion rate and catalytic selectivity when used in the synthesis method, and has long stable operation time in a fixed bed reactor without obvious deactivation.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method takes isophorone nitrile, liquid ammonia and hydrogen as raw materials, and carries out reaction 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 oxides and ionic liquids supported on the carrier, wherein the metal oxides comprise cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or more combinations of transition metal oxides, alkali metal oxides and alkaline earth metal oxides, the carrier is made of a silicon-based material, the ionic liquids are selected from one or two of quaternary phosphine ionic liquids and quaternary ammonium ionic liquids, and the boiling point of the ionic liquids 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 to 250 ℃.
Further, the cation of the ionic liquid is
Wherein X is selected from N or P, R 1 Selected from ethyl or butyl, R 2 Selected from the group consisting of C1-C8 linear, branched or cyclic alkyl groups.
Further preferably, R 2 Selected from methyl, ethyl, butyl, hexyl or octyl.
Further, the anion of the ionic liquid is selected from bis (trifluoromethanesulfonyl) imide anion, tetrafluoroboric acid anion or hexafluorophosphoric acid anion.
Further preferably, the quaternary phosphine ionic liquid is selected from one or more of alkyl triethyl phosphine bis (trifluoromethanesulfonyl) imide salt, alkyl tributyl phosphine bis (trifluoromethanesulfonyl) imide salt, alkyl triethyl phosphine tetrafluoroborate, alkyl tributyl phosphine tetrafluoroborate, alkyl triethyl phosphine hexafluorophosphate and alkyl tributyl phosphine hexafluorophosphate.
Further preferably, the quaternary ammonium ionic liquid is selected from one or more of alkyl hydroxyethylammonium bis (trifluoromethanesulfonyl) imide salt, alkyl triethylammonium bis (trifluoromethanesulfonyl) imide salt, alkyl tributylammonium bis (trifluoromethanesulfonyl) imide salt, alkyl triethylammonium tetrafluoroborate, alkyl tributylammonium tetrafluoroborate, alkyl triethylammonium hexafluorophosphate and alkyl tributylammonium hexafluorophosphate.
The alkyl is selected from the group consisting of C1-C8 linear, branched or cyclic alkyl.
The alkyl group is preferably methyl, ethyl, butyl, hexyl or octyl.
Further, the silicon-based material is selected from the group consisting of spherical molecular sieves.
In some embodiments of the invention, the silicon-based material is selected from the group consisting of one or more of 3A, 4A, and 5A molecular sieves.
In some embodiments of the invention, the specific surface area of the silicon-based material is 200-800 m 2 /g。
In some embodiments of the invention, the silicon-based material has a diameter of 2 to 3mm.
In some embodiments of the invention, the silicon-based material is a hierarchical pore molecular sieve, wherein the outer layer has a macropore thickness of 0.5 to 1mm and the inner layer has a mesopore thickness of 1 to 2.5mm.
In some preferred embodiments of the present invention, the silicon-based material is ZSM-5 of graded pore channels.
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 preparation of the hydrogenation catalyst by the reduction of the supported catalyst can be avoided, and the content and the action of the ionic liquid in the final hydrogenation catalyst are ensured.
Further, the other metal oxide includes a transition metal oxide.
Further, the alkali metal oxide is selected from one or both of sodium oxide and potassium oxide.
Further, the alkaline earth metal is selected from one or both 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 content of the silicon-based material in the supported catalyst is 50 to 80wt%, the content of the ionic liquid is 5 to 30wt%, and the content of the metal oxide is 15 to 40wt%.
In some embodiments of the present invention, the metal oxide comprises, by mass, 25 to 65% cobalt oxide, 3 to 25% manganese dioxide, 3 to 25% transition metal oxide, 1 to 20% alkali metal oxide, and 1 to 20% alkaline earth metal oxide.
In some embodiments of the present invention, the method of synthesizing isophorone diamine comprises the steps of:
1) Loading the catalyst into a fixed bed reactor;
2) Mixing isophorone nitrile and liquid ammonia to obtain a mixture, and adding the mixture into the fixed bed reactor;
3) Introducing hydrogen to react to obtain the isophorone diamine.
