Supported catalyst as well as preparation method and application thereof
By preparing Cu and Ni3N supported carbon catalysts, the problems of high cost and poor stability of Pd-based catalysts were solved, and high conversion and selectivity were achieved in the process of preparing propionic acid by hydrogenation of acrylic acid, which is suitable for large-scale production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-11-20
- Publication Date
- 2026-05-22
AI Technical Summary
Existing Pd-based catalysts for the hydrogenation of acrylic acid to propionic acid suffer from problems such as high catalyst cost, poor stability, and easy polymerization of acrylic acid.
By using Cu and Ni3N supported carbon catalysts, Cu and Ni3N are generated simultaneously through nitriding in an ammonia atmosphere, and their ratio can be flexibly controlled to prepare a supported catalyst with good activity and high stability.
It improves the conversion rate of acrylic acid and the selectivity of propionic acid. The catalyst preparation method is stable and controllable, and is suitable for large-scale production.
Smart Images
Figure BDA0005145178620000081 
Figure BDA0005145178620000091
Abstract
Description
Technical Field
[0001] This application relates to a supported catalyst, its preparation method, and its application, belonging to the field of chemical engineering. Background Technology
[0002] Propionic acid is an important chemical raw material. Propionic acid and its derivatives are widely used in the synthesis of resins, grain preservation, food and feed additives, fragrances, pesticides, and pharmaceutical intermediates. Originally, propionic acid was obtained by condensing and separating gases produced during charcoal manufacturing and coal coking. In the 1950s, a process for producing acetic acid by oxidizing light hydrocarbons was developed abroad. The product contained approximately 10% propionic acid, which was then separated and purified to obtain propionic acid. In addition to hydrocarbon oxidation methods, the United States also has a method using ethylene, CO, and H2 as raw materials to synthesize propionaldehyde via carbonylation, followed by further oxidation to propionic acid. Due to the development of low-pressure carbonylation synthesis processes using rhodium-phosphine complexes as catalysts, the propionaldehyde oxidation method has developed rapidly in recent years. This method is superior to the traditional high-pressure method using cobalt carbonyl catalysts. BASF in Germany uses the Rapa process to produce propionic acid from ethylene, CO, and water. Although there are many methods for synthesizing propionic acid, only the Rapa process, propionaldehyde oxidation method, and light hydrocarbon oxidation method have achieved industrial-scale production. Currently, my country only uses the light hydrocarbon oxidation method to produce a small amount of propionic acid.
[0003] Acrylic acid, as an important raw material for organic synthesis and a monomer for synthetic resins, has an increasingly wide range of applications. More than 85% of acrylic acid is produced using the relatively economical propylene oxidation method, which is also the preferred method for large-scale production. Currently, the world has the capacity to produce inexpensive acrylic acid. Therefore, the hydrogenation of acrylic acid to propionic acid technology holds promise as a cost-effective technology for propionic acid production. Currently, there are few reports on the hydrogenation of acrylic acid to propionic acid, but some progress has been made with Pd-based catalysts. For example, using Pd / SiO2 catalysts at 200℃, propionic acid selectivity can reach 100%; using Pd-Cu and Pd / C catalysts in liquid-phase reactions at reaction temperatures of 20–80℃, acrylic acid conversion can reach 99%. However, Pd-based catalysts still suffer from high catalyst costs, poor catalytic stability, and the tendency of acrylic acid to polymerize under certain reaction conditions. Summary of the Invention
[0004] The method for preparing Cu and Ni3N supported carbon catalysts in this application allows for the simultaneous formation of Cu and Ni3N at a suitable nitriding temperature in an ammonia atmosphere, without the presence of Cu3N. The ratio of Cu to Ni3N in the catalyst can be flexibly adjusted without causing environmental damage; Ni3N possesses noble metal properties, and its substitution for noble metals can reduce material costs. When applied to the hydrogenation of acrylic acid to propionic acid, the catalyst exhibits good activity, high acrylic acid conversion and propionic acid selectivity, and good stability.
[0005] According to one aspect of this application, a supported catalyst is provided, the supported catalyst comprising a carbon support and an active component supported on the surface of the carbon support;
[0006] The active components include elemental copper and Ni3N;
[0007] In the supported catalyst, the loading of elemental copper is 1-2 wt%, and the loading of Ni3N is 1-2 wt%.
[0008] Optionally, in the supported catalyst, the loading of elemental copper is any value of 1 wt%, 1.5 wt%, 2 wt%, or any value between any two, and the loading of Ni3N is any value of 1 wt%, 1.5 wt%, 2 wt%, or any value between any two.
[0009] The carbon carrier is selected from at least one of activated carbon and porous carbon.
