Preparation method of 3-aminopropanol and preparation method of D-panthenol

Abstract

The invention relates to a preparation method of 3-aminopropanol and a preparation method of D-panthenol. The preparation method of the 3-aminopropanol comprises the following steps: mixing homoserine, a ketone catalyst and a solid acid catalyst, carrying out a decarboxylation reaction, and after the reaction is completed, carrying out rectification separation on the reaction liquid to obtain the 3-aminopropanol, the solid acid catalyst is selected from at least one of an acidic metal oxide or a compound of the acidic metal oxide. According to the preparation method disclosed by the invention, the 3-aminopropanol is prepared by a one-pot method, so that the selective yield of the product is high, the process is simple, the cost is relatively low, and industrial production is convenient to realize.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a preparation method of 3-aminopropanol and a preparation method of D-panthenol. Background Art

[0002] 3-aminopropanol is widely used in the pharmaceutical, food and cosmetic industries. In the pharmaceutical industry, it can be used to synthesize anticancer drugs such as cyclophosphamide and quinolone. In the food and cosmetics industries, 3-aminopropanol is mainly used in the preparation of D-panthenol.

[0003] The traditional methods for synthesizing 3-aminopropanol mainly include acrylonitrile method, butyrolactone method, hydroxypropionitrile method, etc. Among them, the acrylonitrile method (see patent CN111056963A) uses an alkali catalyst to react acrylonitrile and phenylethanol to obtain 3-benzyloxypropionitrile, and then in the presence of a hydrogenation catalyst, 3-benzyloxypropionitrile is hydrogenated to obtain 3-aminopropanol. This method has the problems of low reaction conversion rate and low yield. The butyrolactone method (see patent CN103012165A) uses 1,4-butyrolactone as a raw material, opens the ring under the action of hydrazine hydrate, adds sodium nitrite aqueous solution to generate acyl azide, and then rearranges to generate 3-aminopropanol. The process of this method is complicated and the yield is low. The hydroxypropionitrile method is a conventional method for synthesizing 3-aminopropanol. Under the action of a catalyst, 3-hydroxypropionitrile, methanol and liquid ammonia are added to a high-pressure reactor for reaction, and 3-aminopropanol is obtained after purification. The catalyst used in this method is relatively expensive, and more gas is used, and the economic value is not high. All of the above three methods have the problems of low yield and high cost. Summary of the invention

[0004] Based on this, it is necessary to provide a method for preparing 3-aminopropanol and a method for preparing D-panthenol in order to solve the above problems. The preparation method of the present invention prepares 3-aminopropanol by a one-pot process, which not only has a high selectivity and yield of the product, but also has a simple process and low cost, and is easy to realize industrial production.

[0005] A method for preparing 3-aminopropanol comprises the following steps:

[0006] Homoserine, a ketone catalyst and a solid acid catalyst are mixed to carry out a decarboxylation reaction. After the reaction is completed, the reaction liquid is separated by distillation to obtain 3-aminopropanol, wherein the solid acid catalyst is selected from at least one of an acidic metal oxide or a complex of an acidic metal oxide.

[0007] In one embodiment, the molar ratio of the ketone catalyst to the homoserine is 3:1-12:1;

[0008] And / or, the mass ratio of the solid acid catalyst to the homoserine is 0.001:1-0.05:1.

[0009] In one embodiment, the solid acid catalyst is selected from at least one of γ-Al2O3, MoO3, ZrO2, WO3, TiO2, MoO3-ZrO2, WO3-ZrO2, SiO2-TiO2, SiO2-ZrO2, TiO2-ZrO2, SiO2-Al2O3 or B2O3-Al2O3.

[0010] In one embodiment, the ketone catalyst is selected from at least one of cyclohexanone, cyclohexenone, isophorone, carvone, acetophenone or benzophenone.

[0011] In one embodiment, the homoserine is selected from homoserine produced by fermentation or chemical synthesis;

[0012] And / or, the homoserine is at least one selected from L-homoserine, D-homoserine or DL-homoserine.

[0013] In one embodiment, after the reaction is completed and before the reaction solution is distilled and separated, the solid acid catalyst is separated and recovered from the reaction solution and recycled for use in the decarboxylation reaction.