Further, the molar ratio of isophorone nitrile to liquid ammonia is 1:10-100.
Further, the pressure of the hydrogen is 10-50 MPa, the temperature of the reaction is 80-160 ℃ and the time is 0.5-6 h.
Further, the mass airspeed of the mixture is 0.1 to 5 hours -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 a first impregnating solution from metal salt, preheating the carrier, and impregnating the carrier in the first impregnating solution to obtain a supported catalyst precursor;
2) Calcining the supported catalyst precursor to obtain a calcined supported catalyst precursor;
3) Preparing ionic liquid into a second impregnating solution, and impregnating the calcined supported catalyst precursor into the second impregnating solution to obtain the supported catalyst;
4) And reducing the supported catalyst under hydrogen to obtain the catalyst.
Further, the metal salts include cobalt salts, manganese salts, and other metal salts selected from the group consisting of one or more of transition metal salts, alkali metal salts, and alkaline earth metal salts.
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 some embodiments of the invention, the alkali metal salt is an alkali metal nitrate, 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, preferably the alkaline earth metal salt is selected from one or both of calcium nitrate and magnesium nitrate.
In some embodiments of the invention, each metal salt is dissolved in water and mixed to form the first impregnating solution.
In some embodiments of the invention, the ionic liquid is dissolved in ethanol to prepare a second impregnating solution.
In some embodiments of the present invention, the support is preheated in step 1) and then fully contacted with the first impregnating solution, and the impregnated support is filtered, evaporated and dried to obtain the supported catalyst precursor. The preheating temperature of the carrier preheating is 50-400 ℃, preferably, the preheating temperature of the carrier preheating is 60-200 ℃. The drying temperature is 30 to 200 ℃, preferably 60 to 150 ℃.
In other embodiments of the present invention, the carrier preheating and impregnation process is repeated 2-6 times in the step 1), and repeated impregnation can increase the loading amount of the metal active component on the carrier, and can make the distribution of the metal salt on the carrier more uniform, so as to reduce the agglomeration of the metal active component in the final hydrogenation catalyst. And (3) carrying out carrier filtration, evaporation and drying processes after each first impregnating solution is impregnated to obtain a supported catalyst precursor, or carrying out evaporation and drying processes with residual impregnating solution without filtering the carrier after each first impregnating solution is impregnated to obtain the supported catalyst precursor, wherein the supported catalyst precursor can completely support the first impregnating solution of the metal salt on the carrier.
In other embodiments of the present invention, the calcination temperature in step 2) is 100 to 600 ℃ for 1 to 12 hours. Preferably, the calcination temperature is 150-450 ℃ and the time is 4-10 h.
In some embodiments of the invention, the step 3) impregnates the calcined supported catalyst precursor with the second impregnation liquid and dries to obtain the supported catalyst, wherein the impregnation temperature is 50-100 ℃, preferably 40-80 ℃, the drying temperature is 80-150 ℃, preferably 90-130 ℃.
In some embodiments of the invention, the reduction temperature in step 4) is 100 to 400 ℃, 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 step 3) is from 0.05 to 0.5:1.
In some embodiments of the invention, in said step 4), the amount of hydrogen is 0.01 to 1Nm based on 1Kg of said supported catalyst 3 Preferably, the amount of hydrogen is 0.05 to 0.5Nm based on 1Kg of the supported catalyst 3 /h。
Compared with the prior art, the invention has the following advantages:
the isophorone diamine synthesis method has extremely high conversion rate and catalytic selectivity, and simultaneously has the advantages of high reaction rate, short reaction period and low cost.
According to the preparation method, the catalyst is prepared by a hot dipping method, the loading amount of an active component can be improved through repeated hot dipping and evaporation drying, the active metal oxide is obtained after metal salt calcination, then the loading of the ionic liquid is carried out, and then the supported catalyst is reduced, in the reduction process, anions in the ionic liquid can be coordinated and complexed with the metal active component, so that 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, so that the hydrogen absorption capacity of the catalyst is improved, and 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 preparing the catalyst by reduction, 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 load in the catalyst is facilitated.
