CN115414942B - Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof - Google Patents

Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof Download PDF

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CN115414942B
CN115414942B CN202211165225.3A CN202211165225A CN115414942B CN 115414942 B CN115414942 B CN 115414942B CN 202211165225 A CN202211165225 A CN 202211165225A CN 115414942 B CN115414942 B CN 115414942B
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methylamine
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aminopropyl
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CN115414942A (en
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阮建成
石李明
刘福洲
王舒月
沈文波
钱超
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ANQIG BRANCH OF SINOPEC
China Petroleum and Chemical Corp
Zhejiang University ZJU
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China Petroleum and Chemical Corp
Zhejiang University ZJU
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Abstract

The invention relates to a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: mixing the first water-soluble metal salt, the second water-soluble metal salt and water to obtain a mixed bimetallic salt solution; dispersing carbon-based substrates and an equivalent amount of nano-TiO in water 2 As the catalyst load, stirring by ultrasonic until the dispersion is complete, and then adding a corresponding amount of mixed bimetallic salt solution; and (3) placing the mixed bimetallic salt solution under a xenon lamp light source for irradiation stirring reaction, freezing the irradiated mixed bimetallic salt solution into solid, and finally performing vacuum freeze drying on the solid to finally obtain the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine. The catalyst obtained by the invention simplifies the facilities and operation of the N, N-bis (3-aminopropyl) methylamine synthesis production process, and has the characteristics of high activity and good selectivity. The preparation method of the catalyst has the characteristics of wide raw material sources, simple operation, low cost and the like.

Description

Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical industry, in particular to a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, and a preparation method and application thereof.
Background
N, N-bis (3-aminopropyl) methylamine (BAPMA) has a structural formula shown in the following figure:
BAPMA is an important intermediate in fine organic chemical industry and is widely applied to industries such as medicines, pesticides, dyes, petrochemical industry, semiconductor manufacturing, high polymer and the like. Meanwhile, BAPMA is often used as an important precursor of pentamethylene propylene triamine for producing and preparing reverse osmosis nanofiltration membranes, epoxy resin curing accelerators, schiff bases and complexes thereof, medical synthesis intermediates, printing and dyeing wastewater treatment and the like.
At present, N, N-bis (3-aminopropyl) methylamine is mainly obtained by catalytic hydrogenation of N, N-bis (cyanoethyl) methylamine, and catalysts with different active centers have differences in the processes of catalytic hydrogenation and reduction of cyano groups, catalytic activity and selectivity and the like.
The industrial scale hydrogenation of nitriles mostly employs suspended catalysts such as raney nickel and raney cobalt. Hirano et al used a nickel cobalt bimetallic catalyst (Manufacturing method of nitrile compound and catalytic converter null for production:, JP Tgao No. 3156734 (P3156734) B2[ P ]. 2001.) to hydrogenate N, N-bis (cyanoethyl) methylamine under mild reaction conditions (80 ℃,4.5MPa,3.9 h) with a yield of 93%, but the selectivity of the reaction was poor and various byproducts were produced under the action of the catalyst.
Eidamshaus et al use ZrO 2 Supported Ru catalysts as catalysts for fixed bed reactions (METHOD FOR HYDROGENATING NITRILES IN THE PRESENCE OF A Ruthenium CATALYST CARRIED ON ZrO 2 :,US20190169112[P]2019.), the hydrogenation reaction is carried out on N, N-bis (cyanoethyl) methylamine at the temperature of 100 ℃ and 140 bar. Although the conversion rate of the reaction is up to 99%, the reaction conditions are more severe, the selectivity is poor, the product yield is up to 92%, the metal load is up to 15wt%, and the cost is higher.
