A method for preparing isosorbide diamines

Abstract

The application discloses a method for preparing isosorbide diamine. The method comprises the following steps: loading isosorbide diketone and ammonia into a reaction kettle loaded with a catalyst, introducing hydrogen into the reaction kettle, and reacting at 100 DEG C to 200 DEG C for 10-20 hours to generate isosorbide diamine through a reductive amination reaction; the catalyst is a core-shell structure, and is composed of an oxide shell layer and a metal core; the metal in the metal core is a main metal M1 or the main metal M1 and an auxiliary metal M2; the main metal M1 is Fe, Co, Ni or Cu; and the auxiliary metal M2 is Ru, Pd or Pt. The application avoids the essential problems existing in the original process, and realizes green and sustainable production of isosorbide diamine.

Description

Technical Field

[0001] This invention relates to a preparation technology for the biomass product isosorbide diamine, and in particular to a method for preparing isosorbide diamine from isosorbide dione as an initial raw material and a method for preparing a catalyst thereof. Background Technology

[0002] Diamines (referring to primary diamines, H2N-R-NH2, where R represents aliphatic carbon chains, carbon rings, and heterocyclic rings, etc.) are monomers used in the synthesis of polymers such as polyamides and polyimides. Traditionally, diamine production almost entirely relies on fossil resources. Producing diamines from renewable biomass-based resources can reduce this over-reliance on fossil resources, while simultaneously broadening the variety of polymer materials and improving the environmental compatibility of related products. Isosorbide, a biomass-based diol derived from the dehydration of sorbitol, has achieved large-scale production and has become one of the most important biomass-based platform compounds. Therefore, from an application perspective, the catalytic amination of isosorbide to synthesize the corresponding isosorbide diamine is an ideal approach to expanding the utilization of biomass resources and obtaining environmentally compatible polymer materials.

[0003] Beller and Vogt et al. were the first to conduct research on the catalytic amination of isosorbide. Under homogeneous conditions, isosorbide diamine could be obtained, but all of them used noble metal complexes as catalysts, which had drawbacks such as expensive ligands and metal complexes, and difficulty in catalyst recovery. To solve the problem of the existence of homogeneous catalytic systems, Rose's group used the heterogeneous catalyst Ru / C for the catalytic amination of isosorbide to synthesize isosorbide diamine, but the yield of isosorbide diamine was only 10%. Rose's group then tried other supported ruthenium catalysts and bimetallic catalysts, but there was no improvement, further proving that it is impossible to synthesize isosorbide diamine directly from isosorbide in a heterogeneous catalytic system with high yield via catalytic amination.

[0004] Isosorbide dione can be obtained almost quantitatively from isosorbide via catalytic oxidation, and the catalytic amination of ketones is easier than that of alcohols. Therefore, researchers have investigated the reaction process for preparing isosorbide diamine by the amination of isosorbide dione using a heterogeneous catalyst. Patent US201241216 describes a two-step method for preparing isosorbide diamine from isosorbide dione using an enzyme via imidization and hydrogenation, with a yield of 69%. This method has a low yield, cumbersome steps, and difficult separation. Patent US2013116451 describes a method for preparing isosorbide diamine from isosorbide dione using a commercial Ni / Al₂O₃ catalyst, with a yield of 44%. This method also has a low yield and difficult separation.

[0005] This invention provides a novel core-shell catalyst for a one-step method to synthesize isosorbide diamine via catalytic amination of isosorbide dione in high yield. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of current technologies by providing a method for preparing isosorbide diamine. This method employs a core-shell catalyst to synthesize isosorbide diamine in high yield via a one-step catalytic amination of isosorbide dione. The presence of the shell layer plays a stepwise role in the reductive amination process of the ketone. First, the amination of the ketone occurs at the acidic center on the shell, generating an imine; then, the imine diffuses through the shell to the metal core for hydrogenation. Furthermore, the adjustable shell pore size allows for precise control of the reaction pathway and adjustment of the selectivity of the target product. This invention avoids the inherent problems of existing processes, achieving the green and sustainable production of isosorbide diamine.

[0007] The technical solution of this invention is as follows:

[0008] A method for preparing isosorbide diamine, the method comprising the following steps:

[0009] Isosorbide dione and ammonia were loaded into a reactor containing a catalyst. Hydrogen was introduced into the reactor and the reaction was carried out at 100℃~200℃ for 10-20h to produce isosorbide diamine through a reductive amination reaction.