The catalyst is loaded with the specific type of quaternary phosphine ionic liquid or the specific type of quaternary ammonium ionic liquid, the cation of the catalyst is electron-deficient, electron interaction is easily formed between the cation and lone pair electrons on the silicon hydroxyl of the carrier, and the ionic liquid is stably distributed on the surface of the catalyst, so that the catalyst can be recycled, the catalyst can stably run for a long time, the desorption rate of the ionic liquid in the process of recycling or continuous running is extremely low, the service life is longer than 500 hours, the activity of the catalyst is still good, and no obvious deactivation is caused.
Detailed Description
The invention is further described below with reference to examples. 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 which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
1) Preparation of Supported catalyst precursor
Dissolving 60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate in 100ml of water, and uniformly mixing to form a liquid containing active componentsThe body, namely the impregnating solution A. 90g of ZSM-5 molecular sieve carrier with the specific surface of 410m is weighed again 2 And/g, wherein the diameter is about 4mm, the thickness of the large holes on the outer layer is about 1mm, the thickness of the small holes on the inner layer is about 1mm, the small holes on the inner layer are taken out after being preheated to 240 ℃ in a muffle furnace, the small holes are poured into an impregnating solution A, fully contacted with the impregnating solution A for 0.5h for the first time of heat impregnation, the ZSM-5 molecular sieve after heat impregnation is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 ℃; and preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnating solution A, fully contacting for 0.5h, carrying out the second heat impregnation, stirring, evaporating and drying the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnating solution A at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And (3) calcining for 6 hours in an air atmosphere at 280 ℃ after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
20g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, a supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution B is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 65.42 percent, the ionic liquid accounts for 14.54 percent, and the active component accounts for 20.05 percent by weight. The weight of each oxide in the active component is CoO55.84%, mnO respectively 2 16.42％，MgO 8.27％，Fe 2 O 3 8.59％，NiO 10.88％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding into the fixed bed reactor with the catalyst, reacting under the hydrogen pressure of 26MPa and 100 ℃, sampling, filtering to obtain isophorone diamine reaction liquid, and indicating the transfer of IPN under the conditionThe conversion was 100% and the selectivity of isophorone diamine IPDA was 99.45%.
Example 2
1) Preparation of Supported catalyst precursor as in example 1
2) Preparation of Supported catalysts
10g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 70.68% by weight, the ionic liquid accounts for 7.85% by weight, and the active component accounts for 21.46% by weight. The weight of each oxide in the active component is CoO 56.28 percent, mnO respectively 2 16.83％，MgO 8.49％，Fe 2 O 3 8.16％，NiO 10.25％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the mixture into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 97.73%.
Example 3
1) Preparation of Supported catalyst precursor as in example 1
2) Preparation of Supported catalysts
20g of trimethyl hydroxyethyl ammonium bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, and the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalystDrying the precursor for 2 hours at 90 ℃ to obtain the supported catalyst. In the supported catalyst, the molecular sieve accounts for 65.58% by weight, the ionic liquid accounts for 14.57% by weight, and the active component accounts for 19.84% by weight. The weight of each oxide in the active component is CoO56.56%, mnO respectively 2 16.71％，MgO 8.15％，Fe 2 O 3 8.37％，NiO 10.21％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.61%.
