Process for the hydrogenation of a dicyanoethyl tertiary amine with a reduced content of polycondensate

Abstract

The application provides a method for reducing the content of polycondensate in dicyanoethyl tertiary amine hydrogenation. The method uses dicyanoethyl alicyclic tertiary amine as raw material, and the target product is prepared through hydrogenation under the action of a catalyst G-P[BisPN]-M1 / M2O x The catalyst provided by the application can not only reduce the generation of heavy component polycondensate, improve the yield of the target product, but also prolong the service life of the catalyst and improve the production efficiency.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and specifically relates to a method for hydrogenating dicyandiethyl tertiary amine to reduce the content of condensation polymers. Background Technology

[0002] As epoxy resins continue to expand in the field of high-end materials, amine curing agents, as an important component, are playing an increasingly significant role. However, traditional epoxy amine curing agents have many performance problems, such as long surface drying time, poor mechanical properties, or poor corrosion resistance. Therefore, in order to meet market needs, it is very important to obtain high-performance amine curing agents from the source.

[0003] Michael addition modification of acrylonitrile is one of the existing modification strategies for amine curing agents. Modified amine curing agents obtained by hydrogenation of extended cyanoethyl groups often have stronger toughness and higher activity of branched amines, which can better improve the curing rate of the product. Therefore, this modification direction is worth studying and promoting.

[0004] At the molecular level, acrylonitrile-substituted amines can be monomolecularly or bimolecularly substituted, and the differences in molecular structure result in significant variations in their stability and physicochemical properties. Currently, publicly available technical research focuses extensively on the hydrogenation of secondary amines with mononitrile groups, while research on the hydrogenation of bis(nitrile) ethyl tertiary amines is almost nonexistent. Considering the poor thermal stability of bis(nitrile) ethyl tertiary amines due to steric hindrance, the hydrogenation yield is often low. Furthermore, the increased polycondensation byproducts caused by feedstock decomposition often severely inhibit catalyst activity, further exacerbating the production cost of diaminopropyl tertiary amines. Therefore, the hydrogenation process for bis(nitrile) ethyl tertiary amines presents significant challenges.

[0005] Patent document CN 113372241 A discloses a method for preparing bis(nitrile) ethyl tertiary amine, but does not further explain the hydrogenation process of bis(nitrile) ethyl tertiary amine, nor does it mention the difference in hydrogenation between mono(nitrile) ethyl secondary amine and bis(nitrile) ethyl tertiary amine. Patent document CN 101062485 B mentions the mechanism of deactivation and regeneration of nickel-based catalysts. Due to the condensation of nitrile compounds, the activity of the catalyst decreases. The catalyst is further regenerated by ammonolysis. Although this method can extend the service life of the catalyst, the production efficiency is slow and the production process is relatively complex.

[0006] In order to solve the problem of easy deactivation of nitrile hydrogenation catalysts, the patent documents with publication numbers CN 112934250 A and CN 107812534 A both use the impregnation method to prepare supported catalysts that are different from Raney catalysts. Although they can solve the problem of easy deactivation of Raney catalysts to a certain extent, they have not been able to improve the product yield, nor have they suppressed the formation of condensation polymers and their impact on catalyst activity.

[0007] To date, the hydrogenation process of cyanoethylamine compounds, especially cyanoethyl tertiary amines, has been hampered by technical problems such as the production of numerous condensation products and easy catalyst deactivation, which seriously hinders the expansion of modified amines in the field of high-end epoxy curing agents. Summary of the Invention

[0008] The purpose of this invention is to address the problems existing in the hydrogenation process of cyanoethylamines by proposing a method for hydrogenating dicyanoethyl tertiary amines that reduces the content of condensation polymers. This method not only reduces the content of condensation products in the final product, but also allows for the continuous reuse of the catalyst in more reaction batches, thereby reducing catalyst consumption per batch.

[0009] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0010] A method for hydrogenating dicyanoethyl tertiary amine to reduce condensation polymer content, wherein the method uses dicyanoethyl tertiary amine as raw material and reacts with catalyst GP[BisPN]-M1 / M2O. x Under the action of [a specific catalyst], the target product is obtained by hydrogenation; wherein, the metal element M1 in the catalyst is one or more of Co, Cu, Ni, Fe, Pd, and Pt, preferably Co and / or Ni; wherein, M2O x The catalyst is an oxide support for element M2, which is one or more of Al, Si, Ti and Zr, preferably Al and / or Si; wherein, G in the catalyst represents treatment with Grignard reagent and / or Grignard-like reagent; P represents the imprint left after removing the template agent; BisPN represents the adsorption of the template molecule dicyandiethyl alicyclic tertiary amine.