[0010] The molar ratio of reactants is isosorbide dione:ammonia = 1:10-30; hydrogen pressure: 1-6 MPa;

[0011] The catalyst has a core-shell structure, comprising an oxide shell and a metal core; the molar ratio of the oxide shell to the metal core is 0.1–1; the metal core is the catalytically active component.

[0012] The diameter of the metal core is 15–25 nm, and the shell thickness is 5–30 nm.

[0013] The oxide shell is Al2O3, SiO2, or MgO;

[0014] The metal in the metal core is either the main metal M1 or the main metal M1 and the auxiliary metal M2, and the content of the catalytic component is 0.5% to 2% of the molar mass of the main metal.

[0015] The main metal M1 is Fe, Co, Ni or Cu;

[0016] The auxiliary metal M2 is Ru, Pd, or Pt;

[0017] The method for preparing the catalyst includes the following steps:

[0018] (1) Preparation of metal cores:

[0019] The nitrate of the nuclear metal and polyethylene glycol were added sequentially to distilled water. After stirring the solution for 30-60 minutes, urea was added to obtain a mixed solution. The mixture was heated to 80-95°C and reacted for 10-24 hours. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried, and calcined in air at 400-600°C for 2-4 hours to obtain metal oxide nanoparticles.

[0020] In the mixed solution, the concentration of nitrate of the nuclear metal is 1-5 wt%, the concentration of polyethylene glycol (PEG-20000) is 2-6 wt%, and the concentration of urea is 2-6 wt%.

[0021] (2) A shell is formed around the metal core:

[0022] Add 0.2–1 wt% metal oxide nanoparticles to anhydrous ethanol and sonicate for 30–60 min. Then, add a shell-forming reagent, a pore-forming reagent, and NH3·H2O under ultrasonic conditions. After the addition is complete, continue the reaction under ultrasonic conditions for another 30–60 min. Centrifuge, wash with ethanol and distilled water, dry, calcine at 400–600℃ for 2–4 h, and reduce with H2 at 400–600℃ for 2–3 h to obtain the catalyst.

[0023] The molar ratio of metal oxide nanoparticles to shell-forming reagent is 0.1 to 1. The shell-forming reagent of the catalyst is tetraethyl orthosilicate, aluminum isopropoxide or magnesium ethoxide. When the shell is SiO2, the shell-forming reagent is tetraethyl orthosilicate; when the shell is Al2O3, the shell-forming reagent is aluminum isopropoxide; and when the shell is MgO, the shell-forming reagent is magnesium ethoxide.

[0024] The mass of the metal oxide nanoparticles is 0.2–1.0 wt% of anhydrous ethanol; 5–10 g of NH3·H2O is added per 50 g of anhydrous ethanol;

[0025] The pore-forming reagent is octadecyltrimethoxysilane or hexadecyltrimethylammonium bromide, and the molar ratio of the pore-forming reagent to the shell-forming reagent is 0.1 to 0.5.

[0026] The thickness of the catalyst shell is determined by the ratio of oxide shell (shell-forming agent) to metal oxide. The molar ratio of metal oxide to shell-forming agent is 0.1 to 1. As the ratio increases from 0.1 to 1 (molar ratio), the shell thickness tends to increase, from 5 nm to 30 nm.

[0027] The size and distribution of pores in the catalyst shell are determined by the amount of pore-forming reagent. The molar ratio of pore-forming reagent to shell-forming reagent is 0.1–0.5. As the ratio increases from 0.1 to 0.2 (molar ratio), the specific surface area and pore size in the shell tend to increase. The specific surface area increases from 41.75 m² / g. 2 / g increased to 115.70m 2 / g, the average pore size increased from 3.91nm to 4.70nm. As the ratio increased from 0.2 to 0.5 (molar ratio), the specific surface area and pore size in the shell showed a decreasing trend, with the specific surface area increasing from 115.70nm. 2 / g decreased to 61.76m 2 / g, the pore size decreased from 4.70nm to 3.42nm, indicating that too much pore-forming reagent was added, which damaged the pore structure.

[0028] The calcination temperature of the catalyst is 400–600°C;

[0029] The reduction temperature of the catalyst is 400–600°C.

[0030] The essential features of this invention are:

[0031] In the core-shell structured Ni-Ru bimetallic heterogeneous catalyst with silica coating used in this invention, the presence of the silica shell plays a stepwise role in the reductive amination process of ketones. First, the amination of the ketone occurs at the acidic centers on the shell, generating an imine; then, the imine diffuses through the shell to the metal core for hydrogenation. This prevents the ketone from directly hydrogenating to an alcohol, reducing the formation of byproducts.