[0010] According to another aspect of this application, a method for preparing the above-mentioned supported catalyst is provided, comprising the following steps:
[0011] The carbon support was impregnated in an aqueous solution containing the active component precursor, dried, calcined, and nitrided under a nitrogen atmosphere to obtain the supported catalyst.
[0012] The active component precursor includes a copper source and a nickel source;
[0013] The copper source is selected from at least one of copper nitrate and copper sulfate;
[0014] The nickel source is selected from at least one of nickel nitrate and nickel sulfate;
[0015] The solid-liquid ratio of the carbon support to the aqueous solution containing the active component precursor is 1:0.4-0.6 g / ml;
[0016] Optionally, the solid-liquid ratio of the carbon support to the aqueous solution containing the active component precursor is any value among 1:0.4 g / ml, 1:0.5 g / ml, and 1:0.6 g / ml, or any range between the two.
[0017] The soaking time is 12 to 24 hours.
[0018] Optionally, the immersion time is any value among 12h, 18h, and 24h, or a range between any two.
[0019] The drying temperature is 80–120°C;
[0020] Optionally, the drying temperature is any value among 80°C, 90°C, 100°C, 110°C, and 120°C, or a range between any two.
[0021] The drying time is 8 to 20 hours.
[0022] Optionally, the drying time is any value among 8h, 10h, 12h, 14h, 16h, 18h, and 20h, or a range between any two.
[0023] The calcination temperature is 450–650°C;
[0024] Optionally, the calcination temperature is any value among 450°C, 500°C, 550°C, 600°C, and 650°C, or a range between any two.
[0025] The calcination time is 1 to 6 hours;
[0026] Optionally, the calcination time is any value among 1h, 2h, 3h, 4h, 5h, and 6h, or a range between any two.
[0027] The calcination atmosphere is a nitrogen atmosphere.
[0028] The nitriding treatment temperature is 450–550°C;
[0029] Optionally, the nitriding temperature is any value among 450°C, 500°C, and 550°C, or a range between any two.
[0030] The nitriding treatment time is 2 to 4 hours.
[0031] Optionally, the nitriding treatment time is any value among 2h, 3h, and 4h, or a range between any two.
[0032] According to another aspect of this application, a method for preparing propionic acid by hydrogenation of acrylic acid is provided, comprising the following steps:
[0033] In a closed container (high-pressure reactor), raw materials containing acrylic acid and propionic acid are brought into contact with a catalyst, hydrogen gas is introduced to replace the catalyst, and the reaction is carried out to obtain a product containing propionic acid.
[0034] The catalyst is the supported catalyst described above.
[0035] In the raw materials, the mass ratio of acrylic acid to propionic acid is 0.25 to 3.5;
[0036] Optionally, the mass ratio of acrylic acid to propionic acid in the raw materials is any value from 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or any range between the two.
[0037] The mass ratio of acrylic acid to catalyst in the raw materials is 4 to 70.
[0038] Optionally, the mass ratio of acrylic acid to catalyst in the raw material is any value from 4, 10, 20, 30, 40, 50, 60, 70 or any range between the two.
[0039] The hydrogen replacement is performed 2 to 4 times.
[0040] Optionally, the number of hydrogen replacements can be any value among 2, 3, and 4.
[0041] The reaction temperature is 20–80°C;
[0042] Optionally, the temperature of the reaction is any value among 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, and 80°C, or a range between any two.
[0043] The reaction time is 1 to 5 hours;
[0044] Optionally, the reaction time is any value among 1h, 2h, 3h, 4h, and 5h, or a range between any two.
[0045] The reaction is carried out at a pressure of 0.1–0.5 MPa.
[0046] Optionally, the pressure of the reaction is any value of 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, or a range between any two.
[0047] The beneficial effects that this application can produce include:
[0048] 1) The catalyst provided in this application can be applied to the reaction of acrylic acid hydrogenation to prepare propionic acid, and improves the conversion rate of acrylic acid and the selectivity of the propionic acid produced.
[0049] 2) The preparation method of the catalyst provided in this application is stable, controllable, and reproducible.
[0050] 3) The method for preparing propionic acid by hydrogenation of acrylic acid provided in this application uses the catalyst provided in this application, which has a fast reaction rate and high yield, and can be applied to large-scale production. Detailed Implementation
[0051] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0052] The analysis method in the embodiments of this application is as follows:
[0053] Gas chromatography characterization
[0054] The composition of the products from the hydrogenation of acrylic acid to propionic acid was analyzed using an Agilent 7890B gas chromatograph (FID detector, HP-1 column).