The synthesis of N, N-bis (3-aminopropyl) methylamine by the one-step method is relatively rarely reported. Chen et al used raney nickel as the cyano hydrogenation catalyst (An efficient synthesis of N, N, N ', N', N "-pentamethylldipropylethylamine) and used acrylonitrile and methylamine as starting materials to synthesize N, N-bis (cyanoethyl) methylamine in one step in an autoclave: firstly, amination is carried out for 4 hours at normal temperature under a methanol solvent, then hydrogenation reaction is carried out under an alkaline reaction condition of 90 ℃ and 2MPa, and finally, the yield of the N, N-bis (3-aminopropyl) methylamine reaches 85 percent. However, in this process, the Raney nickel catalyst only catalyzes the hydrogenation process, resulting in a longer overall reaction time and lower efficiency.
In summary, many reported production routes of N, N-bis (3-aminopropyl) methylamine mostly take nitrile as raw material and are obtained through hydrogenation, and the problems of poor selectivity, harsh conditions, high cost, low efficiency and the like exist, and continuous production is difficult to realize, so that the development of a technology capable of synthesizing N, N-bis (3-aminopropyl) methylamine in one step is a problem to be solved in the field.
Disclosure of Invention
The invention aims at providing a preparation method of a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, which has the characteristics of simplifying facilities and operation of a production process for synthesizing N, N-bis (3-aminopropyl) methylamine, having high activity and good selectivity for synthesizing N, N-bis (3-aminopropyl) methylamine, and has the characteristics of wide raw material sources, simple operation, low cost and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, which comprises the following steps:
1) Mixing a first water-soluble metal salt, a second water-soluble metal salt and water to obtain a mixed bimetallic salt solution; the first water-soluble metal salt is one or more of sodium nitrate, potassium nitrate and magnesium nitrate, and the second water-soluble metal salt is one or more of nickel nitrate, zinc nitrate and chromium nitrate;
2) Dispersing carbon-based substrates and an equivalent amount of nano-TiO in water 2 As catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, and then adding a corresponding amount of mixed bimetallic salt solution, wherein the mass ratio of metal to catalyst load in the mixed bimetallic salt solution is 0.5-5.0 wt%;
3) And (3) placing the mixed bimetallic salt solution under a xenon lamp light source, irradiating and stirring for reaction for 3-6 hours, wherein the current is 10-20A, freezing the irradiated mixed bimetallic salt solution into solid, and finally performing vacuum freeze drying on the solid under the vacuum degree of 0.001-0.01 MPa and the temperature of minus 60-minus 50 ℃ to finally obtain the composite bimetallic monoatomic catalyst, namely the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine.
The preferable scheme is as follows: the carbon-based substrate is graphene, graphene oxide, carbon nano tube or C 3 N 4 One or more of nitrogen doped graphene.
The preferable scheme is as follows: the freezing time of the mixed bimetallic salt solution after illumination is 2-4 h, and the vacuum freeze drying time of the solid is 23-25 h.
A second object of the present invention is to provide a catalyst for synthesis of N, N-bis (3-aminopropyl) methylamine obtained based on the above preparation method.
A third object of the present invention is to provide the use of the above catalyst for the preparation of N, N-bis (3-aminopropyl) methylamine, by the following method:
adding a composite bimetallic monoatomic catalyst, raw material acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the composite bimetallic monoatomic catalyst to the raw material acrylonitrile and methylamine is 1-5wt%; the inner cavity of the autoclave is replaced by nitrogen, then stirred and reacted for 1.5 to 2.5 hours at the reaction temperature of 80 to 100 ℃ and the reaction pressure of 0.5 to 2.0MPa, then hydrogen is introduced, and the stirred and reacted for 1.5 to 2.5 hours at the temperature of 130 to 160 ℃ while maintaining the pressure of 1.5 to 3 MPa; after the reaction is finished, opening the autoclave, adding a solvent to dissolve the reaction product, and filtering to obtain the product N, N-bis (3-aminopropyl) methylamine.
The preferable scheme is as follows: the stirring reaction time is 2h.