[0014] In one embodiment, the reaction liquid is distilled and separated to recover the ketone catalyst, which is then recycled for use in the decarboxylation reaction.

[0015] In one embodiment, the temperature of the decarboxylation reaction is 120°C-180°C;

[0016] And / or, the pressure of the decarboxylation reaction is 0.5 MPa-4 MPa.

[0017] In one embodiment, the decarboxylation reaction device is selected from a reactor or a fluidized bed.

[0018] A method for preparing D-panthenol comprises the following steps:

[0019] 3-aminopropanol is prepared by the method for preparing 3-aminopropanol as described above;

[0020] D-pantolactone is reacted with the 3-aminopropanol to obtain D-panthenol.

[0021] The preparation method of the present invention, through a one-pot reaction, utilizes the synergistic effect of a ketone catalyst and a solid acid catalyst in a decarboxylation reaction process, and the ketone catalyst and the solid acid catalyst do not react in the decarboxylation reaction process, and can avoid the ketone catalyst from being deactivated due to an isomerization reaction or other side reactions, thereby significantly promoting the conversion of the imine functional group in the decarboxylation reaction process, and reducing the proportion of impurities in the reaction product, thereby improving the selectivity yield of 3-aminopropanol as a whole. In addition, the present invention adopts a specific solid acid catalyst, and can also avoid introducing other impurity ions or initiating side reactions, and further improve the selectivity yield of 3-aminopropanol.

[0022] Therefore, the preparation method provided by the present invention can not only obtain a 3-aminopropanol product with high selectivity and yield, but also has a simple process, low cost, and is easy to realize industrial production, and is particularly suitable for the industrial production of D-panthenol. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 The gas chromatogram of the reaction solution obtained in Example 1 of the present invention;

[0025] Figure 2 The gas chromatogram of 3-aminopropanol obtained in Example 1 of the present invention;

[0026] Figure 3 This is a gas chromatogram of the R-carvone catalyst recovered in Example 1 of the present invention;

[0027] Figure 4 The mass spectrum of the impurities separated and obtained in Comparative Example 1;

[0028] Figure 5 This is the gas chromatogram of R-carvone and related impurities separated in Comparative Example 2. DETAILED DESCRIPTION

[0029] For ease of understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific implementation methods or embodiments, and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the combinations include any two related listed items, any more related listed items, or all related listed items.

[0031] The present invention provides a method for preparing 3-aminopropanol, comprising the following steps:

[0032] Homoserine, a ketone catalyst and a solid acid catalyst are mixed to carry out a decarboxylation reaction. After the reaction is completed, the reaction liquid is separated by distillation to obtain 3-aminopropanol, wherein the solid acid catalyst is selected from at least one of an acidic metal oxide or a complex of an acidic metal oxide.

[0033] The preparation method of the present invention, through a one-pot reaction, utilizes the synergistic effect of a ketone catalyst and a solid acid catalyst in a decarboxylation reaction process, and the ketone catalyst and the solid acid catalyst do not react in the decarboxylation reaction process, and can avoid the ketone catalyst from being deactivated due to an isomerization reaction or other side reactions, thereby significantly promoting the conversion of the imine functional group in the decarboxylation reaction process, and reducing the proportion of impurities in the reaction product, thereby improving the selectivity yield of 3-aminopropanol as a whole. In addition, the present invention adopts a specific solid acid catalyst, and can also avoid introducing other impurity ions or initiating side reactions, and further improve the selectivity yield of 3-aminopropanol.

[0034] In order to further explain the reaction principle of the preparation method of the present invention, combined with the chemical reaction formula shown below, the synergistic catalytic reaction mechanism of the ketone catalyst and the solid acid catalyst is now disassembled step by step:

[0035]

[0036] During the decarboxylation reaction, the amino group in homoserine and the carbonyl group in the ketone catalyst first undergo a first step reaction to form a first intermediate having an imino group and a water molecule, and the first intermediate is deacidified to form a second intermediate. At the same time, under the action of a solid acid catalyst, the second intermediate and the water molecule produced in the first step reaction undergo a second step reaction, thereby producing 3-aminopropanol and a ketone catalyst with high selectivity and yield, with almost no additional impurities generated. Subsequently, high-purity and high-yield 3-aminopropanol can be obtained by simple separation, and the ketone catalyst can be recycled.