[0011] This invention protects the hydrogenation active sites of the catalyst by in-situ adsorption of nitrile groups onto the catalyst's active sites. Furthermore, it utilizes the unsaturation of the α-C atoms of the Grignard reagent and the strong adsorption of condensation reaction active sites on the catalyst surface to poison these side reaction sites. This inhibits further condensation of the intermediate aldehyde imine with the primary amine, achieving a directional conversion of nitrile hydrogenation to primary amine. It also reduces the formation of condensation polymers during hydrogenation, further slowing down the decay of catalyst activity. This not only improves the yield of the target product but also extends the catalyst lifetime and increases production efficiency.

[0012] In this invention, the method includes the following steps: adding the catalyst GP[BisPN]-M1 / M2O to a container. x The solvent is used as a base layer; under H2 atmosphere, the bis(nitrile) ethyl tertiary amine raw material is added and the reaction is continued until hydrogenation is completed; optionally, the catalyst is continuously applied until the catalyst is deactivated.

[0013] In one implementation scheme, the relevant reaction equation is shown below:

[0014]

[0015] In this invention, the dicyandiethyl tertiary amine is a dicyandiethyl alicyclic amine and / or a dicyandiethyl aromatic amine, preferably one or more of dicyandiethyl cyclopentylamine, 2-methyldicyandiethyl cyclopentylamine, dicyandiethyl cyclohexylamine, 2-methyldicyandiethyl cyclohexylamine, 2,3-dimethyl-dicyandiethyl cyclohexylamine, dicyandiethyl aniline, and 2-methyldicyandiethyl aniline, more preferably dicyandiethyl cyclohexylamine and / or dicyandiethyl aniline; preferably, the mass ratio of the dicyandiethyl tertiary amine to the catalyst is (10-100):1, more preferably (40-80):1.

[0016] In this invention, the solvent is a C1-C12 organic solvent, preferably methanol and / or ethanol; preferably, the mass ratio of solvent to catalyst is (10-500):1, more preferably (20-200):1.

[0017] In this invention, the hydrogenation is a semi-continuous process; preferably, the reaction temperature of the hydrogenation is 50–180°C, more preferably 70–150°C; preferably, the reaction pressure of the hydrogenation is absolute pressure 2–8 MPa, more preferably 4–6 MPa; preferably, the reaction time of the hydrogenation is 10–100 min, more preferably 15–35 min. The semi-continuous process is one of the commonly used processes in this field.

[0018] In this invention, the content of condensation polymer in the target product is less than 0.5 wt%.

[0019] Another object of the present invention is to provide a method for preparing the catalyst GP[BisPN]-M1 / M2O x The method.

[0020] A catalyst for preparation GP[BisPN]-M1 / M2O x The method wherein the catalyst is the catalyst used in the above method, and the preparation method of the catalyst is as follows:

[0021] S1: The precursor salt solution of M1 is added to the oxide support of M2 for impregnation, dried and calcined to obtain the catalyst host M1[O] / M2O x ;

[0022] S2: Catalyst bulk M1[O] / M2O x M1 / M2O was obtained by reduction under H2 atmosphere. x ;

[0023] S3: Inject dicyandiethyl alicyclic tertiary amine into the reactor to affect the M1 / M2O ratio. x Adsorption treatment was performed to obtain the catalyst BisPN-M1 / M2O. x ;

[0024] S4: Transfer catalyst BisPN-M1 / M2O x Add Grignard reagent and / or Grignard-like reagent, stir, and filter to obtain catalyst G-BisPN-M1 / M2O. x ;

[0025] S5: Switch the atmosphere to H2 to desorb the catalyst G-BisPN-M1 / M2O. x The target catalyst GP[BisPN]-M1 / M2O was obtained. x .

[0026] In this invention, the precursor salt of M1 in S1 is one or more of hydrochloride, nitrate, acetate and sulfate, preferably hydrochloride and / or nitrate; preferably, the concentration of the precursor salt solution of M1 in S1 is 5 to 50 wt%, more preferably 15 to 35 wt%.

[0027] In this invention, the ratio of the precursor salt of M1 to the oxide support of M2 in S1 is 0.05 to 0.5:1, more preferably 0.1 to 0.35:1.

[0028] In this invention, the immersion time in S1 is 20 to 200 minutes, preferably 60 to 100 minutes.

[0029] In this invention, the drying temperature in S1 is 50-150℃, preferably 80-120℃; the calcination temperature is 300-700℃, preferably 350-550℃; and the calcination time is 1-10h, preferably 3-5h.