The invention has the following technical effects:
1) The preparation principle of the composite bimetallic single-atom catalyst of the invention is as follows: in the process of preparing the catalyst by the photo-deposition method, when the photosensitive material is irradiated by ultraviolet light, electron-hole pairs which are easy to move and have extremely strong activity are generated, photo-generated carrier pairs can freely migrate to the surface of a crystal lattice or other reaction sites in the crystal lattice to form free holes and free electrons, the free holes and the free electrons are immediately captured by surface species, various oxidation-reduction reactions occur, and different metal atoms are anchored on a carrier to form the composite bimetallic monoatomic catalyst. The operation of each step in the preparation process of the catalyst has the following functions: different kinds of metal salts are precursors of different active centers; tiO (titanium dioxide) 2 C 3 N 4 As a photosensitive material, electron holes are generated under illumination; the carbon-based carrier with large specific surface area, special shape and structure is added, so that a loading surface can be provided, dispersion is facilitated, electrons are separated, and rapid recombination of electron holes is prevented; the vacuum freeze drying step is used for removing water in the system at low temperature and retaining the stable structure inside the catalyst; the influence of the corresponding technical parameters on the successful preparation of the catalyst is as follows: the mass ratio of the metal to the carrier is controlled to be 0.5-5.0wt%, agglomeration is formed when the metal is too high, and the activity is insufficient when the metal is too low; the illumination time is controlled to be 3-6 hours, the too low metal is not reduced, and the carrier structure is influenced by the too high metal; the metal salt is selected from sodium salt, potassium salt, magnesium salt, nickel salt, zinc salt and chromium salt,respectively serve as active centers of amination reaction and hydrogenation reaction. The key technical points are as follows: the mass ratio of the metal to the load carrier controls the dispersity of the metal on the surface of the carrier; the illumination time influences the reduction valence state of the metal; the selection of the metal salt influences the type of the active center, and the active site in the former step can be used as a cocatalyst in the latter step, so that the hydrogenation selectivity is improved. In summary, the successful preparation of the catalyst of the invention ensures a one-step synthesis of N, N-bis (3-aminopropyl) methylamine.
2) The composite bimetallic monoatomic catalyst prepared by the invention has the following effects on synthesizing N, N-bis (3-aminopropyl) methylamine: the method simplifies the facilities and the operation of the N, N-bis (3-aminopropyl) methylamine synthetic production process, the traditional production process needs two sets of production devices, the amination and the hydrogenation are separated, and the equipment and the operation are complex; in the invention, only one reactor is adopted, and amination and hydrogenation are carried out successively, so that intermediate products are not required to be separated, and equipment and intermediate operation steps are reduced; the method has the characteristics of high activity and good selectivity for synthesizing the N, N-bis (3-aminopropyl) methylamine, the traditional operation uses Raney nickel or noble metal catalyst for hydrogenation, the method has no promotion effect on the amination reaction, the yield is lower than 93%, and the selectivity is lower than 94%; the catalyst has promotion effect on amination and hydrogenation, the yield is higher than 94.1%, and the selectivity is higher than 96.2%; in addition, the preparation method of the catalyst has the characteristics of wide raw material sources, simple operation, low cost and the like, the transition metal salt and the carbon-based carrier are cheaper and easier to obtain than noble metal, the price of the noble metal catalyst commonly used in industrialization is 1.5 times of that of the transition metal catalyst in the invention, and the metal utilization rate (nearly 100%) of the catalyst is greatly higher than that of the conventional catalyst; the traditional industrial catalyst needs complex operations such as high-temperature roasting, and the catalyst is finished at normal temperature and normal pressure and is simple to operate.
