CN111482178A

CN111482178A - Supported nano nickel-based catalyst and preparation method and application thereof

Info

Publication number: CN111482178A
Application number: CN202010410954.5A
Authority: CN
Inventors: 黄志威; 李雪梅
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2020-04-15
Filing date: 2020-05-15
Publication date: 2020-08-04

Abstract

The invention discloses a supported nano nickel-based catalyst and a preparation method and application thereofIncluding Al₂O₃、ZrO₂、SiO₂And MgO, or a combination of two or more thereof. The method takes 5-diethylamino-2-pentanone obtained by converting 5-chloro-2-pentanone as a raw material to perform continuous reductive amination reaction under the action of a supported nano Ni-based catalyst and ammonia water to obtain the purity>99% of the target product; the catalyst used in the invention has the advantages of low cost, high production efficiency, good stability, simple operation, good safety and convenient industrial production.

Description

Supported nano nickel-based catalyst and preparation method and application thereof

Technical Field

The invention belongs to the technical field of synthesis of medical intermediates, and particularly relates to a supported nano nickel-based catalyst, a preparation method and application thereof, and more particularly relates to application of the supported nano nickel-based catalyst in continuous production of a chloroquine drug key intermediate N, N-diethyl-1, 4-pentanediamine.

Background

Chloroquine phosphate is white crystalline powder, and has no odor and bitter taste. Changing color gradually when meeting light; the aqueous solution shows acidic reaction, is easy to dissolve in water, and is almost insoluble in ethanol, chloroform and diethyl ether. The chemical name of the compound is N ', N' -diethyl-N4- (7-chloro-4-quinolyl) -1, 4-pentanediamine diphosphate, and the molecular formula is as follows: c₁₈H₂₆ClN₃·2H₃PO₄Molecular weight of 515.87, and the structural formula is as follows:

can be used for treating malaria such as malignant malaria and vivax malaria sensitive to chloroquine, and extraintestinal amebiasis, and also has antirheumatic and antiviral effects. With the expansion of the application of chloroquine phosphate in the aspect of antivirus, the demand of the medicine is increased greatly, and the key side chain compound of N, N-diethyl-1, 4-pentanediamine is in short supply.

Currently, N-diethyl-1, 4-pentanediamine is mainly synthesized by reductive amination of 5-diethylamino-2-pentanone in an intermittent high-pressure reaction kettle under the conditions of liquid ammonia and hydrogen by using Raney's nickel as a catalyst, and the reaction is as follows:

the reaction temperature is 95 ℃, the reaction pressure is 0.7-0.8MPa, and the 5-diethylamino-2-pentanone is obtained by chlorinating 3-acetyl propanol and aminating diethylamine; or 3-acetyl propanol is obtained by bromination and diethylamine amination (Hou le shan, mainly compiled "China Fine chemical products Collection-raw materials and intermediates 10396", 2006, P.499, 5-diethylamino-2-pentanone), and the production technology is mature. The Raney nickel catalyst is prepared by dissolving nickel-aluminum alloy into aluminum under strong alkali, generates a large amount of aluminum-containing waste alkali, and has serious environmental pollution. Although the Raney nickel catalyst achieves a yield of more than 88% in the reductive amination reaction of 5-diethylamino-2-pentanone, the catalyst is lost and inactivated in the production process, the production efficiency of the batch tank reaction process is low, and the energy consumption is high, so that the production cost of the target chloroquine side chain compound is high. In addition, the Raney nickel catalyst is improper to operate and is easy to cause fire, and the use of liquid ammonia has larger potential safety hazard. Therefore, the synthesis of the side chain compound needs to develop a novel efficient catalyst, and the production process is improved to improve the production efficiency and safety, and reduce the production cost and environmental pollution.

Disclosure of Invention

The invention mainly aims to provide a supported nano nickel-based catalyst, and a preparation method and application thereof, so as to overcome the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a supported nano nickel-based catalyst which comprises a carrier, and a main active component and an auxiliary agent which are loaded on the carrier, wherein the main active component comprises Ni, the auxiliary agent comprises any one or a combination of more than two of Fe, Co, Cu, Zn, Mn, Ca, L a, Y, Ce and Ga, and the carrier comprises Al₂O₃、ZrO₂、SiO₂And MgO, or a combination of two or more thereof.