Example 4
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of calcium nitrate hexahydrate, 20g of 50wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and the solution containing active components, namely an impregnating solution A, is formed after uniform mixing. 90g of ZSM-5 molecular sieve carrier with the specific surface of 410m is weighed again 2 And/g, wherein the diameter is about 4mm, the thickness of the large holes on the outer layer is about 1mm, the thickness of the small holes on the inner layer is about 1mm, the small holes are preheated to 240 ℃ in a muffle furnace and then poured into the impregnating solution A, fully contacted with the impregnating solution A for 0.5h to carry out first hot impregnation, the ZSM-5 molecular sieve after hot impregnation is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 ℃; the ZSM-5 molecular sieve after the first hot dipping is preheated to 240 ℃, poured into the dipping solution A to be fully contacted for 0.5h for the second hot dipping, the ZSM-5 molecular sieve after the hot dipping and the residual dipping solution A are stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 DEG Ch. And (3) calcining for 6 hours in an air atmosphere at 280 ℃ after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
20g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 64.28 percent, the ionic liquid accounts for 14.28 percent, and the active component accounts for 21.44 percent by weight. The weight of each oxide in the active component is CoO 51.23%, mnO respectively 2 15.52％，CaO16.19％，Fe 2 O 3 7.73％，NiO 9.33％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.36%.
Example 5
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50wt% manganese nitrate aqueous solution, 12g of palladium nitrate dihydrate and 3.1g of potassium nitrate are dissolved in 100ml of water, and the solution containing active components, namely an impregnating solution A, is formed after uniform mixing. 90g of ZSM-5 molecular sieve carrier with the specific surface of 410m is weighed again 2 Per g, diameter about 4mm, outer layer macroporous thickness about 1mm, inner layer medium and small Kong Houdu about 1mm, preheating to 240 deg.C in muffle furnace, and pouring into impregnating solution AFully contacting for 0.5h to carry out first hot dipping, filtering out ZSM-5 molecular sieve after hot dipping, stirring, evaporating and drying for 2h at 80 ℃, and then drying for 4h at 110 ℃; and preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnating solution A, fully contacting for 0.5h, carrying out the second heat impregnation, stirring, evaporating and drying the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnating solution A at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And (3) calcining for 6 hours in an air atmosphere at 280 ℃ after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
20g of methyltributylammonium tetrafluoroborate is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 63.74 percent, the ionic liquid accounts for 14.17 percent, and the active component accounts for 22.09 percent by weight. The weight of each oxide in the active component is CoO 49.37 percent, mnO respectively 2 14.94％，MgO 7.21％，KO 8.34％，PdO 20.13％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.61%.
Example 6
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate and 20g of 50 weight percent nitric acidThe manganese 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 a liquid containing active components, namely an impregnating solution A. 90g of 3A molecular sieve carrier with a specific surface of 196m is weighed again 2 And/g, wherein the diameter is about 4mm, the thickness of the large holes on the outer layer is about 1mm, the thickness of the small holes on the inner layer is about 1mm, the small holes are preheated to 240 ℃ in a muffle furnace and then poured into the impregnating solution A, the impregnated solution A is fully contacted with the impregnated solution A for 0.5h to carry out first heat impregnation, the 3A molecular sieve after heat impregnation is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 ℃; and preheating the 3A molecular sieve subjected to the first heat impregnation to 240 ℃, pouring the 3A molecular sieve into the impregnating solution A to fully contact for 0.5h for the second heat impregnation, stirring, evaporating and drying the 3A molecular sieve subjected to the heat impregnation and the residual impregnating solution A at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And (3) calcining for 6 hours in an air atmosphere at 280 ℃ after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
20g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 65.35 percent by weight, the ionic liquid accounts for 14.52 percent by weight, and the active component accounts for 20.13 percent by weight. The weight of each oxide in the active component is CoO 55.39%, mnO respectively 2 17.24％，MgO 8.29％，Fe 2 O 3 8.44％，NiO 10.64％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the catalyst into the fixed bed reactor filled with the catalyst, reacting under the hydrogen pressure of 26MPa and 100 ℃,sampling and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN under the condition is 100%, and the selectivity of isophorone diamine IPDA is 98.17%.