3) The invention utilizes a composite bimetallic single-atom catalyst to prepare and synthesize N, N-bis (3-aminopropyl) methylamine, and the catalytic principle is as follows: the method comprises the steps that Michael addition reaction is carried out on acrylonitrile and methylamine on a sodium atom active site of a catalyst, active hydrogen on acrylonitrile, cyano and amino forms a transitional hydrogen bond, a lone pair electron on nitrogen nucleophilic attacks a carbon atom on beta position, and the two atoms are subjected to conjugate addition and rearrangement to form an intermediate containing cyano; the intermediate continues to undergo hydrogenation reactions at the nickel atom active sites of the catalyst to form amines. The operation of each step in the synthesis process of the N, N-bis (3-aminopropyl) methylamine has the following functions: the nitrogen replacement is to exhaust the air in the reactor to prevent oxidation or danger of the product; the amination reaction is carried out in the process of stirring reaction for 1.5-2.5 h at the reaction temperature of 80-100 ℃ and the reaction pressure of 0.5-2.0 MPa, the hydrogenation reaction is carried out in the process of stirring reaction for 1.5-2.5 h at the temperature of 130-160 ℃ while maintaining the pressure of 1.5-3 MPa, and the separation of the product by adding solvent and filtering is carried out to obtain the product with higher purity; the effect of the corresponding technical parameters on the successful synthesis of N, N-bis (3-aminopropyl) methylamine is as follows: if the reaction temperature is too low, the reaction activity is insufficient, and if the reaction temperature is too high, the deamination of a reaction intermediate is accelerated, and byproducts are increased; the catalyst has the advantages of insufficient active center and high cost, and waste is caused; the reaction pressure influences the reaction effect, the hydrogen pressure can improve the reaction speed, but the effect of the too high pressure lifting speed is not obvious, even the operation is dangerous, and the key technical points are as follows: the temperature in the reaction process affects the activity and the selectivity, and the optimal temperature is 80-100 ℃ and 130-160 ℃; the mass ratio of the proper catalyst to the reactant is 1-5 wt%; the proper reaction pressure in the hydrogenation process is 1.5-3 MPa.
Drawings
FIG. 1 is an SEM image of the catalyst Na-GO-Ni of the invention;
FIG. 2 is an XRD spectrum of the catalyst Na-GO-Ni of the invention.
As can be seen from fig. 1: the graphene oxide carrier is in a fold shape, and the appearance of the graphene oxide carrier is not obviously affected in the preparation process; the surface of the substrate is made of titanium dioxide serving as a sensitizer with different particle sizes, and the substrate is white; no apparent metal Na, ni-mer or particles were seen, indicating that the metal had a good atomic fraction divergence.
As can be seen from fig. 2: after the X-ray diffraction standard card is compared, only the characteristic peak of the titanium dioxide serving as the sensitizer is observed, but no characteristic peak of Na and Ni crystals is observed, which indicates that no Na and Ni nano-crystalline grains exist in the catalyst, and further verifies that the metal dispersity is higher.
Detailed Description
The present invention will be specifically described with reference to examples below in order to make the objects and advantages of the present invention more apparent. It should be understood that the following text is intended to describe only one or more specific embodiments of the invention and does not limit the scope of the invention strictly as claimed.
1. Preparation example of composite bimetallic monoatomic catalyst
In the following catalyst expression method, graphene is represented by G, graphene oxide is represented by GO, and graphite-like carbon nitride is represented by C 3 N 4 The nitrogen-doped graphene is represented by NG, and the carbon nanotube is represented by C. The vacuum degree of the vacuum freeze dryer is 0.001-0.01 MPa, and the temperature is minus 60-minus 50 ℃.
Preparation example 1, the preparation process of the composite bimetallic single-atom catalyst Na-G-Ni is as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 2.48mg of second water-soluble metal salt nickel nitrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding a mixed bimetallic salt solution, and keeping the metal in the mixed bimetallic salt solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Na-G-Ni with the metal content of 1.0 wt%.
Preparation example 2, the preparation process of the composite bimetallic single-atom catalyst Mg-G-Zn is as follows:
1) Uniformly mixing and dispersing 5.34mg of first water-soluble metal salt magnesium nitrate, 1.46mg of second water-soluble metal salt zinc nitrate hexahydrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) Adding into 20ml deionized waterInto 50mg of graphene substrate and 50mg of nano TiO 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Mg-G-Zn with the metal content of 1.0 wt%.
Preparation example 3, the preparation process of the composite bimetallic monoatomic catalyst K-G-Cr is as follows:
1) Uniformly mixing and dispersing 1.29mg of first water-soluble metal salt potassium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst K-G-Cr with the metal content of 1.0 wt%.