The implementation of the invention also provides a preparation method of the supported nano nickel-based catalyst, which comprises the following steps: the supported nano nickel-based catalyst is prepared by adopting a coprecipitation method and/or a deposition precipitation method.

The invention also provides the application of the supported nano nickel-based catalyst in the continuous production of the N, N-diethyl-1, 4-pentanediamine.

The invention also provides a method for continuously producing N, N-diethyl-1, 4-pentanediamine, which comprises the following steps:

continuously inputting a mixed solution containing 5-diethylamino-2-pentanone and a nitrogen source into a fixed bed reactor filled with a supported nano nickel-based catalyst in a reducing atmosphere to carry out reductive amination reaction to prepare the N, N-diethyl-1, 4-pentanediamine.

Further, the reductive amination reaction conditions include: the temperature is 80-140 ℃, the pressure is 0.1-1.0 MPa, and the feeding mass space velocity is 0.2-1.0 h^-1。

In the invention, the N, N-diethyl-1, 4-pentanediamine is a chloroquine phosphate side chain compound and is a key intermediate of chloroquine medicaments.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention can continuously and efficiently produce the N, N-diethyl-1, 4-pentanediamine, the 5-diethylamino-2-pentanone, ammonia water, ammonia gas or urea are taken as raw materials, the N, N-diethyl-1, 4-pentanediamine is produced by continuous reductive amination reaction in a fixed bed reactor, a reaction product and a catalyst are directly separated in the reaction process, separate filtration or centrifugal treatment is not needed, the production operation flow is simplified, and the production efficiency is obviously improved;

(2) the method takes the supported non-noble metal nickel as the catalyst to realize the continuous stable reductive amination of the 5-diethylamino-2-pentanone and the ammonia water to produce the N, N-diethyl-1, 4-pentanediamine, and has the advantages of low cost of the catalyst, good service life stability, high safety, less pollution, convenience for large-scale industrial production and improvement of economic benefit.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is an XRD characterization of catalyst 4 in example 1 of the present invention;

FIG. 2 is a TEM representation of catalyst 4 in example 1 of the present invention;

FIG. 3 is an XRD characterization of catalyst 7 in example 1 of the present invention;

FIG. 4 is a TEM representation of catalyst 7 in example 1 of the present invention;

FIG. 5 is a continuous reaction stability curve for catalyst number 4 as determined in example 9 of the present invention;

FIG. 6 is a chromatogram of a product fraction of N, N-diethyl-1, 4-pentanediamine obtained in example 9 of the present invention.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

One aspect of the embodiment of the invention provides a supported nano nickel-based catalyst, which comprises a carrier, and a main active component and an auxiliary agent which are supported on the carrier, wherein the main active component comprises Ni, the auxiliary agent comprises any one or a combination of more than two of Fe, Co, Cu, Zn, Mn, Ca, L a, Y, Ce and Ga, and the carrier comprises Al₂O₃、ZrO₂、SiO₂And MgO or a mixture of two or more of themA combination of (a) and (b).

In some specific embodiments, the content of the main active component in the supported nano nickel-based catalyst is 15 to 75 wt%, preferably 20 to 70 wt%.

Furthermore, the content of the auxiliary agent in the supported nano nickel-based catalyst is 0.1-10 wt%.

In another aspect of the embodiments of the present invention, there is provided a preparation method of the supported nano nickel-based catalyst, including: the supported nano nickel-based catalyst is prepared by adopting a coprecipitation method and/or a deposition precipitation method.

In some more specific embodiments, the preparation method may specifically include: and mixing a mixed metal salt solution containing a main active component and an auxiliary agent, an alkali liquor with any one of a metal salt solution of the carrier, a carrier oxide powder solution and a carrier colloidal particle solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the supported nano nickel-based catalyst.

Further, the alkali solution is any one or a combination of two or more of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and a potassium carbonate solution, and is not limited thereto.

Further, the pH value of the mixed solution is kept between 9.0 and 11 during the precipitation treatment.

Further, the aging treatment conditions include: the temperature is 30-100 ℃ and the time is 2-24 h.

Further, the conditions of the roasting treatment include: the temperature is 400 ℃ and 800 ℃, and the time is 2-8 h.