[0032] After adding a pore-forming reagent, the pores in the silica shell increase in number and slightly in size, which promotes the diffusion of substances and improves the yield.

[0033] The mutual doping of Ni and Ru within the shell, with only a small amount of Ru required, enhances the activity of imine hydrogenation and promotes the conversion of intermediates.

[0034] Ultimately, by leveraging the advantages of its core-shell structure and controllable shell pore size, it is possible to achieve efficient and highly selective reduction and amination of isosorbide diamine from isosorbide dione.

[0035] The beneficial effects of this invention are as follows:

[0036] This invention provides a method for synthesizing isosorbide diamine from isosorbide dione, which overcomes the drawbacks of existing production processes, such as high difficulty and low yield. Furthermore, the catalyst used in this invention is simple to prepare; the catalyst shell is composed of Al₂O₃, SiO₂, and MgO, the main active metal M1 is Fe, Co, Ni, and Cu, and the auxiliary metal M2 is Ru, Pd, and Pt. The amount of the auxiliary metal is only 0.5% to 2% of the total auxiliary metal, and the shell support and catalytic active components are inexpensive and readily available.

[0037] The catalytic reaction of this invention is a low-temperature, low-pressure reaction, which does not require sophisticated reaction equipment and improves the economic feasibility of the reaction. The byproducts of the catalytic process are pollution-free, resulting in minimal waste. The conversion rate of isosorbide dione can reach 99%, and the selectivity of isosorbide diamine is 99%.

[0038] In summary, the catalyst described in this invention is simple to prepare, inexpensive and readily available; the reaction raw materials are inexpensive and readily available, produce little waste, and cause no pollution. Attached Figure Description

[0039] Figure 1 The images shown are TEM images of the catalysts obtained in Examples 18 and 25, where... Figure 1 In the image, 'a' represents a TEM image of the Ni@SiO2 catalyst (corresponding to the metal core prepared in Example 1, and subsequently the catalyst prepared according to Example 18). Figure 1 In the image, b is a TEM image of the Ni-Ru@SiO2 catalyst (corresponding to the metal core prepared in Example 5, and then the catalyst prepared according to Example 25);

[0040] Figure 2 TEM images of the catalysts obtained in Examples 24, 25, and 26, wherein, Figure 2 In the image, 'a' is the TEM image of the catalyst obtained in Example 24. Figure 2 b in the image is the TEM image of the catalyst obtained in Example 25. Figure 2 In this context, 'c' refers to the catalyst obtained in Example 26;

[0041] Figure 3 The pore size distribution diagrams are for the catalysts obtained in Examples 25, 27, 28, 29 and 30. Detailed Implementation

[0042] The synthetic route of this invention is shown in the reaction formula below:

[0043]

[0044] The technical features of the present invention are further illustrated below through examples:

[0045] Example 1: Preparation of NiO nanoparticles

[0046] 2.90 g of Ni(NO3)2·6H2O (0.01 mol) was added to 100 mL of distilled water containing 3.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 30 min, 4.5 g of urea was added, and the mixture was heated to 85 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 400 °C for 4 h to obtain Ni nanoparticles.

[0047] Example 2: Preparation of CoO nanoparticles

[0048] 2.91 g of Co(NO3)2·6H2O (0.01 mol) was added to 100 mL of distilled water containing 3.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 30 min, 4.5 g of urea was added, and the mixture was heated to 90 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Co nanoparticles.

[0049] Example 3: Preparation of FeO nanoparticles

[0050] 4.04 g of Fe(NO3)3·9H2O (0.01 mol) was added to 100 mL of distilled water containing 4.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 30 min, 4.5 g of urea was added, and the mixture was heated to 80 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 550 °C for 4 h to obtain Fe nanoparticles.

[0051] Example 4: Preparation of CuO nanoparticles

[0052] 1.44 g of Cu(NO3)2·3H2O (0.01 mol) was added to 100 mL of distilled water containing 4.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 30 min, 5 g of urea was added, and the mixture was heated to 85 °C and reacted for 10 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Cu nanoparticles.

[0053] Example 5: Preparation of NiO-RuO nanoparticles

[0054] 2.90 g Ni(NO3)2·6H2O (0.01 mol) and 0.0225 g RuCl3·xH2O (0.0001 mol, where the mass of Ru is 36-38% of the mass of RuCl3·xH2O) were added to 100 mL of distilled water containing 3.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 85 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 400 °C for 4 h to obtain Ni-Ru nanoparticles.