Preparation example 4, the preparation process of the composite bimetallic single-atom catalyst Na-GO-Cr is as follows:
1) Uniformly mixing and dispersing 20mg of first water-soluble metal salt sodium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene oxide substrate and an equivalent amount of nano TiO were added to 20ml of deionized water 2 As the catalyst load, stirring the mixture by ultrasonic until the mixture is completely dispersed, then adding a corresponding amount of mixed bimetallic salt aqueous solution, and keeping gold in the mixed bimetallic salt aqueous solutionThe method belongs to the following: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Na-GO-Cr with the metal content of 1.0 wt%.
Preparation example 5, composite bimetallic monoatomic catalyst Na-C 3 N 4 The Zn preparation process is as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 20mg of second water-soluble metal salt zinc nitrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 100mg of graphite-like carbon nitride material C was added to 20ml of deionized water 3 N 4 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 23 hours to obtain the composite bimetallic single-atom catalyst Na-GO-Zn with the metal content of 1.0 wt%.
Preparation example 6, the preparation process of the composite bimetallic single-atom catalyst Na-NG-Ni is as follows:
1) Uniformly mixing and dispersing 9.25mg of first water-soluble metal salt sodium nitrate, 7.30mg of second water-soluble metal salt zinc nitrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of nitrogen doped graphene NG and 50mg of nano TiO are added into 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 5.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Na-NG-Ni with the metal content of 5.0 wt%.
Preparation example 7, the preparation process of the composite bimetallic single-atom catalyst Na-G-Ni is as follows:
1) Uniformly mixing and dispersing 0.92mg of first water-soluble metal salt sodium nitrate, 1.24mg of second water-soluble metal salt nickel nitrate and 5ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding a mixed bimetallic salt solution, and keeping the metal in the mixed bimetallic salt solution: catalyst loading = 0.5wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 6 hours, wherein the current is 20A, placing the irradiated solution in a refrigerator, freezing for 2 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Na-G-Ni with the metal content of 0.5 wt%.
Preparation example 8, the preparation process of the composite bimetallic single-atom catalyst Mg-G-Zn is as follows:
1) Uniformly mixing and dispersing 5.34mg of first water-soluble metal salt magnesium nitrate, 1.46mg of second water-soluble metal salt zinc nitrate hexahydrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 4 hours, wherein the current is 15A, placing the irradiated solution in a refrigerator, freezing for 3 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Mg-G-Zn with the metal content of 1.0 wt%.
Preparation example 9, the preparation process of the composite bimetallic monoatomic catalyst K-C-Cr is as follows:
1) Uniformly mixing and dispersing 1.29mg of first water-soluble metal salt potassium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of carbon nanotube substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding mixed bimetallic salt aqueous solution, and keeping metal in the mixed bimetallic salt aqueous solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst K-C-Cr with the metal content of 1.0 wt%.
Preparation example 10, the preparation process of the composite bimetallic single-atom catalyst Na-GO-Ni is as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 2.48mg of second water-soluble metal salt nickel nitrate and 10ml of deionized water to obtain a mixed bimetallic salt solution;
2) 50mg of graphene oxide substrate and 50mg of nano TiO were added to 20ml of deionized water 2 As a catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, then adding a mixed bimetallic salt solution, and keeping the metal in the mixed bimetallic salt solution: catalyst loading = 1.0wt% mass ratio;
3) And (3) placing the mixed solution under a xenon lamp light source, irradiating and stirring for reaction for 3 hours, wherein the current is 10A, placing the irradiated solution in a refrigerator for freezing for 4 hours until the solution becomes solid, and finally placing the solution in a vacuum dryer for drying for 24 hours to obtain the composite bimetallic single-atom catalyst Na-GO-Ni with the metal content of 1.0 wt%.
2. Continuous process for the Synthesis of N, N-bis (3-aminopropyl) methylamine examples
The synthesis method takes acrylonitrile and methylamine as raw materials, and the synthesis reaction equation is as follows:
the specific synthesis steps are as follows:
example 1, 100mg of a composite bimetallic single-atom catalyst Na-G-Ni with the metal content of 1.0wt% and raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 130 ℃ under the pressure of 1.5 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 94.1% and a selectivity of 96.2%.