[0030] In this invention, the reactor temperature in S2 is 200-300°C, preferably 220-280°C.

[0031] In this invention, the H2 flow rate in S2 is 10-1000 ml / min, preferably 200-600 ml / min.

[0032] In this invention, the reduction time in S2 is 2 to 6 hours, preferably 3 to 4 hours.

[0033] In this invention, the temperature in step S3 is 60–120°C, preferably 80–100°C.

[0034] In this invention, the amount of dicyandiethyl alicyclic tertiary amine added in S3 is M1 / M2O. x The amount is 1 to 10 times, more preferably 4 to 6 times.

[0035] In this invention, the adsorption treatment time in S3 is 30-180 min, preferably 60-120 min.

[0036] In this invention, the Grignard reagent and / or Grignard-like reagent in S4 is one or more of RMgX, RZnX, RSnX, RAlX, and RZrX, preferably RMgX and / or RZnX; wherein R is an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group, preferably CH3- and / or C6H5-; X is a halogen, preferably Cl or Br; preferably, the amount of Grignard reagent and / or Grignard-like reagent added is M1 / M2O. x The amount should be 1 to 5 times, preferably 2 to 3 times.

[0037] In this invention, the reaction temperature in S4 is 20–50°C, preferably 30–40°C; the stirring time is 40–160 min, preferably 80–120 min.

[0038] In this invention, the reaction temperature in step S5 is 120–180°C, preferably 140–160°C.

[0039] In this invention, the H2 flow rate in S5 is 10-1000 ml / min, preferably 400-800 ml / min; the desorption treatment time is 0.5-1.5 h, preferably 0.8-1.2 h.

[0040] The above-described method for preparing the catalyst is not the only method for preparing such catalysts. Those skilled in the art can choose other suitable methods as needed to obtain the catalyst of this application.

[0041] Another object of the present invention is to provide a GP[BisPN]-M1 / M2O x catalyst.

[0042] A GP[BisPN]-M1 / M2O x The catalyst is prepared by the above method, wherein the metal element M1 in the catalyst is one or more of Co, Cu, Ni, Fe, Pd, and Pt, preferably Co and / or Ni; M2O x The oxide support for element M2 is defined as one or more of Al, Si, Ti, and Zr, preferably Al and / or Si; wherein, G in catalyst indicates treatment with Grignard reagent and / or Grignard-like reagent; P indicates the imprint left after removal of the template agent; and BisPN indicates the adsorption of the template molecule dicyandiethyl alicyclic tertiary amine.

[0043] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0044] The technical solution of this invention achieves directional catalysis of bis(nitrile) ethyl tertiary amines, reducing the formation of condensation products, increasing the yield of the target product, extending catalyst life, and improving production efficiency. The process of this invention can achieve a 100% conversion rate of bis(nitrile) ethyl tertiary amines, a selectivity of over 98.5% for diaminopropyl tertiary amines, a selectivity of less than 1% for monoaminopropyl alicyclic amines, and a selectivity of less than 0.5% for condensation byproducts. Attached Figure Description

[0045] Figure 1 The XPS analysis results of Mg element in the catalyst in Example 1 are shown.

[0046] Figure 2 XPS analysis results of Zn element in the catalyst in Example 2;

[0047] Figure 3 The XPS analysis results of Al element in the catalyst in Example 2 are shown. Detailed Implementation

[0048] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the listed embodiments.

[0049] To better understand the hydrogenation reaction process for preparing bis(nitrile) ethyl tertiary amine according to the present invention, the hydrogenation is carried out using bis(nitrile) ethyl-cyclohexylamine and bis(nitrile) ethyl aniline as examples. This is merely a corresponding example and is not intended to limit the present invention.

[0050] Sources of reaction raw materials:

[0051] Dinitrile ethyl-cyclohexylamine: purity ≥99%, Wanhua Chemical;

[0052] Dinitrile ethyl-aniline: purity ≥99%, Wanhua Chemical;

[0053] Dicyandiethylcyclopentanamine: Purity ≥ 99%, Wanhua Chemical;

[0054] Methanol: purity ≥ 99.5%, Aladdin reagent;

[0055] Ethanol: purity ≥ 99.5%, Aladdin reagent;

[0056] CoCl2: Purity ≥ 99.7%, Aladdin reagent;

[0057] NiCl2: Purity ≥ 99.7%, Aladdin reagent;

[0058] PdCl2: Purity ≥ 99.7%, Aladdin reagent;

[0059] Al2O3: Purity ≥99%, Inokai;