[0037] By regulating the dosage of homoserine, ketone catalyst and solid acid catalyst, the conversion efficiency of homoserine can be improved, the utilization of raw materials can be maximized, and the preparation cost can be reduced.

[0038] Preferably, the molar ratio of the ketone catalyst to the homoserine is 3:1-12:1, including but not limited to any value among 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1 or a range between any two values.

[0039] Preferably, the mass ratio of the solid acid catalyst to the homoserine is 0.001:1-0.05:1, including but not limited to any point value among 0.001:1, 0.002:1, 0.005:1, 0.008:1, 0.01:1, 0.02:1, 0.05:1 or any range value between two thereof.

[0040] It should be noted that the complex of acidic metal oxides described in the present invention can be a composite product of at least two acidic metal oxides, or a composite product of acidic metal oxides and inorganic oxides, wherein the acidic metal oxides include but are not limited to at least one of Al2O3, MoO3, ZrO2, WO3, and TiO2, and the inorganic oxides include but are not limited to at least one of SiO2 and B2O3.

[0041] Preferably, the solid acid catalyst is selected from at least one of γ-Al2O3, MoO3, ZrO2, WO3, TiO2, MoO3-ZrO2, WO3-ZrO2, SiO2-TiO2, SiO2-ZrO2, TiO2-ZrO2, SiO2-Al2O3 or B2O3-Al2O3, and is further preferably selected from at least one of γ-Al2O3, SiO2-Al2O3, B2O3-Al2O3.

[0042] Preferably, the chemical structure of the ketone catalyst contains at least one six-membered ring structure, and the six-membered ring structure includes cyclohexane, cyclohexene or a benzene ring. More preferably, the ketone catalyst is selected from at least one of cyclohexanone, cyclohexenone, isophorone, carvone, acetophenone or benzophenone.

[0043] It should be noted that the present invention does not limit the configuration of the ketone catalyst. For example, carvone can be selected from R-carvone or D-carvone, preferably R-carvone, which is more conducive to reducing costs. The present invention does not limit the source of homoserine. It can be homoserine produced by fermentation or chemical synthesis, or directly a commercially available homoserine product. Homoserine produced by fermentation or chemical synthesis is preferably used.

[0044] When homoserine prepared by fermentation is reacted, bio-based 3-aminopropanol is obtained; when bio-based 3-aminopropanol and D-pantolactone prepared by fermentation are reacted, fully bio-based D-panthenol is obtained. Compared with non-bio-based panthenol, bio-based panthenol is free from dependence on fossil raw materials, is more environmentally friendly, and better meets the requirements of sustainable development.

[0045] Preferably, the homoserine is selected from at least one of L-homoserine, D-homoserine and DL-homoserine, and more preferably L-homoserine.

[0046] In one embodiment, after the reaction is completed and before the reaction liquid is distilled and separated, the solid acid catalyst is separated and recovered from the reaction liquid and recycled in the decarboxylation reaction, thereby improving the utilization rate of the solid acid catalyst and facilitating further reducing the preparation cost.

[0047] It is understandable that, since the present invention uses a solid acid catalyst, the solid acid catalyst can be separated and recovered from the reaction solution by simple filtration, making the reaction process simple and easy to operate.

[0048] In one embodiment, the reaction liquid is recovered after distillation separation to obtain the ketone catalyst, and recycled for the decarboxylation reaction. Since the ketone catalyst and the solid acid catalyst do not react during the decarboxylation reaction, the loss of the ketone catalyst during the decarboxylation reaction is reduced, the recycling rate of the ketone catalyst is improved, and it is beneficial to further reduce the preparation cost.

[0049] It should be noted that the present invention does not limit the process of distillation separation, and the corresponding distillation conditions can be controlled according to the ketone catalyst used in the preparation method.