[0055] Example 6: Preparation of CoO-RuO nanoparticles

[0056] 2.91 g of Co(NO3)2·6H2O (0.01 mol) and 0.0225 g of RuCl3·xH2O (0.0001 mol, where the mass of Ru is 36-38% of the mass of RuCl3·xH2O) were added to 100 mL of distilled water containing 3.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g of urea was added, and the mixture was heated to 90 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Co-Ru nanoparticles.

[0057] Example 7: Preparation of FeO-RuO nanoparticles

[0058] 4.04 g of Fe(NO3)3·9H2O (0.01 mol) and 0.0225 g of RuCl3·xH2O (0.0001 mol, where the mass of Ru is 36-38% of the mass of RuCl3·xH2O) were added to 100 mL of distilled water containing 4.00 g of polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g of urea was added, and the mixture was heated to 80 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 550 °C for 4 h to obtain Fe-Ru nanoparticles.

[0059] Example 8: Preparation of CuO-RuO nanoparticles

[0060] 1.44 g Cu(NO3)2·3H2O (0.01 mol) and 0.0225 g RuCl3·xH2O (0.0001 mol, where the mass of Ru is 36-38% of the mass of RuCl3·xH2O) were added to 100 mL of distilled water containing 4.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 5 g urea was added, and the mixture was heated to 85 °C and reacted for 10 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Cu-Ru nanoparticles.

[0061] Example 9: Preparation of NiO-PtO Nanoparticles

[0062] 2.90 g Ni(NO3)2·6H2O (0.01 mol) and 0.0337 g PtCl4 (0.0001 mol) were added to 100 mL of distilled water containing 3.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 85 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 400 °C for 4 h to obtain Ni-Pt nanoparticles.

[0063] Example 10: Preparation of CoO-PtO nanoparticles

[0064] 2.91 g Co(NO3)2·6H2O (0.01 mol) and 0.0337 g PtCl4 (0.0001 mol) were added to 100 mL of distilled water containing 3.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 90 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Co-Pt nanoparticles.

[0065] Example 11: Preparation of FeO-PtO nanoparticles

[0066] 4.04 g Fe(NO3)3·9H2O (0.01 mol) and 0.0337 g PtCl4 (0.0001 mol) were added to 100 mL of distilled water containing 4.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 80 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 550 °C for 4 h to obtain Fe-Pt nanoparticles.

[0067] Example 12: Preparation of CuO-PtO nanoparticles

[0068] 1.44 g Cu(NO3)2·3H2O (0.01 mol) and 0.0337 g PtCl4 (0.0001 mol) were added to 100 mL of distilled water containing 4.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 5 g urea was added, and the mixture was heated to 85 °C and reacted for 10 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Cu-Pt nanoparticles.

[0069] Example 13: Preparation of NiO-PdO nanoparticles

[0070] 2.90 g Ni(NO3)2·6H2O (0.01 mol) and 0.0177 g PdCl2 (0.0001 mol) were added to 100 mL of distilled water containing 3.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 85 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 400 °C for 4 h to obtain Ni-Pd nanoparticles.

[0071] Example 14: Preparation of CoO-PdO nanoparticles

[0072] 2.91 g Co(NO3)2·6H2O (0.01 mol) and 0.0177 g PdCl2 (0.0001 mol) were added to 100 mL of distilled water containing 3.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 90 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 4 h to obtain Co-Pd nanoparticles.

[0073] Example 15: Preparation of FeO-PdO nanoparticles

[0074] 4.04 g Fe(NO3)3·9H2O (0.01 mol) and 0.0177 g PdCl2 (0.0001 mol) were added to 100 mL of distilled water containing 4.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 4.5 g urea was added, and the mixture was heated to 80 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 550 °C for 4 h to obtain Fe-Pd nanoparticles.

[0075] Example 16: Preparation of CuO-PdO nanoparticles

[0076] 1.44 g Cu(NO3)2·3H2O (0.01 mol) and 0.0177 g PdCl2 (0.0001 mol) were added to 100 mL of distilled water containing 4.00 g polyethylene glycol (PEG-20000). After stirring the solution for 60 min, 5 g urea was added, and the mixture was heated to 85 °C and reacted for 24 h. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried at 100 °C for 10 h, and calcined in air at 500 °C for 10 h to obtain Cu-Pd nanoparticles.