[0060] SiO2: Purity ≥99%, Inokai;

[0061] CH3MgCl: Purity ≥98%, Inokai;

[0062] C6H5ZnBr: Purity ≥98%, Inokai;

[0063] CH3AlCl: Purity ≥98%, Inokai;

[0064] CH3AlBr: Purity ≥98%, Inokai;

[0065] Raney nickel: purity ≥98%, Xunkai;

[0066] Test method:

[0067] Gas chromatography: An Agilent 7890 and DB-5 (30 mm × 0.25 mm ID × 0.25 μm) column were used. The injector temperature was 280 °C and the detector temperature was 300 °C. The temperature program was as follows: initial column temperature 50 °C, hold for 2 min; increase to 80 °C at 5 °C / min, hold for 0 min; increase to 300 °C at 15 °C / min, hold for 15 min. The component content was determined by normalization.

[0068] Example 1

[0069] Catalyst preparation:

[0070] S1: 10g of 15wt% CoCl2 aqueous solution was added to 10g of Al2O3 support for equal volume impregnation. After impregnation for 60min, it was dried at 80℃ and calcined at 350℃ for 3h to obtain the catalyst host Co2O3 / Al2O3.

[0071] S2: The catalyst host Co2O3 / Al2O3 obtained in S1 is fixed in a tubular reactor, and high-temperature reduction is carried out at 220℃ for 3h while maintaining H2 flow rate of 200ml / min to obtain Co / Al2O3.

[0072] S3: Under N2 purging conditions, the tubular reactor was cooled to 80°C, and 43g of liquid dicyandiethylcyclohexylamine was injected into the S2 tubular reactor. The reduced catalyst host Co / Al2O3 was adsorbed for 60min to obtain the catalyst BisPN-Co / Al2O3.

[0073] S4: The catalyst BisPN-Co / Al2O3 was transferred to a batch reactor. Under N2 protection, 21.4 g of CH3MgCl reagent was added to the batch reactor. After stirring at 30°C for 80 min, the catalyst G-BisPN-Co / Al2O3 was obtained by filtration through a Buchner funnel.

[0074] S5: Switch the gas to H2, and further desorb the catalyst G-BisPN-Co / Al2O3 at 140℃ for 0.8h under the condition of H2 flow rate of 400ml / min, and finally obtain the catalyst GP[BisPN]-Co / Al2O3.

[0075] XPS analysis of Mg in the catalyst is attached. Figure 1 .

[0076] Hydrogenation reaction:

[0077] 1g of catalyst GP[BisPN]-Co / Al2O3 and 200g of methanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 70℃ under an H2 atmosphere and pressurized to an absolute pressure of 4MPa with H2. 40g of dicyandiethylcyclohexylamine was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 35 minutes until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropylcyclohexylamine reached 98.6%, the selectivity of deamination by-product was 0.5%, the selectivity of monoaminopropylcyclohexylamine was 0.5%, and the selectivity of polycondensation by-product was 0.4%.

[0078] Example 2

[0079] Catalyst preparation:

[0080] S1: 10g of 35wt% NiCl2 aqueous solution was added to 10g of SiO2 support for equal volume impregnation. After impregnation for 100min, it was dried at 120℃ and calcined at 550℃ for 5h to obtain the catalyst body Ni2O3 / SiO2.

[0081] S2: The catalyst host Co2O3 / Al2O3 obtained in S1 is fixed in a tubular reactor, and Ni / SiO2 is obtained by high-temperature reduction at 280℃ for 4h while maintaining H2 flow rate of 600ml / min.

[0082] S3: Under N2 purging conditions, the tubular reactor was cooled to 120°C, and 70g of liquid dicyandiethylcyclohexylamine was injected into the S2 tubular reactor. The reduced catalyst host Co / Al2O3 was adsorbed for 120min to obtain the catalyst BisPN-Ni / SiO2.

[0083] S4: Further, the catalyst BisPN-Ni / SiO2 was transferred to a batch reactor. Under N2 protection, 34.75g of C6H5ZnBr reagent was added to the batch reactor. After stirring at 40°C for 120min, the catalyst G-BisPN-Ni / SiO2 was obtained by filtration through a Buchner funnel.

[0084] S5: Finally, the gas was switched to H2, and the catalyst G-BisPN-Ni / SiO2 was further desorbed at 160℃ for 1.2h at an H2 flow rate of 800ml / min to obtain the catalyst GP[BisPN]-Ni / SiO2.

[0085] XPS analysis of Zn in the catalyst is attached. Figure 2 .

