A kind of preparation method of 3-aminopropanol

Abstract

The invention provides a method for preparing 3-aminopropanol, wherein 3-hydroxypropanal is dissolved in a solvent and reacted with excess liquid ammonia, and then hydrogenated under the action of a catalyst to prepare 3-aminopropanol. The preparation method of the invention has the advantages of high conversion rate, high yield and high safety.

Description

Technical Field

[0001] The invention belongs to the technical field of compound preparation, and particularly relates to a method for preparing 3-aminopropanol. Background Art

[0002] 3-aminopropanol is widely used in the fields of daily chemical care products, food and pharmaceutical intermediates. In the pharmaceutical field, it can be used for the synthesis of anticancer drugs such as cyclophosphamide and cyclopentane. In the field of daily chemical care products and food, 3-aminopropanol is mainly used for the preparation of D-panthenol. Panthenol has the same metabolic process as vitamin B5 in the body, so it is also called provitamin B5. In the food industry and the field of daily chemicals, it is used as a nutritional supplement and enhancer to promote the metabolism of human protein, fat and sugar, maintain the skin and mucous membranes, improve hair gloss, enhance immunity, and prevent the occurrence of diseases. It can also be used as a skin care agent, which is a deeply penetrating moisturizer, stimulates the growth of epithelial cells, promotes wound healing, and has an anti-inflammatory effect. In recent years, with the improvement of people's living standards, the application of panthenol in daily chemical products has been continuously improved, especially in hair care products and other topical cosmetics. The application is becoming more and more extensive, which has greatly driven the market demand for 3-aminopropanol.

[0003] There are many methods for synthesizing 3-aminopropanol in the prior art, mainly acrylonitrile method, 1,4-butyrolactone method, ketoxime method, etc. CN111056963A patent application discloses using acrylonitrile as raw material, reacting with phenylethyl alcohol under an alkali catalyst, separating 3-benzyloxypropionitrile from the resulting reaction solution, and hydrogenating 3-benzyloxypropionitrile in a liquid phase reaction system in the presence of a hydrogenation catalyst, separating 3-aminopropanol from the resulting reaction solution. The acrylonitrile method has low starting raw material cost, but the reaction conversion rate is not high and the yield is low. The main reason for the low yield is that the 3-hydroxypropionitrile generated in the reaction process is further condensed with acrylonitrile to generate a large amount of by-product dicyanoethyl ether (see patent US2579580). Although existing patents (see US5268499, CN1189449C, JP1989090160A) report that dicyanoethyl ether can be converted into 3-hydroxypropionitrile and acrylonitrile by pyrolysis to improve the total utilization rate of raw materials, this undoubtedly increases the reaction process, thereby increasing the production cost. CN103012165A discloses a method of using 1,4-butyrolactone as a raw material, opening the ring under the action of hydrazine hydrate, adding sodium nitrite aqueous solution to generate acyl azide, and then rearranging to generate 3-aminopropanol. This method not only has a complicated process, but also has a low yield of the target product 3-aminopropanol, which is not suitable for scaled-up production. Feng Xiaoliang et al. disclose a method of synthesizing cyclohexanone oxime using cyclohexanone as a raw material, then condensing it with acrylonitrile, and then preparing 3-aminopropanol by catalytic hydrogenation and cracking. This method will also produce amine by-products, and there are also problems such as cumbersome steps, poor selectivity of the target product, and low product yield. The above disclosed method for preparing 3-aminopropanol has the problems of complicated steps, high toxicity of raw materials, poor safety, low selectivity, low yield, etc. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing 3-aminopropanol with simple process, high selectivity and high yield in view of the deficiencies in the prior art.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing 3-aminopropanol, comprising dissolving 3-hydroxypropanal in a solvent and reacting it with excess liquid ammonia, and then hydrogenating it under the action of a catalyst to obtain 3-aminopropanol. In the preparation method, 3-hydroxypropanal and liquid ammonia are used as raw materials to prepare the 3-aminopropanol product, and the reaction principle is that 3-hydroxypropanal reacts with liquid ammonia to generate a hydroxyimine intermediate, which is rapidly hydrogenated and reduced to 3-aminopropanol in a catalyst and hydrogen atmosphere under certain reaction conditions, and the process is as shown in the following formulas (1) and (2), and the obtained 3-aminopropanol can be refined by a distillation method. The catalyst can be a catalyst used for conventional imino hydrogenation reduction, such as Raney nickel. The use of a solvent ensures the dissolution of hydrogen and 3-imino-1-propanol, and a solvent that is easily separated from 3-aminopropanol is more preferred.

[0007] (1);

[0008] (2).

[0009] The preparation method of the present invention uses excess liquid ammonia, which is conducive to the generation of hydroxyimine intermediates, and can also inhibit the reaction of 3-hydroxypropanal with the generated 3-aminopropanol, and further produce di(3-hydroxypropyl)amine byproducts, thereby improving the yield and conversion rate. The raw materials use 3-hydroxypropanal, liquid ammonia, and hydrogen. Compared with the acrylonitrile method, the 1,4-butyrolactone method, and the ketoxime method, the raw materials have low toxicity and high safety.

[0010] As a further improvement of the technical solution, the solvent is an alcohol solvent, such as methanol, ethanol, butanol, tert-butanol, amyl alcohol, etc. Liquid ammonia has a high solubility in the solvent, which is beneficial to the intermediate reaction. At the same time, the selected solvent also has a high solubility for hydrogen, which is beneficial to the hydrogenation reduction reaction.

[0011] As a further improvement of the technical solution, in order to balance the viscosity and solubility of the reaction system, the alcohol solvent is one of methanol, ethanol and tert-butanol.