[0077] Example 17: Preparation of microporous Ni@SiO2, Co@SiO2, Fe@SiO2, Cu@SiO2 catalysts

[0078] Add 0.25g of NiO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.0697g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.1 between the shell-forming agent and the metal core) and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 2h, and reduce to H2 at 500℃ for 2h.

[0079] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain the same).

[0080] Ultimately, four types of materials were obtained: microporous Ni@SiO2, Co@SiO2, Fe@SiO2, and Cu@SiO2 catalysts.

[0081] Example 18: Preparation of microporous Ni@SiO2, Co@SiO2, Fe@SiO2, Cu@SiO2 catalysts

[0082] Add 0.25g of NiO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 between the shell-forming agent and the metal core) and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 2h, and reduce to H2 at 500℃ for 2h.

[0083] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: microporous Ni@SiO2, Co@SiO2, Fe@SiO2, and Cu@SiO2 catalysts.

[0084] Example 19: Preparation of microporous Ni@SiO2, Co@SiO2, Fe@SiO2, Cu@SiO2 catalysts

[0085] Add 0.25 g of NiO nanoparticles to 50 g of anhydrous ethanol and sonicate for 30 min. Then, in an ultrasonic bath, add 0.6970 g of tetraethyl orthosilicate (corresponding to a molar ratio of 1:1 between the shell-forming agent and the metal core) and 10 g of NH3·H2O sequentially under ultrasonic treatment (60 min). Dry at 80 °C for 10 h, calcine at 550 °C for 2 h, and reduce to H2 at 500 °C for 2 h.

[0086] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: microporous Ni@SiO2, Co@SiO2, Fe@SiO2, and Cu@SiO2 catalysts.

[0087] Example 20: Preparation of mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts

[0088] Add 0.25g of NiO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.0627g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.1 for pore-forming reagent to shell-forming reagent), 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 2h, and reduce to H2 at 500℃ for 2h.

[0089] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts.

[0090] Example 21: Preparation of mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts

[0091] Add 0.25 g of NiO nanoparticles to 50 g of anhydrous ethanol and sonicate for 30 min. Then, in an ultrasonic bath, add 0.1254 g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.2 for pore-forming reagent to shell-forming reagent), 0.3485 g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10 g of NH3·H2O sequentially under ultrasonic treatment (60 min). Dry at 80 °C for 10 h, calcine at 550 °C for 2 h, and reduce to H2 at 500 °C for 2 h.

[0092] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts.

[0093] Example 22: Preparation of mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts

[0094] 0.25 g of NiO nanoparticles were added to 50 g of anhydrous ethanol and subjected to ultrasonic treatment for 30 min. Then, in an ultrasonic bath, 0.1881 g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.3 for pore-forming reagent to shell-forming reagent), 0.3485 g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10 g of NH3·H2O were added sequentially under ultrasonic treatment (60 min). The mixture was dried at 80 °C for 10 h, calcined at 550 °C for 2 h, and reduced to H2 at 500 °C for 2 h.

[0095] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts.

[0096] Example 23: Preparation of mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts

[0097] 0.25 g of NiO nanoparticles were added to 50 g of anhydrous ethanol and subjected to ultrasonic treatment for 30 min. Then, in an ultrasonic bath, 0.3135 g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.5 for pore-forming reagent to shell-forming reagent), 0.3485 g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10 g of NH3·H2O were added sequentially under ultrasonic treatment (60 min). The mixture was dried at 80 °C for 10 h, calcined at 550 °C for 2 h, and reduced to H2 at 500 °C for 2 h.

[0098] The other steps are the same as above, except that NiO nanoparticles are replaced with CoO, FeO, and CuO nanoparticles respectively (molar amounts remain unchanged). Finally, four materials are obtained: mesoporous meso-Ni@SiO2, meso-Co@SiO2, meso-Fe@SiO2, and meso-Cu@SiO2 catalysts.

[0099] Example 24: Preparation of microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts

[0100] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.0697g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.1 between the shell-forming reagent and the metal core) and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0101] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain unchanged). Finally, twelve materials are obtained: microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts.

[0102] Example 25: Preparation of microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts

[0103] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 between the shell-forming reagent and the metal core) and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0104] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain unchanged). Finally, twelve materials are obtained: microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts.