[0086] Hydrogenation reaction:

[0087] 1g of catalyst GP[BisPN]-Ni / SiO2 and 200g of ethanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 150℃ under an H2 atmosphere and pressurized to an absolute pressure of 6MPa with H2. 80g of dicyandiethylcyclohexylamine was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 15 minutes until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropylcyclohexylamine reached 98.8%, the selectivity of deamination by-product was 0.7%, the selectivity of monoaminopropylcyclohexylamine was 0.2%, and the selectivity of polycondensation by-product was 0.3%.

[0088] Example 3

[0089] Catalyst preparation:

[0090] S1: 10g of 25wt% PdCl2 aqueous solution was added to 10g of SiO2 support for equal volume impregnation. After impregnation for 80min, it was dried at 100℃ and calcined at 450℃ for 4h to obtain the catalyst host PdO / SiO2.

[0091] S2: The catalyst substrate PdO / SiO2 obtained in S1 is fixed in a tubular reactor, and Pd / SiO2 is obtained by high-temperature reduction at 250℃ for 3.5h while maintaining H2 flow rate at 400ml / min.

[0092] S3: Under N2 purging conditions, the tubular reactor was cooled to 90°C, and 58g of liquid dicyandiethyl aniline was injected into the S2 tubular reactor. The reduced catalyst substrate Pd / SiO2 was adsorbed for 100min to obtain the catalyst BisPN-Pd / SiO2.

[0093] S4: Further, the catalyst BisPN-Pd / SiO2 was transferred to a batch reactor. Under N2 protection, 23g of CH3AlCl reagent was added to the batch reactor. After stirring at 35°C for 100min, the catalyst G-BisPN-Pd / SiO2 was obtained by filtration through a Buchner funnel.

[0094] S5: Finally, the gas was switched to H2, and the catalyst G-BisPN-Pd / SiO2 was further desorbed at 150℃ for 1h under the condition of H2 flow rate of 600ml / min, and finally the catalyst GP[BisPN]-Pd / SiO2 was obtained.

[0095] XPS analysis of Al in the catalyst is attached. Figure 3 .

[0096] Hydrogenation reaction:

[0097] 2g of catalyst GP[BisPN]-Co / Al2O3 and 200g of methanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 130℃ under an H2 atmosphere and pressurized to an absolute pressure of 5MPa with H2. 120g of dicyandiethyl aniline was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 25 minutes until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropyl aniline reached 98.9%, the selectivity of deamination by-product was 0.5%, the selectivity of monoaminopropyl aniline was 0.3%, and the selectivity of polycondensation by-product was 0.3%.

[0098] Example 4

[0099] Catalyst preparation:

[0100] S1: 10g of 20wt% NiCl2 aqueous solution was added to 10g of Al2O3 support for equal volume impregnation. After impregnation for 80min, it was dried at 100℃ and calcined at 450℃ for 3h to obtain the catalyst body Ni2O3 / Al2O3.

[0101] S2: The catalyst substrate Ni2O3 / Al2O3 obtained in S1 is fixed in a tubular reactor, and Ni / Al2O3 is obtained by high-temperature reduction at 260℃ for 3 hours while maintaining H2 flow rate of 500 ml / min.

[0102] S3: Under N2 purging conditions, the tubular reactor was cooled to 90°C, and 65g of liquid dicyandiethyl aniline was injected into the S2 tubular reactor. The reduced catalyst substrate Ni / Al2O3 was subjected to adsorption treatment for 100min to obtain the catalyst BisPN-Ni / Al2O3.

[0103] S4: Further, the catalyst BisPN-Ni / Al2O3 was transferred to a batch reactor. Under N2 protection, 32.75g of CH3AlBr reagent was added to the batch reactor. After stirring at 30°C for 100min, the catalyst G-BisPN-Ni / Al2O3 was obtained by filtration through a Buchner funnel.

[0104] S5: Finally, the gas was switched to H2, and the catalyst G-BisPN-Ni / Al2O3 was further desorbed at 150℃ for 1h under the condition of H2 flow rate of 600ml / min, and finally the catalyst GP[BisPN]-Ni / Al2O3 was obtained.

[0105] Hydrogenation reaction:

[0106] 1.5g of catalyst GP[BisPN]-Ni / Al2O3 and 195g of ethanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 130℃ under an H2 atmosphere and pressurized to an absolute pressure of 5MPa with H2. 105g of dicyandiethyl aniline was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 30 minutes until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropyl aniline reached 99.1%, the selectivity of deamination by-product was 0.5%, the selectivity of monoaminopropyl aniline was 0.2%, and the selectivity of polycondensation by-product was 0.2%.