[0050] In one embodiment, the temperature of the decarboxylation reaction is 120°C-180°C, preferably 140°C-180°C; and / or the pressure of the decarboxylation reaction is 0.5MPa-4MPa. The one-pot reaction process adopted by the present invention can avoid the complicated operation of frequent heating and cooling in the traditional preparation process and the generation of impurities during the material transfer operation, which not only further improves the selectivity yield of 3-aminopropanol, but also simplifies the preparation process and facilitates industrial production.

[0051] It is understandable that the present invention does not limit the time of the decarboxylation reaction. By performing gas chromatography on the reaction solution, when the gas phase appearance of 3-aminopropanol in the reaction solution remains substantially unchanged, the reaction is terminated.

[0052] The present invention does not limit the device for the decarboxylation reaction, but preferably uses a reaction kettle or a fluidized bed.

[0053] The present invention also provides a method for preparing D-panthenol, comprising the following steps:

[0054] S1, preparing 3-aminopropanol by the preparation method of 3-aminopropanol as described above;

[0055] S2, reacting D-pantolactone with the 3-aminopropanol to obtain D-panthenol.

[0056] It should be noted that the present invention does not limit the reaction process of D-pantolactone and 3-aminopropanol, that is, the preparation method of 3-aminopropanol provided by the present invention can be applied to the existing reaction process of D-pantolactone and 3-aminopropanol, thereby realizing the efficient production of D-pantolactone, reducing the preparation cost of D-pantolactone, and further improving the industrial production of D-pantolactone.

[0057] Hereinafter, the preparation method of the 3-aminopropanol and the preparation method of D-panthenol will be further described by the following specific examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If no specific conditions are specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are followed. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be obtained commercially.

[0058] Example 1

[0059] 50 g (0.42 mol) of L-homoserine as a substrate was added to a 500 mL autoclave, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160°C and the reaction pressure was 0.6 MPa. After reacting for 1 hour, the reaction liquid was subjected to gas chromatography test. At this time, the gas phase appearance of 3-aminopropanol in the reaction liquid remained basically unchanged, such as Figure 1 As shown, the yield of 3-aminopropanol obtained in this example is 93.2%. The SiO2-Al2O3 catalyst is recovered by filtration, and the reaction solution is further distilled to obtain 3-aminopropanol, and the R-carvone catalyst is recovered. The obtained 3-aminopropanol is tested by gas chromatography, and the results are as follows: Figure 2 As shown, the purity of 3-aminopropanol obtained in this example reaches 99.4%. The recovered R-carvone catalyst was also tested by gas chromatography, and the results are as follows: Figure 3 As shown, it can be seen that the purity of the recovered R-carvone catalyst reaches 99.5%.

[0060] Example 2

[0061] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 567.8 g (3.78 mol) of R-carvone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.65 MPa, and the reaction solution was subjected to gas chromatography after 0.5 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged. It can be seen that the yield of 3-aminopropanol prepared in this embodiment is 93.6%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0062] Example 3

[0063] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 126.2 g (0.84 mol) of R-carvone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.65 MPa, and the reaction solution was subjected to gas chromatography after 2.5 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged. It can be seen that the yield of 3-aminopropanol prepared in this embodiment is 83.1%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0064] Example 4

[0065] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 220.7 g (1.47 mol) of R-carvone catalyst and 2.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.6 MPa, and the reaction solution was subjected to gas chromatography after 1 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged, and it can be seen that the yield of 3-aminopropanol prepared in this embodiment was 91.4%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0066] Example 5

[0067] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 180° C., the reaction pressure was 1 MPa, and the reaction solution was subjected to gas chromatography after 1 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged, indicating that the yield of 3-aminopropanol obtained in this embodiment was 85.6%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0068] Example 6

[0069] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of γ-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.62 MPa, and the reaction solution was subjected to gas chromatography after 1.5 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged, and it can be seen that the yield of 3-aminopropanol prepared in this embodiment was 85.4%. The γ-Al2O3 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0070] Example 7

[0071] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of B2O3-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.62 MPa, and the reaction solution was subjected to gas chromatography after 1.5 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged, and it can be seen that the yield of 3-aminopropanol prepared in this embodiment was 89.7%. The B2O3-Al2O3 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0072] Example 8

[0073] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 203.2 g (1.47 mol) of isophorone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 0.77 MPa, and the reaction solution was subjected to gas chromatography after 1.5 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged, and it was known that the yield of 3-aminopropanol obtained in this embodiment was 87.5%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the isophorone catalyst was recovered.