[0105] Example 26: Preparation of microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts

[0106] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.6970g of tetraethyl orthosilicate (corresponding to a molar ratio of 1:1 between the shell-forming reagent and the metal core) and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0107] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain unchanged). Finally, twelve materials are obtained: microporous Ni-Ru@SiO2, Ni-Pt@SiO2, Ni-Pd@SiO2, Co-Ru@SiO2, Co-Pt@SiO2, Co-Pd@SiO2, Fe-Ru@SiO2, Fe-Pt@SiO2, Fe-Pd@SiO2, Cu-Ru@SiO2, Cu-Pt@SiO2, and Cu-Pd@SiO2 catalysts.

[0108] Example 27: Preparation of mesoporous meso-Ni-Ru@SiO2, meso-Ni-Pt@SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO2, meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, and meso-Cu-Pd@SiO2 catalysts

[0109] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.0627g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.1 for pore-forming reagent to shell-forming reagent), 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0110] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain the same). Ultimately, twelve materials are obtained: mesoporous meso-Ni-Ru@SiO2, meso-Ni-PtO, etc. @SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO 2. meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, meso-Cu-Pd@SiO2 catalyst.

[0111] Example 28: Preparation of mesoporous meso-Ni-Ru@SiO2, meso-Ni-Pt@SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO2, meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, and meso-Cu-Pd@SiO2 catalysts

[0112] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.1254g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.2 for pore-forming reagent to shell-forming reagent), 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0113] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain the same). Ultimately, twelve materials are obtained: mesoporous meso-Ni-Ru@SiO2, meso-Ni-PtO, etc. @SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO 2. meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, meso-Cu-Pd@SiO2 catalyst.

[0114] Example 29: Preparation of mesoporous meso-Ni-Ru@SiO2, meso-Ni-Pt@SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO2, meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, and meso-Cu-Pd@SiO2 catalysts

[0115] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.1881g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.3 for pore-forming reagent to shell-forming reagent), 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0116] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain the same). Ultimately, twelve materials are obtained: mesoporous meso-Ni-Ru@SiO2, meso-Ni-PtO, etc. @SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO 2. meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, meso-Cu-Pd@SiO2 catalyst.

[0117] Example 30: Preparation of mesoporous meso-Ni-Ru@SiO2, meso-Ni-Pt@SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO2, meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, and meso-Cu-Pd@SiO2 catalysts

[0118] Add 0.25g of NiO-RuO nanoparticles to 50g of anhydrous ethanol and sonicate for 30min. Then, in an ultrasonic bath, add 0.3135g of octadecyltrimethoxysilane (corresponding to a molar ratio of 0.5 for pore-forming reagent to shell-forming reagent), 0.3485g of tetraethyl orthosilicate (corresponding to a molar ratio of 0.5 for shell-forming reagent to metal core), and 10g of NH3·H2O sequentially under ultrasonic treatment (60min). Dry at 80℃ for 10h, calcine at 550℃ for 4h, and reduce to H2 at 550℃ for 3h.

[0119] The other steps are the same as above, except that the NiO-RuO nanoparticles are replaced with NiO-PtO, NiO-PdO, CoO-RuO, CoO-PtO, CoO-PdO, FeO-RuO, FeO-PtO, FeO-PdO, CuO-RuO, CuO-PtO, and CuO-PdO nanoparticles (molar amounts remain the same). Ultimately, twelve materials are obtained: mesoporous meso-Ni-Ru@SiO2, meso-Ni-PtO, etc. @SiO2, meso-Ni-Pd@SiO2, meso-Co-Ru@SiO2, meso-Co-Pt@SiO2, meso-Co-Pd@SiO2, meso-Fe-Ru@SiO 2. meso-Fe-Pt@SiO2, meso-Fe-Pd@SiO2, meso-Cu-Ru@SiO2, meso-Cu-Pt@SiO2, meso-Cu-Pd@SiO2 catalyst.

[0120] Example 31: Preparation of microporous and mesoporous Ni-Ru@Al2O3 and Ni-Ru@MgO catalysts

[0121] The preparation method is the same as above, except that aluminum isopropoxide and magnesium ethoxide are used instead of tetraethyl orthosilicate, and other conditions remain unchanged.

[0122] Figure 1 In the image, 'a' represents a TEM image of the Ni@SiO2 catalyst (corresponding to the metal core prepared in Example 1, and subsequently the catalyst prepared according to Example 18). Figure 1 b in the figure is a TEM image of the Ni-Ru@SiO2 catalyst (corresponding to the metal core prepared in Example 5, and then the catalyst prepared according to Example 25). The TEM image shows that the diameter of the metal core is 15-25 nm.