[0107] Example 5

[0108] Catalyst preparation:

[0109] S1: 10g of 15wt% CoCl2 aqueous solution was added to 10g of SiO2 support for equal volume impregnation. After impregnation for 70min, it was dried at 90℃ and calcined at 400℃ for 3h to obtain the catalyst host Co2O3 / SiO2.

[0110] S2: The catalyst host Co2O3 / SiO2 obtained in S1 is fixed in a tubular reactor, and high-temperature reduction is carried out at 230℃ for 3h while maintaining H2 flow rate of 400ml / min to obtain Co / SiO2.

[0111] S3: Under N2 purging conditions, the tubular reactor was cooled to 90°C, and 43g of liquid dicyandiethylcyclopentanamine was injected into the S2 tubular reactor. The reduced catalyst substrate Ni / Al2O3 was subjected to adsorption treatment for 110min to obtain the catalyst BisPN-Co / SiO2.

[0112] S4: Further, the catalyst BisPN-Co / SiO2 was transferred to a batch reactor. Under N2 protection, 32.04 g of CH3AlCl reagent was added to the batch reactor. After stirring at 30°C for 100 min, the catalyst G-BisPN-Co / SiO2 was obtained by filtration through a Buchner funnel.

[0113] S5: Finally, the gas was switched to H2, and the catalyst G-BisPN-Co / SiO2 was further desorbed at 150℃ for 1 h at an H2 flow rate of 600 ml / min to obtain the catalyst GP[BisPN]-Co / SiO2.

[0114] Hydrogenation reaction:

[0115] 2.0 g of catalyst GP[BisPN]-Co / SiO2 and 200 g of methanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 150 °C under an H2 atmosphere. The pressure was increased to 5 MPa with H2. 120 g of dicyandiethylcyclopentanamine was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 25 min until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropylcyclopentanamine reached 99.2%, the selectivity of deamination by-product was 0.3%, the selectivity of monoaminopropylcyclopentanamine was 0.2%, and the selectivity of polycondensation by-product was 0.3%.

[0116] Example 6

[0117] Catalyst preparation:

[0118] S1: 10g of 25wt% Ni(NO3)2 aqueous solution was added to 10g of Al2O3 support for equal volume impregnation. After impregnation for 90min, it was dried at 110℃ and calcined at 500℃ for 4h to obtain the catalyst body Ni2O3 / Al2O3.

[0119] S2: The catalyst substrate Ni2O3 / Al2O3 obtained in S1 is fixed in a tubular reactor, and Ni / Al2O3 is obtained by high-temperature reduction at 270℃ for 4 hours while maintaining H2 flow rate of 500 ml / min.

[0120] S3: Under N2 purging conditions, the tubular reactor was cooled to 90°C, and 53g of liquid 2-methyldicyandiethyl aniline was injected into the S2 tubular reactor. The reduced catalyst substrate Ni / Al2O3 was subjected to adsorption treatment for 90min to obtain the catalyst BisPN-Ni / Al2O3.

[0121] S4: Further, the catalyst BisPN-Ni / Al2O3 was transferred to a batch reactor. Under N2 protection, 21.01g of C6H5ZnBr reagent was added to the batch reactor. After stirring at 30°C for 110min, the catalyst G-BisPN-Ni / Al2O3 was obtained by filtration through a Buchner funnel.

[0122] S5: Finally, the gas was switched to H2, and the catalyst G-BisPN-Ni / Al2O3 was further desorbed at 160℃ for 1h under the condition of H2 flow rate of 700ml / min, and finally the catalyst GP[BisPN]-Ni / Al2O3 was obtained.

[0123] Hydrogenation reaction:

[0124] 2.0 g of catalyst GP[BisPN]-Ni / Al2O3 and 200 g of ethanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 140 °C under an H2 atmosphere. The pressure was increased to 6 MPa with H2. 100 g of 2-methyldicyanoethyl aniline was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 35 min until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of 2-methyldiaminopropyl aniline reached 99.1%, the selectivity of deamination byproduct was 0.4%, the selectivity of 2-methylmonoaminopropyl aniline was 0.3%, and the selectivity of polycondensation byproduct was 0.2%.

[0125] Comparative Example 1

[0126] Compared to hydrogenation reactions using conventional catalysts.