[0055] The conversion rate and selectivity calculations in the embodiments of this application are as follows:
[0056] Acrylic acid conversion rate = (mass of acrylic acid consumed) * 100% / (mass of acrylic acid feed)
[0057] Propionic acid selectivity = (mass of propionic acid product * 100%) / (mass of acrylic acid reacted)
[0058] Example 1: Preparation of Catalyst
[0059] Activated carbon with a solid-liquid ratio of 1:0.6 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 20 h, it was dried at 100 °C for 18 h, calcined at 550 °C for 2 h under a nitrogen atmosphere, and then nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 1. # .
[0060] Example 2 Preparation of Catalyst
[0061] Activated carbon with a solid-liquid ratio of 1:0.4 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 16 h, dried at 120 °C for 12 h, calcined at 450 °C for 6 h under a nitrogen atmosphere, and nitrided at 550 °C for 4 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1 wt%, Ni3N content 2 wt%), denoted as catalyst 2. # .
[0062] Example 3: Preparation of Catalyst
[0063] Porous carbon with a solid-liquid ratio of 1:0.45 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 18 h, dried at 110 °C for 16 h, calcined at 500 °C for 4 h under a nitrogen atmosphere, and nitrided at 500 °C for 3 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 2 wt%, Ni3N content 1 wt%), denoted as catalyst 3. # .
[0064] Example 4: Preparation of Catalyst
[0065] Activated carbon with a solid-liquid ratio of 1:0.55 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 24 h, it was dried at 80 °C for 14 h, calcined at 650 °C for 2 h under a nitrogen atmosphere, and then nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1 wt%, Ni3N content 2 wt%), denoted as catalyst 4. # .
[0066] Example 5: Preparation of Catalyst
[0067] Activated carbon with a solid-liquid ratio of 1:0.5 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 22 h, it was dried at 90 °C for 8 h, calcined at 600 °C for 3 h under a nitrogen atmosphere, and then nitrided at 550 °C for 3 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 5. # .
[0068] Example 6 Preparation of Catalyst
[0069] Porous carbon with a solid-liquid ratio of 1:0.6 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 12 h, dried at 100 °C for 10 h, calcined at 550 °C for 5 h under a nitrogen atmosphere, and nitrided at 500 °C for 4 h under an ammonia atmosphere to obtain a Cu and Ni3N supported carbon catalyst (Cu content 2 wt%, Ni3N content 1 wt%), denoted as catalyst 6. # .
[0070] Example 7 Preparation of Catalyst
[0071] Activated carbon with a solid-liquid ratio of 1:0.5 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 14 h, it was dried at 80 °C for 18 h, calcined at 450 °C for 4 h under a nitrogen atmosphere, and then nitrided at 550 °C for 4 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 7. # .
[0072] Example 8: Preparation of Catalyst
[0073] Activated carbon with a solid-liquid ratio of 1:0.45 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 20 h, it was dried at 120 °C for 12 h, calcined at 550 °C for 6 h under a nitrogen atmosphere, and nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1 wt%, Ni3N content 2 wt%), denoted as catalyst 8. # .
[0074] Example 9 Preparation of Catalyst
[0075] Porous carbon with a solid-liquid ratio of 1:0.55 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left for 18 h, dried at 110 °C for 10 h, calcined at 500 °C for 3 h under a nitrogen atmosphere, and nitrided at 500 °C for 3 h under an ammonia atmosphere to obtain a Cu and Ni3N supported carbon catalyst (Cu content 2 wt%, Ni3N content 1 wt%), denoted as catalyst 9. # .
[0076] Example 10 Preparation of Catalyst
[0077] Activated carbon with a solid-liquid ratio of 1:0.4 g / ml was impregnated in a solution of copper nitrate and nickel nitrate, left to stand for 14 h, dried at 90 °C for 14 h, calcined at 650 °C for 3 h under a nitrogen atmosphere, and nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1 wt%, Ni3N content 2 wt%), denoted as catalyst 10. # .
[0078] Example 11 Preparation of Catalyst
[0079] Activated carbon with a solid-liquid ratio of 1:0.55 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 24 h, dried at 100 °C for 16 h, calcined at 600 °C for 2 h under a nitrogen atmosphere, and nitrided at 550 °C for 4 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 2 wt%, Ni3N content 1 wt%), denoted as catalyst 11. # .
[0080] Example 12 Preparation of Catalyst
[0081] Activated carbon with a solid-liquid ratio of 1:0.5 g / ml was impregnated in a copper sulfate and nickel sulfate solution. After standing for 22 h, it was dried at 110 °C for 8 h, calcined at 550 °C for 3 h under a nitrogen atmosphere, and nitrided at 500 °C for 3 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 12. # .
[0082] Example 13 Preparation of Catalyst
[0083] Porous carbon with a solid-liquid ratio of 1:0.45 g / ml was impregnated in a solution of copper nitrate and nickel nitrate, left to stand for 16 h, dried at 120 °C for 18 h, calcined at 500 °C for 5 h under a nitrogen atmosphere, and nitrided at 550 °C for 3 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1 wt%, Ni3N content 2 wt%), denoted as catalyst 13. # .
