A catalyst for the hydrogenation of 3-hydroxypropionitrile to 3-aminopropanol and a method for the preparation thereof
Patent Information
- Application Number
- CN202610584635.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-29
- Publication Date
- 2026-09-15
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, specifically to a catalyst for the hydrogenation of 3-hydroxypropionitrile to 3-aminopropanol and its preparation method. Background Technology
[0002] 3-Aminopropanol is an important organic synthetic intermediate widely used in the pharmaceutical, cosmetic, and chemical industries. Using 3-aminopropanol as a raw material, it can be used to synthesize antitumor drugs such as cyclophosphamide, cardiovascular drugs such as serotonin, and precursors of vitamin B5. It can also be used to prepare moisturizers, surfactants, preservatives, and dye and coating additives.
[0003] The existing methods for synthesizing 3-aminopropanol mainly include the following: (1) Catalytic hydrogenation method using 3-hydroxypropionitrile as raw material. Under the catalysis of Raney nickel, 3-hydroxypropionitrile reacts with liquid ammonia and hydrogen to generate 3-aminopropanol. (2) Hydrogenation-hydrolysis method using 3-methoxypropionitrile as raw material. 3-methoxypropionitrile reacts with hydrogen to generate 3-methoxypropylamine, which is then hydrolyzed to obtain 3-aminopropanol. (3) Chlorination-ammonolysis method using 1,3-propanediol as raw material. 1,3-propanediol reacts with hydrogen chloride to generate 3-chloropropanol, which is then ammonolyzed to obtain 3-aminopropanol. (4) Hydration-catalytic hydrogenation method using acrylonitrile as raw material. Acrylonitrile undergoes hydration to generate 3-hydroxypropionitrile, which is then catalytically hydrogenated to obtain 3-aminopropanol. Among them, the catalytic hydrogenation method using 3-hydroxypropionitrile as a raw material is currently the most widely used industrial route for the synthesis of 3-aminopropanol. However, the conversion rate of 3-hydroxypropionitrile is low and the selectivity of 3-aminopropanol is poor, which affects the yield and purity of 3-aminopropanol. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a method for preparing a catalyst and to apply the obtained catalyst to the hydrogenation of 3-hydroxypropionitrile to synthesize 3-aminopropanol, thereby improving the conversion rate of 3-hydroxypropionitrile and the yield and purity of 3-aminopropanol.
[0005] The technical problem to be solved by this invention is achieved by the following technical solution:
[0006] One objective of this invention is to provide a method for preparing a catalyst, comprising the following steps:
[0007] S1. Dissolve manganese salt and yttrium salt in water to obtain a metal salt solution;
[0008] S2. The carrier is immersed in the metal salt solution prepared in step S1. After immersion, the carrier is filtered, dried, and calcined to obtain the precursor.
[0009] S3. The precursor prepared in step S2 is reduced and activated to obtain the catalyst.
[0010] Furthermore, the manganese salt includes, but is not limited to, at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, and their hydrates.
[0011] Furthermore, the yttrium salt includes, but is not limited to, at least one of yttrium sulfate, yttrium chloride, yttrium nitrate, yttrium acetate, and their hydrates.
[0012] Furthermore, the carrier includes, but is not limited to, at least one of activated alumina, molecular sieve, activated carbon, titanium dioxide, and calcined diatomaceous earth.
[0013] Furthermore, the impregnation is performed with the assistance of ultrasound. Ultrasonic treatment promotes the adsorption of metal ions onto the carrier surface, thereby increasing the loading of the active metal component.
[0014] Furthermore, the molar ratio of manganese salt to yttrium salt is (4~5):1; the ratio of the total mass of manganese salt and yttrium salt to the mass of the carrier is 1:(1~10). Strict control of the molar ratio of manganese salt to yttrium salt is necessary; too little or too much yttrium salt will prevent the active metal yttrium and manganese from exerting a synergistic effect. Controlling the mass ratio of metal salt to carrier not only improves metal utilization and reduces costs but also regulates the density of active sites.
[0015] Furthermore, the calcination is carried out in an air atmosphere. Even further, the calcination temperature is 500~700℃, and the time is 1~8 h.