[0127] 2g of Raney nickel catalyst and 200g of ethanol were added to the reactor. The reactor was purged three times with N2 and H2 respectively. The reactor was heated to 130℃ under an H2 atmosphere and pressurized to an absolute pressure of 5MPa with H2. 120g of dicyandiethylcyclohexylamine was continuously added through a feed pump. After the feed was completed, the reactor was reacted for 40 minutes until hydrogen absorption was completed. The reaction solution was collected and sampled for chromatographic analysis. The selectivity of diaminopropylcyclohexylamine reached 96.5%, the selectivity of deamination by-product was 1.2%, the selectivity of monoaminopropylcyclohexylamine was 0.8%, and the selectivity of polycondensation by-product was 1.5%.

[0128] The application of this invention is not limited to the above embodiments. For those skilled in the art, any modifications or changes made in accordance with the spirit of this invention are included within the scope of protection intended by this invention.

Claims

1. A method for preparing the catalyst GP[BisPN]-M1 / M2O x The method is characterized by, The catalyst is prepared by: S1: The precursor salt solution of M1 is added to the oxide support of M2 for impregnation, dried and calcined to obtain the catalyst host M1[O] / M2O x ; S2: Catalyst bulk M1[O] / M2O x M1 / M2O was obtained by reduction under H2 atmosphere. x ; S3: Inject dicyandiethyl alicyclic tertiary amine into the reactor to affect the M1 / M2O ratio. x Adsorption treatment was performed to obtain the catalyst BisPN-M1 / M2O. x ; S4: Transfer catalyst BisPN-M1 / M2O x Add Grignard reagent and / or Grignard-like reagent, stir, and filter to obtain catalyst G-BisPN-M1 / M2O. x ; S5: Switch the atmosphere to H2 to desorb the catalyst G-BisPN-M1 / M2O. x The target catalyst GP[BisPN]-M1 / M2O was obtained. x ; Wherein, M1 is one or more of Co, Cu, Ni, Fe, Pd, and Pt; M2O x The oxide support for element M2 is indicated, where M2 is one or more of Al, Si, Ti, and Zr; BisPN indicates the adsorption of the template molecule dicyandiethyl alicyclic tertiary amine; G represents a Grignard reagent and / or a Grignard-like reagent.

2. The method for preparing the catalyst according to claim 1, characterized in that, The precursor salt of M1 in S1 is one or more of hydrochloride, nitrate, acetate and sulfate. And / or, the ratio of the precursor salt of M1 to the oxide support of M2 in S1 is 0.05 to 0.5:1; And / or, the immersion time in S1 is 20 to 200 minutes; And / or, the drying temperature in S1 is 50–150℃; the calcination temperature is 300–700℃; and the calcination time is 1–10h.

3. The method for preparing the catalyst according to claim 2, characterized in that, The precursor salt of M1 in S1 is a hydrochloride and / or a nitrate; The concentration of the precursor salt solution of M1 in S1 is 5-50 wt%; And / or, the ratio of the precursor salt of M1 to the oxide support of M2 in S1 is 0.1 to 0.35:1; And / or, the immersion time in S1 is 60 to 100 minutes; And / or, the drying temperature in S1 is 80-120℃; the calcination temperature is 350-550℃; and the calcination time is 3-5h.

4. The method for preparing the catalyst according to claim 3, characterized in that, The concentration of the precursor salt solution of M1 in S1 is 15–35 wt%.

5. The method for preparing the catalyst according to claim 1, characterized in that, The reactor temperature in S2 is 200–300°C; And / or, the H2 flow rate in S2 is 10–1000 ml / min; And / or, the reduction time in S2 is 2 to 6 hours.

6. The method for preparing the catalyst according to claim 5, characterized in that, The reactor temperature in S2 is 220–280°C; And / or, the H2 flow rate in S2 is 200–600 ml / min; And / or, the reduction time in S2 is 3 to 4 hours.

7. The method for preparing the catalyst according to claim 1, characterized in that, The temperature in S3 is 60–120°C; And / or, the amount of dicyandiethyl alicyclic tertiary amine added in S3 is M1 / M2O x 1 to 10 times the amount; And / or, the adsorption treatment time in S3 is 30–180 min.

8. The method for preparing the catalyst according to claim 7, characterized in that, The temperature in S3 is 80–100°C; And / or, the amount of dicyandiethyl alicyclic tertiary amine added in S3 is M1 / M2O x 4 to 6 times the amount; And / or, the adsorption treatment time in S3 is 60–120 min.

9. The method for preparing the catalyst according to claim 1, characterized in that, The Grignard reagent and / or Grignard-like reagent in S4 is one or more of RMgX, RZnX, RSnX, RAlX, and RZrX; wherein R is an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group; and X is a halogen. And / or, the reaction temperature in S4 is 20–50°C; the stirring time is 40–160 min.