[0074] Example 9

[0075] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave as a substrate, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 140° C., the reaction pressure was 0.5 MPa, and the reaction solution was subjected to gas chromatography after 3 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution was basically unchanged, and it can be seen that the yield of 3-aminopropanol prepared in this embodiment was 85.3%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the R-carvone catalyst was recovered.

[0076] Example 10

[0077] 50 g (0.42 mol) of L-homoserine was added as a substrate to a 500 mL autoclave, and then 141.3 g (1.47 mol) of cyclohexenone catalyst and 1.5 g of SiO2-Al2O3 catalyst were added. The temperature was raised to 160° C., and the reaction pressure was 2.1 MPa. After reacting for 2 h, the reaction solution was subjected to a gas chromatography test. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged. It can be seen that the yield of 3-aminopropanol obtained in this embodiment was 84.4%. The SiO2-Al2O3 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the cyclohexenone catalyst was recovered.

[0078] Embodiment 11

[0079] 50 g (0.42 mol) of D-homoserine was added to a 500 mL autoclave as a substrate, and then 252.3 g (2.1 mol) of acetophenone catalyst and 0.5 g of MoO3-ZrO2 catalyst were added. The temperature was raised to 120° C., the reaction pressure was 1.9 MPa, and the reaction solution was subjected to gas chromatography after 3 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged, and it can be seen that the yield of 3-aminopropanol obtained in this embodiment was 82.1%. The MoO3-ZrO2 catalyst was recovered by filtration, and the reaction solution was further separated by rectification to obtain 3-aminopropanol, and the acetophenone catalyst was recovered.

[0080] Example 12

[0081] 50 g (0.42 mol) of L-homoserine was added as a substrate to a 500 mL autoclave, and then 161.5 g (1.68 mol) of cyclohexenone catalyst and 1.5 g of WO3-ZrO2 catalyst were added. The temperature was raised to 160° C., the reaction pressure was 2.1 MPa, and the reaction solution was subjected to gas chromatography after 2 h of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged, indicating that the yield of 3-aminopropanol obtained in this embodiment was 85.4%. The WO3-ZrO2 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the cyclohexenone catalyst was recovered.

[0082] Embodiment 13

[0083] 50 g (0.42 mol) of L-homoserine was added as a substrate to a 500 mL autoclave, and then 141.3 g (1.47 mol) of cyclohexenone catalyst and 1.5 g of SiO2-TiO2 catalyst were added. The temperature was raised to 160° C., and the reaction pressure was 2.1 MPa. After reacting for 2 h, the reaction solution was subjected to a gas chromatography test. At this time, the gas phase appearance of 3-aminopropanol in the reaction solution remained substantially unchanged. It can be seen that the yield of 3-aminopropanol obtained in this embodiment was 84.9%. The SiO2-TiO2 catalyst was recovered by filtration, and the reaction solution was further subjected to rectification and separation to obtain 3-aminopropanol, and the cyclohexenone catalyst was recovered.

[0084] Comparative Example 1

[0085] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave, and then 220.7 g (1.47 mol) of R-carvone catalyst was added, the temperature was raised to 160° C., the reaction pressure was 0.6 MPa, and the reaction liquid was subjected to gas chromatography after 1 hour of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction liquid remained basically unchanged, and it was known that the yield of 3-aminopropanol obtained in this comparative example was 42.5%. The reaction liquid was subjected to rectification and separation, and the separated intermediate was subjected to mass spectrometry test. The test results are as follows: Figure 4 shown.

[0086] Comparative Example 2

[0087] 50 g (0.42 mol) of L-homoserine was added to a 500 mL autoclave, and then 220.7 g (1.47 mol) of R-carvone catalyst and 1.5 g of strong acid cationic resin were added, the temperature was raised to 160° C., the reaction pressure was 0.6 MPa, and the reaction liquid was subjected to gas chromatography after 1 hour of reaction. At this time, the gas phase appearance of 3-aminopropanol in the reaction liquid was basically unchanged, and it can be seen that the yield of 3-aminopropanol obtained in this comparative example was 62.3%, and the strong acidic cationic resin in the reaction liquid of this comparative example had poor high temperature resistance, which led to its easy deactivation.