Further, the reduction treatment conditions comprise that the temperature is 350-750 ℃ and the time is 2-10h in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 80-100m L/min.

In some more specific embodiments, the preparation method of the supported nano nickel-based catalyst comprises:

weighing active metal nickel and metal salt of an auxiliary agent according to a proportion at room temperature, adding deionized water to prepare a solution A with the total concentration of the active metal and the auxiliary agent salt being 0.1-1.0 mol/L, preparing an alkali solution B with the concentration being 1-6 mol/L, adding metal salt of a carrier or commercially available oxide powder or colloidal particles according to a proportion in a reaction tank, adding deionized water (the addition amount is 10 times of that of the carrier metal salt or commercially available oxide powder or colloidal particles) to fully stir and mix uniformly, then dropping the salt solution A and the alkali solution B into the reaction tank under rapid stirring, keeping the pH value of 9-11 in the precipitation process, heating to 30-100 ℃ after the precipitation is finished, aging for 2-24h, filtering after the aging is finished, washing with the deionized water until the filtrate is neutral, drying the filter cake at 110 ℃ for 12h, roasting at 400-800 ℃ for 2-8h, tabletting, sieving for 20-40 mesh catalyst particles, filling 4g in a fixed bed reactor, and finally heating to 350-750 ℃ in a hydrogen atmosphere (the flow rate of 80-100m L/min) to activate the.

In another aspect of the embodiments of the present invention, there is also provided an application of the supported nano nickel-based catalyst in the continuous production of N, N-diethyl-1, 4-pentanediamine.

Yet another aspect of embodiments of the present invention provides a method for continuously producing N, N-diethyl-1, 4-pentanediamine, comprising:

In some more specific embodiments, the conditions of the reductive amination reaction include: the temperature is 80-140 ℃, the pressure is 0.1-1.0 MPa, and the feeding mass space velocity is 0.2-1.0 h^-1。

Further, the nitrogen source includes any one or a combination of two or more of ammonia, and urea, and is not limited thereto.

Further, the reducing atmosphere is formed of a reducing gas.

Further, the reducing gas includes hydrogen and/or a mixed gas containing hydrogen.

Further, the molar ratio of the reducing gas to the 5-diethylamino-2-pentanone is 5-20: 1.

Further, the molar ratio of the 5-diethylamino-2-pentanone to the nitrogen source is 1: 2-8.

In some more specific embodiments, the method further comprises: further comprising: 5-diethylamino-2-pentanone, a nitrogen source and an alcohol solvent are mixed to form a mixed solution. The alcohol solvent can increase the miscibility of the 5-diethylamino-2-pentanone with ammonia water, ammonia gas or urea.

Further, the alcohol solvent includes any one or a combination of two or more of methanol, ethanol, propanol, and isopropanol, and is not limited thereto.

Further, the mass ratio of the alcohol solvent to 5-diethylamino-2-pentanone is 1-3: 1.

In the invention, the synthesis method of the 5-diethylamino-2-pentanone comprises the following steps: reacting 5-chloro-2-pentanone with diethylamine at 90-120 ℃ for 4-10h in protective atmosphere, dissolving the obtained solid product with NaOH solution, standing for layering, collecting upper-layer organic matter, distilling at normal pressure to evaporate low-boiling point diethylamine, and distilling at reduced pressure to obtain 5-diethylamino-2-pentanone with purity of more than 98.5%.

Further, the protective atmosphere includes any one of an inert gas atmosphere and a nitrogen gas atmosphere, and is not limited thereto.

Further, the dosage ratio of the 5-chloro-2-pentanone to the diethylamine is 1: 1.5-3.

Further, the pressure of the protective atmosphere is 0.25-1 MPa.

The invention provides a method for continuously and efficiently synthesizing a target chloroquine key side chain compound (N, N-diethyl-1, 4-pentanediamine), which uses a cheap, efficient and stable supported nano non-noble metal catalyst to realize the continuous reductive amination reaction of 5-diethylamino-2-pentanone in a fixed bed reactor, reduces the separation process, loss and inactivation of the catalyst, obviously improves the production efficiency and safety of the chloroquine key side chain compound, reduces the production cost and reduces three wastes.