Example 7
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and the solution containing active components, namely an impregnating solution A, is formed after uniform mixing. 90g of ZSM-5 molecular sieve carrier with the specific surface of 410m is weighed again 2 And/g, wherein the diameter is about 4mm, the thickness of the large holes on the outer layer is about 1mm, the thickness of the small holes on the inner layer is about 1mm, the small holes are preheated to 240 ℃ in a muffle furnace and then poured into the impregnating solution A, fully contacted with the impregnating solution A for 0.5h to carry out first hot impregnation, the ZSM-5 molecular sieve after hot impregnation is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 ℃; and preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnation liquid A, fully contacting for 0.5h, carrying out the second heat impregnation, filtering the ZSM-5 molecular sieve subjected to the heat impregnation, and drying for 4h at 110 ℃. At this time, 70% of the total mass of the metal nitrate is loaded on the molecular sieve, and the catalyst precursor is obtained by calcining for 6 hours in an air atmosphere at 280 ℃ after drying.
2) Preparation of Supported catalysts
20g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 69.59 percent, the ionic liquid accounts for 14.47 percent, and the active component accounts for 14.94 percent by weight. The weight of each oxide in the active component is CoO 55.43%, mnO respectively 2 16.88％，MgO 8.19％，Fe 2 O 3 8.62％，NiO 10.87％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 98.22%.
Example 8
1) Preparation of Supported catalyst precursor
60g of cobalt nitrate hexahydrate, 15g of magnesium nitrate hexahydrate, 20g of 50wt% manganese nitrate aqueous solution, 12g of nickel nitrate hexahydrate and 3.1g of ferric nitrate nonahydrate are dissolved in 100ml of water, and the solution containing active components, namely an impregnating solution A, is formed after uniform mixing. 90g of ZSM-5 molecular sieve carrier with the specific surface of 410m is weighed again 2 And/g, wherein the diameter is about 4mm, the thickness of the large holes on the outer layer is about 1mm, the thickness of the small holes on the inner layer is about 1mm, the small holes are preheated to 240 ℃ in a muffle furnace and then poured into the impregnating solution A, fully contacted with the impregnating solution A for 0.5h to carry out first hot impregnation, the ZSM-5 molecular sieve after hot impregnation is filtered out, stirred, evaporated and dried for 2h at 80 ℃, and then dried for 4h at 110 ℃; and preheating the ZSM-5 molecular sieve subjected to the first heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnating solution A, fully contacting for 0.5h, carrying out the second heat impregnation, stirring, evaporating and drying the ZSM-5 molecular sieve subjected to the heat impregnation and the residual impregnating solution A at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And preheating the ZSM-5 molecular sieve subjected to the second heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnation liquid A, fully contacting for 0.5h, carrying out the third heat impregnation, filtering out the ZSM-5 molecular sieve subjected to the heat impregnation, stirring, evaporating and drying at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And preheating the ZSM-5 molecular sieve subjected to the third heat impregnation to 240 ℃, pouring the ZSM-5 molecular sieve into the impregnation liquid A, fully contacting for 0.5h, carrying out the fourth heat impregnation, filtering out the ZSM-5 molecular sieve subjected to the heat impregnation, stirring, evaporating and drying at 80 ℃ for 2h, and then drying at 110 ℃ for 4h. And (3) calcining for 6 hours in an air atmosphere at 280 ℃ after drying to obtain the supported catalyst precursor.
2) Preparation of Supported catalysts
20g of tributyl hexyl phosphine bis (trifluoromethanesulfonyl) imide salt is dissolved in 20ml of ethanol to prepare an impregnating solution B, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 65.41 percent, the ionic liquid accounts for 14.53 percent, and the active component accounts for 20.06 percent by weight. The weight of each oxide in the active component is CoO 55.54%, mnO respectively 2 17.03％，MgO 8.12％，Fe 2 O 3 8.59％，NiO 10.72％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 99.29%.
Comparative example 1
The catalyst in this comparative example was not loaded with ionic liquid
1) A supported catalyst precursor was prepared in the same manner as in example 7, except that the molecular sieve was 76.55% by weight and the active component was 23.45% by weight. The weight of each oxide in the active component is CoO55.79%, mnO respectively 2 17.12％，MgO 8.16％，Fe 2 O 3 8.45％，NiO10.48％。
2) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
3) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.25h -1 Adding the isophorone diamine into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling, and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 87.1%.