[0088] Comparative Example 3

[0089] 50 g of L-homoserine (0.42 mol) was added to a 500 mL autoclave, and then 220.7 g of R-carvone catalyst (1.47 mol) was added, the temperature was raised to 160° C., the reaction pressure was 0.6 MPa, and after reacting for 1 hour, the temperature was lowered to room temperature, the reaction solution was transferred to a 1 L three-necked flask, 200 mL (3 mol / L) of hydrochloric acid was added, the temperature was raised to 60° C. and stirred vigorously for 2 hours, the obtained 3-aminopropanol hydrochloride was distributed in the water layer with a yield of 73.9%, R-carvone and related impurities were distributed in the organic layer, and R-carvone and related impurities were tested by gas chromatography, and the results were as follows: Figure 5 As shown, it can be seen that the comparative example produces too many types of impurities, because hydrochloric acid causes the R-carvone catalyst to undergo an isomerization reaction, which not only causes the R-carvone catalyst to be partially deactivated, but also reduces the recovery and utilization of the R-carvone catalyst. In addition, since hydrochloric acid is used in this comparative example, not only is the reaction under high temperature and high pressure extremely demanding on the equipment material, but it also requires pressure reduction and temperature reduction to add an acid catalyst, resulting in a complicated preparation method.

[0090] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0091] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing 3-aminopropanol, characterized in that: The preparation method comprises the following steps: Homoserine, a ketone catalyst and a solid acid catalyst are mixed to carry out a decarboxylation reaction. After the reaction is completed, the reaction liquid is separated by distillation to obtain 3-aminopropanol, wherein the solid acid catalyst is selected from at least one of an acidic metal oxide or a complex of an acidic metal oxide.

2. The method for preparing 3-aminopropanol according to claim 1, characterized in that The molar ratio of the ketone catalyst to the homoserine is 3:1-12:1; And / or, the mass ratio of the solid acid catalyst to the homoserine is 0.001:1-0.05:

1.

3. The method for preparing 3-aminopropanol according to claim 1 or 2, characterized in that: The solid acid catalyst is selected from at least one of γ-Al2O3, MoO3, ZrO2, WO3, TiO2, MoO3-ZrO2, WO3-ZrO2, SiO2-TiO2, SiO2-ZrO2, TiO2-ZrO2, SiO2-Al2O3 or B2O3-Al2O3.

4. The method for preparing 3-aminopropanol according to claim 1 or 2, characterized in that: The ketone catalyst is selected from at least one of cyclohexanone, cyclohexenone, isophorone, carvone, acetophenone or benzophenone.

5. The method for preparing 3-aminopropanol according to claim 1 or 2, characterized in that: The homoserine is selected from homoserine produced by fermentation or chemical synthesis; And / or, the homoserine is selected from at least one of L-homoserine, D-homoserine and DL-homoserine.

6. The method for preparing 3-aminopropanol according to claim 1, characterized in that: After the reaction is completed and before the reaction liquid is distilled and separated, the solid acid catalyst is separated and recovered from the reaction liquid and recycled for use in the decarboxylation reaction.

7. The method for preparing 3-aminopropanol according to claim 1, characterized in that: The reaction liquid is recovered after distillation and separation to obtain the ketone catalyst, which is circulated for use in the decarboxylation reaction.

8. The method for preparing 3-aminopropanol according to claim 1, characterized in that: The temperature of the decarboxylation reaction is 120°C-180°C; And / or, the pressure of the decarboxylation reaction is 0.5 MPa-4 MPa.

9. The method for preparing 3-aminopropanol according to claim 1, characterized in that: The decarboxylation reaction device is selected from a reactor or a fluidized bed.

10. A method for preparing D-panthenol, characterized in that: The steps include: 3-aminopropanol is prepared by the preparation method of 3-aminopropanol according to any one of claims 1 to 9; D-pantolactone is reacted with the 3-aminopropanol to obtain D-panthenol.

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