[0016] Furthermore, the reduction activation is carried out in a hydrogen atmosphere with a hydrogen volume hourly space velocity of 500–2000 h⁻¹. -1 Furthermore, the reduction and activation temperature is 500~800℃, the pressure is 0.1~0.5 MPa, and the time is 1~8 h.
[0017] In this invention, moisture is removed by drying, metal ions are converted into metal oxides by calcination, and metal oxides are converted into elemental metals by reduction activation.
[0018] A second objective of this invention is to provide a catalyst prepared by the aforementioned preparation method.
[0019] A third objective of this invention is to provide the application of the catalyst in the hydrogenation of 3-hydroxypropionitrile to synthesize 3-aminopropanol.
[0020] Furthermore, the amount of the catalyst used is 0.1-2% of the mass of 3-hydroxypropionitrile.
[0021] The beneficial effects of this invention are:
[0022] 1. The catalyst preparation method provided by this invention has the characteristics of simple operation, mild conditions and low equipment requirements, and is suitable for large-scale production.
[0023] 2. When the catalyst described in this invention is applied to the hydrogenation synthesis of 3-aminopropanol from 3-hydroxypropionitrile, the conversion rate of 3-hydroxypropionitrile and the selectivity of 3-aminopropanol can be significantly improved, the generation of by-products can be reduced, and the reaction time can be shortened, resulting in high yield and high purity of 3-aminopropanol.
[0024] 3. The catalyst described in this invention can be recycled, making it green and environmentally friendly, and greatly reducing the cost of the catalyst. Detailed Implementation
[0025] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.
[0026] The following examples illustrate the source of raw materials:
[0027] Activated alumina was purchased from Gongyi Qixin Water Purification Materials Co., Ltd., with a specific surface area ≥300 m². 2 / g.
[0028] The activated carbon was purchased from Henan Tingyuan Activated Carbon Co., Ltd., with a specific surface area ≥750 m². 2 / g.
[0029] ZSM-5 molecular sieves were purchased from Shandong Hefeng Environmental Protection Technology Co., Ltd., with a specific surface area ≥350 m². 2 / g.
[0030] Calcined diatomite was purchased from Shijiazhuang Hualang Mineral Products Trading Co., Ltd., grade II, with a content ≥98%.
[0031] Raney nickel FSC-4110 was purchased from Hangzhou Fangsheng New Materials Co., Ltd.
[0032] The RaneCAT-1200 nickel was purchased from Shanghai Xunkai Chemical Technology Co., Ltd.
[0033] The Raney nickel RCF-CF-80-4 was purchased from Jiangsu Raney Metal Technology Co., Ltd.
[0034] Example 1
[0035] Catalyst preparation:
[0036] S1. Dissolve manganese chloride (5.03 g, 0.04 mol) and yttrium chloride (1.95 g, 0.01 mol) in 50 mL of deionized water to obtain a metal salt solution;
[0037] S2. 20 g of activated alumina is impregnated in the metal salt solution prepared in step S1 under ultrasonic assistance (ultrasonic frequency of 25 kHz, ultrasonic power of 100 W, ultrasonic time of 5 h). After impregnation, it is filtered, dried in an oven at 60℃ for 12 h, and calcined in air atmosphere (calcination temperature of 700℃, calcination time of 3 h) to obtain the precursor.
[0038] S3, in a hydrogen atmosphere (volume hourly space velocity of 1000 h⁻¹) -1 The precursor prepared in step S2 was reduced and activated (the reduction and activation temperature was 650℃, the pressure was 0.3 MPa, and the time was 5 h) to obtain the catalyst.
[0039] Example 2
[0040] Catalyst preparation:
[0041] S1. Dissolve manganese sulfate (7.55 g, 0.05 mol) and yttrium sulfate (2.05 g, 0.01 mol) in 50 mL of deionized water to obtain a metal salt solution;
[0042] S2. 15 g of activated carbon is impregnated in the metal salt solution prepared in step S1. The impregnation is carried out under ultrasonic assistance (ultrasonic frequency of 25 kHz, ultrasonic power of 100 W, ultrasonic time of 4 h). After impregnation, the carbon is filtered, dried in an oven at 80℃ for 8 h, and calcined in air atmosphere (calcination temperature of 600℃, calcination time of 5 h) to obtain the precursor.