[0084] Example 14 Preparation of Catalyst
[0085] Activated carbon with a solid-liquid ratio of 1:0.4 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 12 h, dried at 80 °C for 16 h, calcined at 650 °C for 2 h under a nitrogen atmosphere, and nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 14. # .
[0086] Example 15 Preparation of Catalyst
[0087] Activated carbon with a solid-liquid ratio of 1:0.6 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 20 h, it was dried at 90 °C for 12 h, calcined at 450 °C for 6 h under a nitrogen atmosphere, and nitrided at 500 °C for 4 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 2 wt%, Ni3N content 1 wt%), denoted as catalyst 15. # .
[0088] Example 16 Preparation of Catalyst
[0089] Porous carbon with a solid-liquid ratio of 1:0.6 g / ml was impregnated in a copper sulfate and nickel sulfate solution, left to stand for 18 h, dried at 100 °C for 18 h, calcined at 600 °C for 4 h under a nitrogen atmosphere, and nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu and Ni3N supported carbon catalyst (Cu content 1.5 wt%, Ni3N content 1.5 wt%), denoted as catalyst 16. # .
[0090] Preparation of catalyst in Comparative Example 1
[0091] Activated carbon with a solid-liquid ratio of 1:0.6 g / ml was impregnated in a solution of copper nitrate and nickel nitrate. After standing for 20 h, it was dried at 100 °C for 18 h, calcined at 550 °C for 2 h under a nitrogen atmosphere, and then nitrided at 450 °C for 2 h under an ammonia atmosphere to obtain Cu, Ni3N supported carbon catalyst (Cu content 1.5 wt%), denoted as catalyst 17. # .
[0092] Example 17: Evaluation of the Catalyst's Reaction
[0093] The catalyst 1 obtained above # ~16 # This method is applied to the hydrogenation of acrylic acid to prepare propionic acid. A catalyst, acrylic acid, and propionic acid are added to a high-pressure reactor. After purging with hydrogen, the temperature is raised to the reaction temperature, a certain pressure is maintained, the reaction speed is adjusted, and the pressure is released after a period of reaction. The reaction mixture is filtered, and the liquid is analyzed using gas chromatography.
[0094] The reaction conditions and results are shown in Table 1.
[0095] Table 1
[0096]
[0097]
[0098] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A supported catalyst, characterized in that, The supported catalyst includes a carbon support and an active component supported on the surface of the carbon support; The active components include elemental copper and Ni3N; In the supported catalyst, the loading of elemental copper is 1-2 wt%, and the loading of Ni3N is 1-2 wt%. The carbon carrier is selected from at least one of activated carbon and porous carbon.
2. A method for preparing the supported catalyst according to claim 1, characterized in that, Includes the following steps: The carbon support was impregnated in an aqueous solution containing the active component precursor, dried, calcined, and nitrided under an ammonia atmosphere to obtain the supported catalyst.
3. The preparation method according to claim 2, characterized in that, The active component precursor includes a copper source and a nickel source; The copper source is selected from at least one of copper nitrate and copper sulfate; The nickel source is selected from at least one of nickel nitrate and nickel sulfate; The solid-liquid ratio of the carbon support to the aqueous solution containing the active component precursor is 1:0.4-0.6 g / ml; The soaking time is 12 to 24 hours.
4. The preparation method according to claim 2, characterized in that, The drying temperature is 80–120°C; The drying time is 8 to 20 hours.
5. The preparation method according to claim 2, characterized in that, The calcination temperature is 450–650°C; The calcination time is 1 to 6 hours; The calcination atmosphere is a nitrogen atmosphere.
6. The preparation method according to claim 2, characterized in that, The nitriding treatment temperature is 450–550°C; The nitriding treatment time is 2 to 4 hours.
7. A method for preparing propionic acid by hydrogenation of acrylic acid, characterized in that, Includes the following steps: In a sealed container, raw materials containing acrylic acid and propionic acid are brought into contact with a catalyst, hydrogen gas is introduced to replace the catalyst, and the reaction is carried out to obtain a product containing propionic acid. The catalyst is the supported catalyst as described in claim 1.
8. The method according to claim 7, characterized in that, In the raw materials, the mass ratio of acrylic acid to propionic acid is 0.25 to 3.5; The mass ratio of acrylic acid to catalyst in the raw materials is 4 to 70.
9. The method according to claim 7, characterized in that, The hydrogen replacement is performed 2 to 4 times.
10. The method according to claim 7, characterized in that, The reaction temperature is 20–80°C; The reaction time is 1 to 5 hours; The reaction is carried out at a pressure of 0.1–0.5 MPa.