[0123] Figure 2 In the image, 'a' is a TEM image of the catalyst obtained in Example 24, where the molar ratio of the shell-forming agent to the metal core is 0.1. Figure 2 In Figure 'b', the TEM image of the catalyst obtained in Example 25 shows a molar ratio of 0.5 between the shell-forming agent and the metal core. Figure 2 In the image, 'c' is a TEM image of the catalyst obtained in Example 26, where the molar ratio of the shell-forming agent to the metal core is 1. From... Figure 2 It can be seen that as the molar ratio of metal oxide to shell-forming reagent increases from 0.1 to 1 (molar ratio), the shell thickness tends to increase, increasing from 5 nm to 30 nm.

[0124] Figure 3 The figures show the pore size distribution of the catalysts in Examples 25, 27, 28, 29, and 30, where the catalyst is Ni-Ru@SiO2. a b corresponds to Example 25, meso-Ni-Ru@SiO2 a,b,c Corresponding to Example 27, meso-Ni-Ru@SiO2 a,b,d Corresponding to Example 28, meso-Ni-Ru@SiO2 a,b,e Corresponding to Example 29, meso-Ni-Ru@SiO2 a,b,f Corresponding to Example 30. The average pore size values ​​of the corresponding catalysts are listed in Table 1.

[0125] Table 1. Average pore size and specific surface area of ​​Ni-Ru@SiO2 and meso-Ni-Ru@SiO2 catalysts.

[0126]

[0127]

[0128] The molar ratio of the main metal Ni to the auxiliary metal Ru is 80. b The molar ratio of the shell-forming reagent to the metal core is 0.5. c The molar ratio of pore-forming reagent to shell-forming reagent is 0.1. d The molar ratio of pore-forming reagent to shell-forming reagent is 0.2. e The molar ratio of pore-forming reagent to shell-forming reagent is 0.3. f The molar ratio of pore-forming reagent to shell-forming reagent is 0.5.

[0129] Depend on Figure 3 As shown in Table 1, the specific surface area and pore size in the shell increase as the molar ratio increases from 0.1 to 0.2. The specific surface area increases from 41.75 m² / s². 2 / g increased to 115.70m 2 / g, the average pore size increased from 3.91nm to 4.70nm. As the ratio increased from 0.2 to 0.5 (molar ratio), the specific surface area and pore size in the shell showed a decreasing trend, with the specific surface area increasing from 115.70nm. 2 / g decreased to 61.76m 2 / g, the pore size decreased from 4.70nm to 3.42nm, indicating that too much pore-forming reagent was added, which damaged the pore structure.

[0130] Example 32: Reductive Amination of Isosorbide Dione

[0131] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of Ni nanoparticle catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia water (5 mL, ammonia concentration of 25%, containing 66 mmol of ammonia). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 49%.

[0132] Example 33: Reductive Amination of Isosorbide Dione

[0133] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of microporous Ni@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 73%.

[0134] Example 34: Reductive Amination of Isosorbide Dione

[0135] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of microporous Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 81%.

[0136] Example 35: Reductive Amination of Isosorbide Dione

[0137] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 87%.

[0138] Example 36: Reductive Amination of Isosorbide Dione

[0139] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 8 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 64%.

[0140] Example 37: Reductive Amination of Isosorbide Dione

[0141] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (2 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 69%.

[0142] Example 38: Reductive Amination of Isosorbide Dione

[0143] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (6 MPa) and temperature (100 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 62%.

[0144] Example 39: Reductive Amination of Isosorbide Dione

[0145] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (120 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 83%.

[0146] Example 40: Reductive Amination of Isosorbide Dione

[0147] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia (5 mL). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (110 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed using an external standard method with an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 86%.

[0148] Example 41: Reductive Amination of Isosorbide Dione

[0149] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia water (3 mL, ammonia concentration of 25%, containing 39 mmol of ammonia). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (110 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed by external standard method with evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity of isosorbide diamine was 59%.

[0150] Example 42: Reductive Amination of Isosorbide Dione

[0151] The reaction was carried out in a 25 mL stainless steel reactor, with the addition of mesoporous meso-Ni-Ru@SiO2 catalyst (0.05 mg), isosorbide dione (0.143 g, 5 mmol), and ammonia water (7 mL, ammonia concentration of 25%, containing 92 mmol of ammonia). Before the reaction, the reactor was purged five times with H2 to replace residual air. Hydrogenation was then carried out at a constant H2 pressure (4 MPa) and temperature (110 °C) with a stirring rate of 1500 rpm. After 12 h of reaction, the liquid product was separated from the catalyst and further analyzed by external standard method using an evaporative light detector. The conversion rate of isosorbide dione was 99%, and the selectivity for isosorbide diamine was 87%.