[0043] S3, in a hydrogen atmosphere (volume hourly space velocity of 500 h⁻¹) -1 The precursor prepared in step S2 was reduced and activated (the reduction and activation temperature was 700℃, the pressure was 0.2 MPa, and the time was 4 h) to obtain the catalyst.
[0044] Example 3
[0045] Catalyst preparation:
[0046] S1. Dissolve manganese nitrate (8.05 g, 0.045 mol) and yttrium nitrate (3.83 g, 0.01 mol) in deionized water to obtain a metal salt solution;
[0047] S2. 25 g of ZSM-5 molecular sieve was impregnated in the metal salt solution prepared in step S1. The impregnation was carried out under ultrasonic assistance (ultrasonic frequency of 25 kHz, ultrasonic power of 200 W, ultrasonic time of 3 h). After impregnation, the mixture was filtered, dried in an oven at 80℃ for 6 h, and calcined in air atmosphere (calcination temperature of 500℃, calcination time of 8 h) to obtain the precursor.
[0048] S3, in a hydrogen atmosphere (volume hourly space velocity of 2000 h⁻¹) -1 The precursor prepared in step S2 was reduced and activated (the reduction and activation temperature was 800℃, the pressure was 0.1 MPa, and the time was 5 h) to obtain the catalyst.
[0049] Example 4
[0050] Catalyst preparation:
[0051] S1. Dissolve manganese acetate dihydrate (13.4 g, 0.05 mol) and yttrium acetate (2.55 g, 0.01 mol) in deionized water to obtain a metal salt solution;
[0052] S2. 35 g of calcined diatomaceous earth was impregnated in the metal salt solution prepared in step S1 under ultrasonic assistance (ultrasonic frequency of 25 kHz, ultrasonic power of 50 W, ultrasonic time of 5 h). After impregnation, the mixture was filtered, dried in an oven at 70℃ for 5 h, and calcined in air atmosphere (calcination temperature of 550℃, calcination time of 5 h) to obtain the precursor.
[0053] S3, in a hydrogen atmosphere (volume hourly space velocity of 1000 h⁻¹) -1 The precursor prepared in step S2 was reduced and activated (the reduction and activation temperature was 700℃, the pressure was 0.2 MPa, and the time was 8 h) to obtain the catalyst.
[0054] Comparative Example 1
[0055] The catalyst was prepared according to the method of Example 1, except that the molar ratio of manganese chloride to yttrium chloride in step S1 was adjusted to 3:1.
[0056] Comparative Example 2
[0057] The catalyst was prepared according to the method of Example 1, except that the molar ratio of manganese chloride to yttrium chloride in step S1 was adjusted to 6:1.
[0058] Example 5
[0059] The catalysts prepared in Examples 1-4 and Comparative Examples 1-2, as well as a commercially available Raney nickel catalyst, were used to synthesize 3-aminopropanol. The yield and purity of the product 3-aminopropanol are shown in Table 1.
[0060] Synthesis of 3-aminopropanol:
[0061] 3-hydroxypropionitrile (711 g, 10 mol), liquid ammonia (341 g, 20 mol), 25 g catalyst, and 500 mL methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95 °C and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio of 3:1) to obtain 3-aminopropanol.
[0062] Table 1. Yield and purity of product 3-aminopropanol
[0063] Example 1 96.8 99.92 Example 2 97.4 99.93 Example 3 97.0 99.91 Example 4 96.5 99.92 Comparative Example 1 87.4 98.94 Comparative Example 2 81.2 98.90 Raney Nickel FSC-4110 94.5 99.91 Raney Nickel RaneCAT-1200 90.4 98.72 Raney Nickel RCF-CF-80-4 91.3 98.45
[0064] As can be seen from Table 1, compared with commercially available Raney nickel catalysts, the catalysts prepared in Examples 1-4 of this invention have excellent catalytic performance and can substantially improve the yield of 3-aminopropanol.
[0065] To further improve the catalytic performance of the catalyst described in this invention, when calcined diatomaceous earth is used as the support, the calcined diatomaceous earth is pretreated to enhance its adsorption capacity and increase the loading of metal active components on it.