[0012] As a further improvement of the technical solution, in order to balance the separation cost and solubility performance, the mass ratio of 3-hydroxypropanal to alcohol solvent is 1.0:1.0~10.0.

[0013] As a further improvement of the technical solution, in order to balance the reaction efficiency and yield, the reaction temperature is 20°C to 80°C, and the reaction pressure is 0.5 to 4.0 MPa.

[0014] As a further improvement of the technical solution, if the amount of liquid ammonia is too high, it will also increase the difficulty and energy consumption of liquid ammonia separation. In step 1, the feed ratio of liquid ammonia to 3-hydroxypropionaldehyde is 1.1-10.0:1.0.

[0015] As a further improvement of the technical solution, in order to balance the cost and catalytic efficiency, the catalyst is Raney Ni or Pd / C.

[0016] As a further improvement of the technical solution, in order to improve production efficiency, the hydrogenation reaction is a fixed bed reaction, and the feed mass space velocity of 3-hydroxypropanal is 0.1-1.0h -1 .

[0017] The present invention has outstanding substantial characteristics and significant progress compared with the prior art. Specifically, the preparation method of the present invention has high yield and selectivity due to the use of excess liquid ammonia. Furthermore, the raw materials used in the preparation method have low toxicity and high safety. The preparation method of the present invention has the advantages of high conversion rate, high yield and high safety. DETAILED DESCRIPTION

[0018] The technical solution of the present invention is further described in detail below through specific implementation methods, but the content of the present invention is not limited to the following embodiments.

[0019] Comparative Example

[0020] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 20°C, hydrogen was introduced, and the hydrogen pressure was controlled at 0.5 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:1.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:1.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.1 h -1 The reaction materials were reacted in a fixed bed reactor, and the obtained mixed product was separated and refined by distillation to obtain 3-aminopropanol product. The conversion rate of 3-hydroxypropanal was 74.3%, and the yield of 3-aminopropanol was 38.6%.

[0021] Example 1

[0022] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 20°C, hydrogen was introduced, and the hydrogen pressure was controlled at 0.5 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:1.1, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:1.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.1 h -1The reaction materials were reacted in a fixed bed reactor, and the obtained mixed product was separated and refined by distillation to obtain 3-aminopropanol product. The conversion rate of 3-hydroxypropanal was 85.2%, and the yield of 3-aminopropanol was 51.3%.

[0023] Example 2

[0024] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 80°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.4%, and the yield of 3-aminopropanol is 82.3%.

[0025] Example 3

[0026] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 4.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:10.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:10.1. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to be 1.0 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.3%, and the yield of 3-aminopropanol is 94.5.

[0027] Example 4

[0028] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to be 1.0 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.2%, and the yield of 3-aminopropanol is 95.6%.

[0029] Example 5

[0030] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:3.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.6%, and the yield of 3-aminopropanol is 96.1%.

[0031] Example 6

[0032] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:3.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 95.4%, and the yield of 3-aminopropanol is 86.3%.

[0033] Example 7

[0034] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The ethanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to be 1.0 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 97.3%, and the yield of 3-aminopropanol is 95.4%.

[0035] Example 8

[0036] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The ethanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.6%, and the yield of 3-aminopropanol is 97.5%.

[0037] Example 9

[0038] The fixed reactor was loaded with 50 g of Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The ethanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.7 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.3%, and the yield of 3-aminopropanol is 96.5%.

[0039] Example 10

[0040] The fixed reactor was loaded with 50 g of Pd-C catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The ethanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.7 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.3%, and the yield of 3-aminopropanol is 93.1%.

[0041] Embodiment 11

[0042] The fixed reactor was loaded with 50 g of Pd-C catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The tert-butyl alcohol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.7 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 98.6%, and the yield of 3-aminopropanol is 95.1%.

[0043] Example 12

[0044] The fixed reactor was loaded with 50 g Raney Ni catalyst and N 2 After full replacement, the reactor temperature was controlled at 50°C, hydrogen was introduced, and the hydrogen pressure was controlled at 2.0 MPa. The tert-butyl alcohol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:10.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain a 3-aminopropanol product. The conversion rate of 3-hydroxypropanal is 99.7%, and the yield of 3-aminopropanol is 97.0%.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or some technical features can be replaced by equivalents without departing from the spirit of the technical solution of the present invention, which should be included in the scope of the technical solution for protection of the present invention.

Claims

1. A method for preparing 3-aminopropanol, characterized in that: 50 g of Raney Ni catalyst was loaded into the fixed reactor, and after being fully replaced with N2, the reactor temperature was controlled to be 50°C, and hydrogen was introduced to control the hydrogen pressure to be 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction materials was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:5.

0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to be 1.0 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain 3-aminopropanol product.

2. A method for preparing 3-aminopropanol, characterized in that: 50 g of Raney Ni catalyst was loaded into the fixed reactor, and after being fully replaced with N2, the reactor temperature was controlled to be 50°C, hydrogen was introduced, and the hydrogen pressure was controlled to be 2.0 MPa. The methanol solution of 3-hydroxypropanal and liquid ammonia were mixed in a static mixer and introduced into the fixed bed reactor. The molar ratio of 3-hydroxypropanal to liquid ammonia in the mixed reaction material was 1.0:5.0, and the mass ratio of 3-hydroxypropanal to methanol solvent was 1.0:3.

0. The feed flow rate of the mixed material was adjusted to control the mass space velocity of 3-hydroxypropanal to be 0.5 h -1 The reaction materials are reacted in a fixed bed reactor, and the obtained mixed product is separated and refined by distillation to obtain 3-aminopropanol product.