The product of the invention is mainly N, N-diethyl-1, 4-pentanediamine and the main byproduct is 5-diethylamino-2-pentanol through Agilent 7890A/5975C GC-MS combined analysis. The product was quantitatively analyzed by Agilent 7890A gas chromatography, HP-5 capillary chromatography.

The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.

Example 1: preparation and characterization of supported nano nickel-based catalyst

The supported nanometer nickel-based catalyst is prepared by a coprecipitation method, active metal nickel and metal salt of an auxiliary agent are weighed according to a proportion at room temperature, deionized water is added to prepare a solution A with the total concentration of the active metal and the auxiliary agent salt being 0.1 mol/L, and NaOH with the concentration of 4 mol/L and Na with the concentration of₂CO₃Adding metal salt or commercial oxide powder or colloid particles of a carrier into a reaction tank in proportion, adding deionized water (the addition amount is 10 times of that of the carrier metal salt or commercial oxide powder or colloid particles), fully stirring and uniformly mixing, then simultaneously dripping a salt solution A and an alkali solution B into the reaction tank under rapid stirring, keeping the pH value of the precipitation process to be 9.5-10, heating to 80 ℃ after the precipitation is finished, aging for 4h, filtering after the aging is finished, washing by using the deionized water until the filtrate is neutral, drying a filter cake at 110 ℃ for 12h, roasting at 500 ℃ for 4h, tabletting and screening 20-40 mesh catalyst particles, filling 4g into a fixed bed reactor, heating to 550 ℃ in a hydrogen atmosphere (the flow rate is 80-100m L/min), reducing and activating for 4h to obtain an activated catalyst, reducing and activating a small amount of screened powder catalyst under the same condition, and then reducing and activating in 1% O₂-N₂XRD and transmission electron microscopy characterization (TEM) are carried out after room temperature passivation is carried out for 2h in the gas flow, and fig. 1 and fig. 2 are respectively XRD and TEM characterization images of the catalyst 4 in the table 1 of the embodiment; FIGS. 3 and 4 are XRD and TEM representations of catalyst 7 of Table 1 in this example, respectively; the different catalyst compositions and metallic nickel grain sizes are shown in table 1. The catalyst has good dispersibility, and the grain size is below 8 nm.

TABLE 1 catalyst Synthesis conditions, compositions and characterization results

^*The Arabic numerals in front of the active metal and the auxiliary agent represent mass percent, and the proportion in brackets is a molar ratio.

Example 2

The preparation process and the composition of the catalyst are the same as those of the catalyst 1, except that the concentration of the metal salt solution A is 0.5mo L/L, the catalyst is aged for 2h at 100 ℃, washed and dried, then roasted for 2h at 800 ℃, and reduced and activated for 2h at 750 ℃ to obtain a catalyst 8, and XRD (X-ray diffraction) characterization results show that the grain size of the reduced and activated catalyst is 6.2 nm;

example 3

The preparation process of the catalyst is the same as that of the catalyst 5, except that the concentration of the metal salt solution A is 1.0mo L/L, the catalyst is aged for 24h at 30 ℃, washed and dried, then roasted for 8h at 400 ℃, and reduced and activated for 10h at 350 ℃ to obtain a catalyst 9, and XRD (X-ray diffraction) characterization results show that the grain size of the reduced and activated catalyst is 5.8 nm;

example 4

The preparation and composition of the catalyst were the same as in example 3, except that 1 mol/L Na₂CO₃Instead of 4 mol/L NaOH and 1 mol/L Na₂CO₃Controlling the pH value of the mixed alkali in the precipitation process to be 9.0 to obtain a catalyst 10, wherein XRD (X-ray diffraction) characterization results show that the grain size of the reduction activation catalyst is 5.2 nm;

example 5

The preparation process and composition of the catalyst are the same as those of example 3, except that 6 mol/L KaOH is used to replace 4 mol/L NaOH and 1 mol/L Na₂CO₃Controlling the pH value of the mixed alkali in the precipitation process to be 9.0 to obtain a catalyst 10, wherein XRD (X-ray diffraction) characterization results show that the grain size of the reduction activation catalyst is 6.0 nm;

example 6: amination reaction performance of mixture of 5-diethylamino-2-pentanone, ammonia water and alcohol solvent catalyzed by different catalysts

1) Synthesizing 5-diethylamino-2-pentanone, weighing 400g of 5-chloro-2-pentanone and 640g of diethylamine, adding into a 2L reaction kettle, sealing the kettle, and introducing 0.45MPa N₂Heating to 110 ℃ for reaction for 6h, cooling and decompressing, dissolving the solid product by using 1 mol/L NaOH, standing for layering, collecting the upper-layer organic matter, distilling at normal pressure to evaporate low boiling pointDiethylamine, then vacuum distilling to obtain purity>98.5% of 5-diethylamino-2-pentanone.