[0152] Note: Since the amount of catalyst used is low, ordinary weighing methods cannot be used. We will uniformly disperse the catalyst in ammonia water and measure the volume of ammonia water.

[0153] Matters not covered in this invention are common knowledge.

Claims

1. A method for preparing isosorbide diamine, characterized in that, The method includes the following steps: Isosorbide dione and ammonia were loaded into a reactor containing a catalyst. Hydrogen was introduced into the reactor and the reaction was carried out at 100℃~200℃ for 10-20h to produce isosorbide diamine through a reductive amination reaction. The molar ratio of reactants is isosorbide dione:ammonia = 1:10-30; hydrogen pressure: 1-6 MPa; The catalyst has a core-shell structure, comprising an oxide shell and a metal core; the molar ratio of the oxide shell to the metal core is 0.1 to 1. The oxide shell is SiO2; The metal in the metal core is either the main metal M1 or the main metal M1 and the auxiliary metal M2, and the content of the catalytic component is 0.5% to 2% of the molar mass of the main metal. The main metal M1 is Ni; the auxiliary metal M2 is Ru, Pd, or Pt; The method for preparing the catalyst includes the following steps: (1) Preparation of metal cores: The nitrate of the nuclear metal and polyethylene glycol were added sequentially to distilled water. After stirring the solution for 30-60 minutes, urea was added to obtain a mixed solution. The mixture was heated to 80-95°C and reacted for 10-24 hours. The precipitate was collected by centrifugation, washed with ethanol and distilled water, dried, and calcined in air at 400-600°C for 2-4 hours to obtain metal oxide nanoparticles. In the mixed solution, the concentration of nitrate of the nuclear metal is 1-5 wt%, the concentration of polyethylene glycol is 2-6 wt%, and the concentration of urea is 2-6 wt%. (2) A shell is formed around the metal core: Metal oxide nanoparticles were added to anhydrous ethanol and subjected to ultrasonic treatment for 30–60 min. Then, a shell-forming reagent, a pore-forming reagent, and NH3·H2O were added under ultrasonic conditions. After the addition was complete, the reaction was continued under ultrasonic conditions for 30–60 min. The mixture was centrifuged, washed with ethanol and distilled water, dried, calcined at 400℃–600℃ for 2–4 h, and then reduced to H2 at 400℃–600℃ for 2–3 h to obtain the catalyst. The molar ratio of metal oxide nanoparticles to shell-forming reagent is 0.1 to 1, and the shell-forming reagent of the catalyst is tetraethyl orthosilicate, aluminum isopropoxide, or magnesium ethoxide. The mass of the metal oxide nanoparticles is 0.2–1.0 wt% of anhydrous ethanol; 5–10 g of NH3·H2O is added per 50 g of anhydrous ethanol; The pore-forming reagent is octadecyltrimethoxysilane or hexadecyltrimethylammonium bromide, and the molar ratio of the pore-forming reagent to the shell-forming reagent is 0.1 to 0.

5.

2. The method for preparing isosorbide diamine as described in claim 1, characterized in that, The diameter of the metal core is 15-25 nm, and the shell thickness is 5 nm to 30 nm.

3. The method for preparing isosorbide diamine as described in claim 1, characterized in that, In the preparation of catalysts, the thickness of the catalyst shell is determined by the ratio of the shell-forming reagent to the metal oxide. The molar ratio of metal oxide to shell-forming reagent is 0.1 to 1. As the molar ratio increases from 0.1 to 1, the shell thickness tends to increase, from 5 nm to 30 nm.

4. The method for preparing isosorbide diamine as described in claim 1, characterized in that, In catalyst preparation, the size and distribution of pores in the catalyst shell are determined by the amount of pore-forming reagent. As the molar ratio of pore-forming reagent to shell-forming reagent increases from 0.1 to 0.2, the specific surface area and pore size in the shell tend to increase, with the specific surface area increasing from 41.75 m². 2 / g increased to 115.70m 2 / g, the average pore size increased from 3.91 nm to 4.70 nm; however, as the molar ratio increased from 0.2 to 0.5, the specific surface area and pore size in the shell tended to decrease, with the specific surface area decreasing from 115.70 nm. 2 / g decreased to 61.76m 2 / g, the pore size decreased from 4.70nm to 3.42nm.

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