Example 2 100Mg of composite bimetallic single-atom catalyst Mg-G-Zn with metal content of 1.0wt% and raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 90 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 130 ℃ under the pressure of 2.0 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 95.3% and a selectivity of 98.6%.
Example 3 adding 100mg of a composite bimetallic single-atom catalyst K-G-Cr with a metal content of 1.0wt% and raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 100 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 130 ℃ under the pressure of 2.5 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 96.0% and a selectivity of 97.6%.
Example 4, 100mg of a composite bimetallic single-atom catalyst Na-GO-Cr with the metal content of 1.0wt% and raw materials acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 85 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 140 ℃ under the pressure of 2.0 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 96.5% and a selectivity of 97.9%.
EXAMPLE 5A composite bimetallic monoatomic catalyst Na-C having a metal content of 1.0wt% 3 N 4 100mg of Zn, acrylonitrile as a raw material and methylamine as a raw material are added into an autoclave, and the mass ratio of the catalyst to the raw material is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 150 ℃ under the pressure of 2.0 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 94.4% and a selectivity of 96.9%.
Example 6 adding 100mg of a composite bimetallic single-atom catalyst Na-NG-Ni with a metal content of 5.0wt% and raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 90 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 160 ℃ under the pressure of 2.0 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 94.3% and a selectivity of 95.7%.
Example 7, 100mg of a composite bimetallic single-atom catalyst Na-NG-Ni with the metal content of 5.0wt% and raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 1.0 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 150 ℃ under the pressure of 2.0 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 95.0% and a selectivity of 97.7%.
Example 8 adding 100mg of a composite bimetallic single-atom catalyst Na-NG-Ni with a metal content of 5.0wt% and raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the catalyst to the raw materials is 1%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 150 ℃ under the pressure of 1.5 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 94.0% and a selectivity of 96.7%.
Example 9 adding 100mg of a composite bimetallic single-atom catalyst Na-NG-Ni with a metal content of 5.0wt% and raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the catalyst to the raw materials is 5%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 2.0 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 150 ℃ under the pressure of 3 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 94.5% and a selectivity of 96.5%.
Example 10 adding 100mg of a composite bimetallic single-atom catalyst Na-GO-Ni with a metal content of 1.0wt% and a raw material acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the catalyst to the raw material is 2%; the inner cavity of the autoclave is subjected to gas replacement by utilizing nitrogen, and then stirred and reacted for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; introducing hydrogen, and stirring and reacting for 2 hours at 130 ℃ under the pressure of 1.5 MPa; after the reaction, the autoclave was opened, and the reaction product was dissolved by adding a solvent and filtered to obtain the product N, N-bis (3-aminopropyl) methylamine in a yield of 95.1% and a selectivity of 96.5%.
The synthesis example is only a part of N, N-bis (3-aminopropyl) methylamine, the composite bimetallic monoatomic catalyst obtained in the preparation example can be effectively used for synthesizing the N, N-bis (3-aminopropyl) methylamine, and the yield and the selectivity of the N, N-bis (3-aminopropyl) methylamine can reach more than 95%.
Comparative example 1-1, the following catalyst preparation conditions in catalyst preparation example 1 were changed: the metal content was 10.0wt% and the other preparation conditions were kept unchanged, which was used for the synthesis of N, N-bis (3-aminopropyl) methylamine in a procedure equivalent to example 1 above. The result was that the yield of N, N-bis (3-aminopropyl) methylamine was 54.5% and the selectivity was 65.2%.
Comparative examples 1-2 the following catalyst preparation conditions in catalyst preparation example 1 were changed: the synthesis procedure for N, N-bis (3-aminopropyl) methylamine was identical to example 1 above, except that activated carbon was used as the carbon-based substrate, with the other preparation conditions remaining unchanged. The result was that the yield of N, N-bis (3-aminopropyl) methylamine was 44.5% and the selectivity was 54.6%.