2) Preparing a reaction solution: weighing 5-diethylamino-2-pentanone, organic alcohol solvent and 25% strong ammonia water according to the mass ratio of 1:1:3 to prepare reaction liquid.

3) Fixed bed reaction: pumping the prepared reaction liquid into a fixed bed reactor through a high-pressure constant flow pump, and reacting at the temperature of 100 ℃ and H₂Pressure 0.5MPa, H₂The molar ratio of the raw material to the 5-diethylamino-2-pentanone is 10:1, and the feed mass space velocity is 0.20h^-1The amination reaction performance of different supported nano Ni-based catalysts is researched under the condition, and a sample after 6 hours of stabilization is taken for gas chromatography analysis. The results in Table 2 show that the yields of the target N, N-diethyl-1, 4-pentanediamine are all above 90% and can reach 97.0% at most, which indicates that the catalyst synthesized by the invention can efficiently catalyze the reductive amination reaction of 5-diethylamino-2-pentanone and ammonia.

TABLE 2 reductive amination Performance of 5-diethylamino-2-pentanone catalyzed by different catalysts

Catalyst numbering	Alcohol solvent	Conversion (%)	Selectivity (%)	Yield (%)
					1	Methanol	97.3	93.2	90.7
2	Ethanol	98.6	94.1	92.8
					3	Ethanol	96.8	95.4	92.3
4	Ethanol	99.8	97.2	97.0
					5	Propanol(s)	99.2	96.9	96.1
6	Propanol(s)	96.7	96.3	93.1
					7	Isopropanol (I-propanol)	98.3	96.4	94.8
8	Ethanol	97.5	94.8	92.4
					9	Ethanol	98.4	95.7	94.1
10	Ethanol	99.1	96.2	95.3
					11	Ethanol	98.2	95.4	93.7

Example 7: amination reaction performance of 5-diethylamino-2-pentanone under different reaction conditions

No. 4 catalyst was used to study the ratio of 5-diethylamino-2-pentanone (here abbreviated as "aminopentanone") to ammonia water to ethanol, the reaction temperature, and H₂Pressure, feed Aminopentanone Mass space velocity, H₂The amination performance was affected by the molar ratio to cyclopentanone, and the results are shown in table 3, after 6h of equilibration the samples were taken for gas chromatography analysis. It can be seen that under the mild reaction conditions of the present invention, for example, the temperature is not higher than 140 ℃ and the pressure is not higher than 1MPa, the high yield of N, N-diethyl-1, 4-pentanediamine can be conveniently realized by adjusting the reaction process parameters (A)>90%) of the compound.

TABLE 3.4 amination Performance of catalyst No. 4 under different reaction conditions

Example 8:

weighing 5-diethylamino-2-pentanone, ethanol, 25% concentrated ammonia water and urea according to the mass ratio of 1:1:1:1 to prepare a reaction solution, pumping the prepared reaction solution into a fixed bed reactor filled with a No. 4 catalyst through a high-pressure constant flow pump (the catalyst filling and reduction are the same as in example 1), and carrying out H-flow reaction at the reaction temperature of 120 ℃ and the reaction temperature of 120 DEG C₂Pressure 0.5MPa, H₂The molar ratio of the raw material to the 5-diethylamino-2-pentanone is 10:1, and the feed mass space velocity is 0.50h^-1The amination reaction performance of different supported nano Ni-based catalysts is researched under the condition, a sample after 6h stabilization is taken for gas chromatography analysis, the conversion rate of the raw material is 99.3%, and the yield of the N, N-diethyl-1, 4-pentanediamine is 95.6%.