It can be seen that the selectivity of the isophorone diamine synthesis reaction from isophorone nitrile is significantly reduced when no ionic liquid is supported in the catalyst. The reason is that when the catalyst is not loaded with ionic liquid, the catalyst has no function of absorbing hydrogen and no function of preventing agglomeration of metal components, the airspeed 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 type of catalyst-supported ionic liquid in this comparative example is not within the scope of the present invention
1) Preparation of Supported catalyst precursor as in example 6
2) Preparation of Supported catalysts
20g of pyridine hydrochloride (boiling point 222-224 ℃) is prepared into an impregnating solution B in 20ml of ethanol, the supported catalyst precursor and the impregnating solution B are fully contacted at 60 ℃ until the impregnating solution is fully supported on the supported catalyst precursor, and the supported catalyst is obtained by drying at 90 ℃ for 2 hours. In the supported catalyst, the molecular sieve accounts for 65.38 percent, the ionic liquid accounts for 14.53 percent, and the active component accounts for 20.09 percent by weight. The weight of each oxide in the active component is CoO 55.55%, mnO respectively 2 16.96％，MgO 8.14％，Fe 2 O 3 8.5％，NiO 10.85％。
3) Preparation of the catalyst
100g of the prepared supported catalyst was charged into a fixed bed reactor, and then an on-line reduction treatment of the supported catalyst was performed under a pure hydrogen atmosphere at a reduction treatment temperature of 250℃for 48 hours to obtain a catalyst.
4) Preparation of isophorone diamine
Isophorone nitrile IPN and liquid ammonia are mixed in a molar ratio of 1:50, and the space velocity of the mass liquid material is 0.5h -1 Adding the mixture into the fixed bed reactor with the catalyst, reacting at the hydrogen pressure of 26MPa and the temperature of 100 ℃, sampling and filtering to obtain isophorone diamine reaction liquid, wherein the result shows that the conversion rate of IPN is 100% and the selectivity of isophorone diamine IPDA is 89.8%.
It can be seen that when the boiling point of the ionic liquid supported in the catalyst is lower than the temperature at which the supported catalyst is reduced to the catalyst, the ionic liquid is lost during the catalyst preparation process, resulting in a decrease in the selectivity of the reaction for synthesizing isophorone diamine from isophorone nitrile.
Example 9
The procedure for the preparation of isophorone diamine in step 4) shown in example 1 was run continuously, with the same reaction conditions, and the data are shown in table 1 below. Therefore, the catalyst can stably and continuously run for more than 500 hours, and the catalytic activity is not obviously reduced.
TABLE 1
| Run length/h | Conversion rate | Selectivity of |
| 10 | 100％ | 99.52％ |
| 50 | 100％ | 99.45％ |
| 100 | 100％ | 99.37％ |
| 200 | 100％ | 99.28％ |
| 500 | 100％ | 99.31％ |
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (15)
1. The method for synthesizing isophorone diamine takes isophorone nitrile, liquid ammonia and hydrogen as raw materials, and carries out reaction in the presence of a catalyst to obtain isophorone diamine, and is characterized in that: the catalyst is obtained by a reduction reaction of a supported catalyst; the supported catalyst comprises a carrier, and metal oxides and ionic liquid supported on the carrier, wherein the metal oxides comprise cobalt oxide, manganese dioxide and other metal oxides, the other metal oxides are selected from one or more combinations of transition metal oxides, alkali metal oxides and alkaline earth metal oxides, and the transition metal oxides are selected from one or more combinations of titanium dioxide, chromium trioxide, ferric oxide, nickel oxide, copper oxide, zinc oxide, molybdenum trioxide and palladium oxide; the carrier is a silicon-based material, the ionic liquid is one or two selected from 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; the quaternary phosphine ionic liquid is selected from one or a combination of more of alkyl triethyl phosphine bis (trifluoromethanesulfonyl) imine salt, alkyl tributyl phosphine bis (trifluoromethanesulfonyl) imine salt, alkyl triethyl phosphine tetrafluoroborate, alkyl tributyl phosphine tetrafluoroborate, alkyl triethyl phosphine hexafluorophosphate and alkyl tributyl phosphine hexafluorophosphate; the quaternary ammonium ionic liquid is selected from one or a combination of a plurality of trialkyl hydroxyethyl ammonium bis (trifluoromethanesulfonyl) imide salt, 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; the alkyl is a C1-C8 linear, branched or cyclic alkyl.