10. The method for preparing the catalyst according to claim 9, characterized in that, The Grignard reagent and / or Grignard-like reagent in S4 are RMgX and / or RZnX; wherein R is CH3- and / or C6H5-; and X is Cl or Br; The amount of the formative reagent and / or format-like reagent added in S4 is M1 / M2O. x 1 to 5 times the amount; And / or, the reaction temperature in S4 is 30–40°C; the stirring time is 80–120 min.

11. The method for preparing the catalyst according to claim 10, characterized in that, The amount of the formative reagent and / or format-like reagent added in S4 is M1 / M2O. x Two to three times the amount.

12. The method for preparing the catalyst according to claim 1, characterized in that, The reaction temperature in S5 is 120–180°C; And / or, the H2 flow rate in S5 is 10–1000 ml / min; the desorption treatment time is 0.5–1.5 h.

13. The method for preparing the catalyst according to claim 12, characterized in that, The reaction temperature in S5 is 140–160°C; And / or, the H2 flow rate in S5 is 400–800 ml / min; the desorption treatment time is 0.8–1.2 h.

14. A GP[BisPN]-M1 / M2O x The catalyst is prepared by the method according to any one of claims 1-13, wherein the metal element M1 in the catalyst is one or more of Co, Cu, Ni, Fe, Pd, and Pt; M2O x The oxide support for element M2 is indicated, where M2 is one or more of Al, Si, Ti, and Zr; BisPN indicates the adsorption of the template molecule dicyandiethyl alicyclic tertiary amine.

15. The catalyst according to claim 14, characterized in that, The metal element M1 in the catalyst is Co and / or Ni; M2 is Al and / or Si.

16. A method for hydrogenating dicyandiethyl tertiary amine with reduced condensation polymer content, wherein the hydrogenation method uses a catalyst prepared by any one of claims 1-13, or a catalyst as described in claim 14 or 15, characterized in that, The method uses dicyandiethyl tertiary amine as a raw material, and is carried out in the presence of the catalyst GP[BisPN]-M1 / M2O. x Under the influence of hydrogenation, the target product is obtained. The metal element M1 in the catalyst is one or more of Co, Cu, Ni, Fe, Pd, and Pt; Among them, M2O x The oxide support for element M2 is one or more of Al, Si, Ti, and Zr. In this context, BisPN represents the adsorption of the template molecule dicyandiethyl alicyclic tertiary amine.

17. The method according to claim 16, characterized in that, The metal element M1 in the catalyst is Co and / or Ni, and M2 is Al and / or Si.

18. The method according to claim 16 or 17, characterized in that, The method includes the following steps: adding the catalyst GP[BisPN]-M1 / M2O to a container. x The solvent is used as a base layer; under H2 atmosphere, the bis(nitrile) ethyl tertiary amine raw material is added and the reaction is continued until hydrogenation is completed; optionally, the catalyst is continuously applied until the catalyst is deactivated.

19. The method according to claim 18, characterized in that, The dicyandiethyl tertiary amine is a dicyandiethyl alicyclic amine and / or a dicyandiethyl aromatic amine; And / or, the solvent is a C1-C12 organic solvent; And / or, the hydrogenation is a semi-continuous process; And / or, the content of condensation polymers in the target product is less than 0.5 wt%.

20. The method according to claim 19, characterized in that, The dicyandiethyl tertiary amine is one or more of the following: dicyandiethylcyclopentylamine, 2-methyldicyandiethylcyclopentylamine, dicyandiethylcyclohexylamine, 2-methyldicyandiethylcyclohexylamine, 2,3-dimethyl-dicyandiethylcyclohexylamine, dicyandiethyl aniline, and 2-methyldicyandiethyl aniline. The mass ratio of the dicyandiethyl tertiary amine to the catalyst is (10-100):1; And / or, the solvent is methanol and / or ethanol; The mass ratio of solvent to catalyst is (10–500):1; And / or, the hydrogenation is a semi-continuous process; The hydrogenation reaction temperature is 50–180°C; The hydrogenation reaction pressure is absolute pressure 2-8 MPa; The hydrogenation reaction time is 10 to 100 minutes.

21. The method according to claim 20, characterized in that, The dicyandiethyl tertiary amine is dicyandiethyl cyclohexylamine and / or dicyandiethyl aniline; The mass ratio of the dicyandiethyl tertiary amine to the catalyst is (40-80):1; The mass ratio of solvent to catalyst is (20-200):1; The hydrogenation reaction temperature is 70–150°C; The hydrogenation reaction pressure is absolute pressure 4-6 MPa; The hydrogenation reaction time is 15–35 min.

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