Example 9: continuous reaction stability study of catalyst

The ratio of the amino pentanone to the ammonia water to the ethanol is 1:1:3, the temperature is 120 ℃, and the H pressure is 0.5MPa₂Pressure, 0.25h^-1Mass space velocity, H₂The continuous reaction stability of the catalyst No. 4 is studied under the condition that the molar ratio of the catalyst to the amino pentanone is 5:1, and samples are taken every 6-10 hours for gas chromatography analysis. From the results of FIG. 5, it can be seen that the catalyst maintained good stability and the yield of N, N-diethyl-1, 4-pentanediamine was maintained at about 95% after 500 hours of operation. Distilling the collected reaction solution under reduced pressure, collecting 83-85 deg.C fraction, analyzing by gas chromatography to obtain purity of over 99.5%, and chromatogram shown in figure 6, wherein peak 1 represents ethanol solvent; peak 2 represents an impurity; peak 3 represents N, N-diethyl-1, 4-pentanediamine.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. A supported nano nickel-based catalyst is characterized by comprising a carrier, and a main active component and an auxiliary agent which are loaded on the carrier, wherein the main active component comprises Ni, the auxiliary agent comprises any one or a combination of more than two of Fe, Co, Cu, Zn, Mn, Ca, L a, Y, Ce and Ga, and the carrier comprises Al₂O₃、ZrO₂、SiO₂And MgO, or a combination of two or more thereof.

2. The supported nano nickel-based catalyst according to claim 1, characterized in that: the content of the main active component in the supported nano nickel-based catalyst is 15-75 wt%, and preferably 20-70 wt%;

and/or the content of the auxiliary agent in the supported nano nickel-based catalyst is 0.1-10 wt%.

3. The method for preparing the supported nano nickel-based catalyst according to claim 1 or 2, characterized by comprising: the supported nano nickel-based catalyst is prepared by adopting a coprecipitation method and/or a deposition precipitation method.

4. The method for preparing the supported nano nickel-based catalyst according to claim 3, comprising:

and mixing a mixed metal salt solution containing a main active component and an auxiliary agent, an alkali liquor with any one of a metal salt solution of the carrier, a carrier oxide powder solution and a carrier colloidal particle solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the supported nano nickel-based catalyst.

5. The method for preparing the supported nano nickel-based catalyst according to claim 4, wherein: the alkali liquor is any one or the combination of more than two of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and potassium carbonate solution;

and/or, the pH value of the mixed solution is kept between 9.0 and 11 during the precipitation treatment;

and/or, the aging treatment conditions include: the temperature is 30-100 ℃, and the time is 2-24 h;

and/or the conditions of the roasting treatment comprise: the temperature is 400 ℃ and 800 ℃, and the time is 2-8 h;

and/or the reduction treatment conditions comprise that the temperature is 350-750 ℃ in a hydrogen atmosphere, the time is 2-10h, and the flow rate of the hydrogen is 80-100m L/min.

6. Use of the supported nano nickel-based catalyst according to claim 1 or 2 for the continuous production of N, N-diethyl-1, 4-pentanediamine.

7. A method for continuously producing N, N-diethyl-1, 4-pentanediamine, which is characterized by comprising the following steps:

8. The process for the continuous production of N, N-diethyl-1, 4-pentanediamine according to claim 7, wherein the reductive amination reaction conditions comprise: the temperature is 80-140 ℃, the pressure is 0.1-1.0 MPa, and the feeding mass space velocity is 0.2-1.0 h^-1。

9. The process for continuously producing N, N-diethyl-1, 4-pentanediamine according to claim 7, characterized in that: the nitrogen source comprises any one or the combination of more than two of ammonia water, ammonia gas and urea;

and/or the reducing atmosphere is formed by a reducing gas; preferably, the reducing gas comprises hydrogen and/or a mixed gas containing hydrogen; preferably, the molar ratio of the reducing gas to the 5-diethylamino-2-pentanone is 5-20: 1;

and/or the molar ratio of the 5-diethylamino-2-pentanone to the nitrogen source is 1: 2-8.

10. The process for continuously producing N, N-diethyl-1, 4-pentanediamine according to claim 7, characterized by further comprising: mixing 5-diethylamino-2-pentanone, a nitrogen source and an alcohol solvent to form a mixed solution;

preferably, the alcohol solvent comprises any one or a combination of more than two of methanol, ethanol, propanol and isopropanol; preferably, the mass ratio of the alcohol solvent to the 5-diethylamino-2-pentanone is 1-3: 1.