[0066] Furthermore, the calcined diatomaceous earth is pretreated before use. The pretreatment method is as follows: octyl glucoside is dissolved in deionized water, then the calcined diatomaceous earth is added, and the mixture is heated to 150-180°C under stirring for a hydrothermal reaction for 8-12 hours. After cooling to room temperature, the mixture is filtered, washed with water, and dried. Preferably, the mass ratio of the calcined diatomaceous earth to octyl glucoside is 10:(2-3).
[0067] Example 5
[0068] The catalyst was prepared according to the method of Example 4, except that the calcined diatomaceous earth in step S2 was pretreated.
[0069] Pretreatment of calcined diatomaceous earth: 20 g of octyl glucoside was dissolved in deionized water, then 100 g of calcined diatomaceous earth was added. The mixture was heated to 150℃ and hydrothermally reacted for 12 h with stirring. After cooling to room temperature, the mixture was filtered, washed with water, and dried in an oven at 70℃ for 12 h. The yield of 3-aminopropanol was 98.4%, and the purity was 99.93%.
[0070] Example 6
[0071] The catalyst was prepared according to the method of Example 4, except that the calcined diatomaceous earth in step S2 was pretreated.
[0072] Pretreatment of calcined diatomaceous earth: 30 g of octyl glucoside was dissolved in deionized water, and then 100 g of calcined diatomaceous earth was added. The mixture was heated to 180℃ and hydrothermally reacted for 8 h with stirring. After cooling to room temperature, the mixture was filtered, washed with water, and dried in an oven at 60℃ for 12 h. The yield of 3-aminopropanol was 98.9%, and the purity was 99.92%.
[0073] Example 7
[0074] The catalyst was prepared according to the method of Example 4, except that the calcined diatomaceous earth in step S2 was pretreated.
[0075] Pretreatment of calcined diatomaceous earth: 25 g of octyl glucoside was dissolved in deionized water, then 100 g of calcined diatomaceous earth was added. The mixture was heated to 160℃ and hydrothermally reacted for 10 h with stirring. After cooling to room temperature, the mixture was filtered, washed with water, and dried in an oven at 80℃ for 8 h. The yield of 3-aminopropanol was 98.7%, and the purity was 99.93%.
[0076] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a catalyst, characterized in that, Includes the following steps: S1. Dissolve manganese salt and yttrium salt in water to obtain a metal salt solution; S2. The carrier is immersed in the metal salt solution prepared in step S1. After immersion, the carrier is filtered, dried, and calcined to obtain the precursor. S3. The precursor prepared in step S2 is reduced and activated to obtain the catalyst.
2. The preparation method according to claim 1, characterized in that: The manganese salt is selected from at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, and their hydrates.
3. The preparation method according to claim 1, characterized in that: The yttrium salt is selected from at least one of yttrium sulfate, yttrium chloride, yttrium nitrate, yttrium acetate, and their hydrates.
4. The preparation method according to claim 1, characterized in that: The carrier is selected from at least one of activated alumina, molecular sieve, activated carbon, titanium dioxide, and calcined diatomaceous earth.
5. The preparation method according to claim 1, characterized in that: The molar ratio of the manganese salt to the yttrium salt is (4~5):1; the ratio of the total mass of the manganese salt and the yttrium salt to the mass of the carrier is 1:(1~10).
6. The preparation method according to claim 1, characterized in that: The calcination is carried out in an air atmosphere; preferably, the calcination temperature is 400~700℃ and the time is 1~10 h.
7. The preparation method according to claim 1, characterized in that: The reduction and activation are carried out in a hydrogen atmosphere with a hydrogen volume hourly space velocity of 500–2000 h⁻¹. -1 Preferably, the reduction and activation temperature is 500~800℃, the pressure is 0.1~0.5MPa, and the time is 1~8 h.
8. The catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the catalyst according to claim 8 in the hydrogenation of 3-hydroxypropionitrile to synthesize 3-aminopropanol.
10. The application according to claim 9, characterized in that: The amount of catalyst used is 0.1-2% of the mass of 3-hydroxypropionitrile.