Comparative example 2-1, catalyst preparation, was identical to catalyst preparation example 1, in that the synthesis reaction procedure for N, N-bis (3-aminopropyl) methylamine was identical to that of example 1 described above, except that the reaction temperature of "80℃and the reaction pressure of 0.5 MPa" in example 1 were changed to "60℃and normal pressure", and the remaining reaction conditions were maintained. The result was that the yield of N, N-bis (3-aminopropyl) methylamine was 34.5% and the selectivity was 40.2%.
Comparative examples 2-2, catalyst preparation were identical to catalyst preparation example 1, and the synthesis reaction procedure for N, N-bis (3-aminopropyl) methylamine was the same as that of example 1, except that "introducing hydrogen gas", stirring reaction was carried out for 2 hours while maintaining the pressure at 2.0MPa and 150℃was changed to "introducing hydrogen gas", stirring reaction was carried out for 1 hour while maintaining the pressure at 0.5MPa and 100℃was carried out, and the remaining reaction conditions were maintained unchanged. The result was that the yield of N, N-bis (3-aminopropyl) methylamine was 39.2% and the selectivity was 46.5%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention. Structures, devices and methods of operation not specifically described and illustrated herein, unless otherwise indicated and limited, are implemented according to conventional means in the art.

Claims (6)

1. A method for preparing a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, which is characterized by comprising the following steps:
1) Mixing a first water-soluble metal salt, a second water-soluble metal salt and water to obtain a mixed bimetallic salt solution; the first water-soluble metal salt is one or more of sodium nitrate, potassium nitrate and magnesium nitrate, and the second water-soluble metal salt is one or more of nickel nitrate, zinc nitrate and chromium nitrate;
2) Dispersing carbon-based substrates and an equivalent amount of nano-TiO in water 2 As catalyst load, stirring by ultrasonic until the catalyst is completely dispersed, and then adding a corresponding amount of mixed bimetallic salt solution, wherein the mass ratio of metal to catalyst load in the mixed bimetallic salt solution is 0.5-5.0 wt%;
3) And (3) placing the mixed bimetallic salt solution under a xenon lamp light source, irradiating and stirring for reaction for 3-6 hours, wherein the current is 10-20A, freezing the irradiated mixed bimetallic salt solution into solid, and finally performing vacuum freeze drying on the solid under the vacuum degree of 0.001-0.01 MPa and the temperature of minus 60-minus 50 ℃ to finally obtain the composite bimetallic monoatomic catalyst, namely the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine.
2. The method for preparing the catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as claimed in claim 1, wherein: the carbon-based substrate is graphene, graphene oxide, carbon nano tube or C 3 N 4 One or more of nitrogen doped graphene.
3. The method for preparing the catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as claimed in claim 1, wherein: the freezing time of the mixed bimetallic salt solution after illumination is 2-4 h, and the vacuum freeze drying time of the solid is 23-25 h.
4. A catalyst for N, N-bis (3-aminopropyl) methylamine synthesis obtained by the process as claimed in any one of claims 1 to 3.
5. Use of the catalyst according to claim 4 for the preparation of N, N-bis (3-aminopropyl) methylamine, characterized in that the method of application is as follows:
adding a composite bimetallic monoatomic catalyst, raw material acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the composite bimetallic monoatomic catalyst to the raw material acrylonitrile and methylamine is 1-5wt%; the inner cavity of the autoclave is replaced by nitrogen, then stirred and reacted for 1.5 to 2.5 hours at the reaction temperature of 80 to 100 ℃ and the reaction pressure of 0.5 to 2.0MPa, then hydrogen is introduced, and the stirred and reacted for 1.5 to 2.5 hours at the temperature of 130 to 160 ℃ while maintaining the pressure of 1.5 to 3 MPa; after the reaction is finished, opening the autoclave, adding a solvent to dissolve the reaction product, and filtering to obtain the product N, N-bis (3-aminopropyl) methylamine.
6. Use of the catalyst according to claim 5 for the preparation of N, N-bis (3-aminopropyl) methylamine, characterized in that: the stirring reaction time is 2h.
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