2. The method of synthesizing isophorone diamine according to claim 1, wherein: the temperature of the reduction reaction is 100-400 ℃.
3. The process for the synthesis of isophorone diamine according to claim 2, wherein: the temperature of the reduction reaction is 150-250 ℃.
4. The process for the synthesis of isophorone diamine according to claim 1, wherein: the silicon-based material is selected from one or a combination of more of 3A, 4A and 5A molecular sieves; and/or the silicon-based material is a hierarchical pore molecular sieve, wherein the thickness of the macropores of the outer layer is 0.5-1 mm, and the thickness of the mesopores of the inner layer is 1-2.5 mm.
5. The process for the synthesis of isophorone diamine according to claim 1, wherein: the silicon-based material is ZSM-5 with graded pore channels.
6. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: 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.
7. 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%.
8. A process for the synthesis of isophorone diamine according to any one of claims 1 to 4, wherein: in the metal oxide, the cobalt oxide accounts for 25 to 65 weight percent, the manganese dioxide accounts for 3 to 25 weight percent, the transition metal oxide accounts for 3 to 25 weight percent, the alkali metal oxide accounts for 1 to 20 weight percent, and the alkaline earth metal oxide accounts for 1 to 20 weight percent.
9. 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) Loading the catalyst into a fixed bed reactor;
2) Mixing isophorone nitrile and liquid ammonia to obtain a mixture, and adding the mixture into the fixed bed reactor;
3) Introducing hydrogen to react to obtain the isophorone diamine.
10. According to claim 9The method for synthesizing isophorone diamine is characterized in that: the molar ratio of isophorone nitrile to 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 airspeed of the mixture is 0.1 to 5h -1 。
11. A catalyst as claimed in any one of claims 1 to 10.
12. A method for preparing the catalyst of claim 11, wherein: the preparation method comprises the following steps:
1) Preparing a first impregnating solution from metal salt, preheating the carrier, and impregnating the carrier in the first impregnating solution to obtain a supported catalyst precursor;
2) Calcining the supported catalyst precursor to obtain a calcined supported catalyst precursor;
3) Preparing ionic liquid into a second impregnating solution, and impregnating the calcined supported catalyst precursor into the second impregnating solution to obtain the supported catalyst;
4) And reducing the supported catalyst under hydrogen to obtain the catalyst.
13. The method for preparing a catalyst according to claim 12, wherein: the metal salts include cobalt salts, manganese salts, and other metal salts selected from the group consisting of one or more of transition metal salts, alkali metal salts, and alkaline earth metal salts; the transition metal salt is selected from one or a combination of a plurality of titanium nitrate, chromium nitrate, ferric nitrate, nickel nitrate, copper nitrate, zinc nitrate, molybdenum nitrate and palladium nitrate.
14. The method for preparing a catalyst according to claim 12, wherein: the carrier is fully contacted with the first impregnating solution after being preheated in the step 1), the impregnated carrier is filtered, evaporated and dried to obtain a supported catalyst precursor, and the preheating temperature of the carrier is 50-400 ℃; and/or the calcining temperature in the step 2) is 100-600 ℃ and the time is 1-12 h; and/or, impregnating the calcined supported catalyst precursor in the step 3) with the second impregnating solution, and drying to obtain the supported catalyst, wherein the calcining temperature is 100-600 ℃, the time is 1-12 h, and the drying temperature is 80-150 ℃; and/or, the reduction temperature in the step 4) is 100-400 ℃ and the reduction time is 4-48 h.
15. The method for preparing a catalyst according to claim 12, wherein: repeating the preheating and the impregnation of the carrier for 2 to 6 times in the step 1); 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 to 1Nm based on 1Kg of the supported catalyst 3 /h。
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