CN113121368A - Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof - Google Patents

Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof Download PDF

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CN113121368A
CN113121368A CN202110562414.3A CN202110562414A CN113121368A CN 113121368 A CN113121368 A CN 113121368A CN 202110562414 A CN202110562414 A CN 202110562414A CN 113121368 A CN113121368 A CN 113121368A
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catalyst
metal
aminopropanol
gamma
kettle
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刘树蓬
刘磊
张冬竹
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Hefei Huaheng Biological Engineering Co ltd
Anhui Huaheng Biotechnology Co Ltd
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Hefei Huaheng Biological Engineering Co ltd
Anhui Huaheng Biotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy

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Abstract

The invention relates to a method for preparing gamma-aminopropanol by one-step catalytic hydrogenation, which comprises the following steps of carrying out hydrogenation reaction on beta-alanine and hydrogen in a reaction solvent in the presence of a metal catalyst to obtain the gamma-aminopropanol. The method has the advantages of high yield, high purity of the prepared gamma-aminopropanol, simple and convenient operation, cheap and easily obtained raw materials, safety, controllability, greenness, environmental protection, more excellent cost, suitability for industrial production and the like, and obviously improves the quality, yield, effectiveness and safety of the gamma-aminopropanol prepared product.

Description

Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof.
Background
Gamma-aminopropanol is an important fine chemical intermediate, is widely applied to the fields of medicine, daily chemicals and the like, and is used as a preparation precursor of medicaments (cyclophosphamide, propranolol and the like) and daily chemicals (provitamin B)5Also known as panthenol) raw material, and has wide market prospect.
Gamma-aminopropanol is prepared by reacting 3-hydroxypropionitrile with hydrogen in the presence of ammonia. The production and supply of 3-hydroxypropionitrile affects the industrialization of γ -aminopropanol. The 3-hydroxypropionitrile is mainly synthesized by an acrylonitrile hydration method, an ethylene oxide method or a 2-chloroethanol cyanidation method. The acrylonitrile hydration method takes acrylonitrile as a substrate, and reacts in an alkaline aqueous solution to form an organic mixture containing 3-hydroxypropionitrile, bis (cyanoethyl) ester and acrylonitrile, and then the 3-hydroxypropionitrile is prepared by adopting an evaporation-extraction process; the ethylene oxide method takes ethylene oxide and cyanohydrin as raw materials to react in sodium carboxylate cation exchange resin, and 3-hydroxypropionitrile is prepared by rectifying and purifying reaction products; the 2-chloroethanol cyanidation method takes chloroethanol and sodium cyanide (hydrocyanic acid) as raw materials to react to prepare the 3-hydroxypropionitrile. However, the acrylonitrile hydration method and the ethylene oxide method have the problems of complex process, more byproducts, low product yield, difficult wastewater treatment and the like, and the 2-chloroethanol cyanidation method takes a highly toxic substance sodium cyanide (hydrocyanic acid) as a raw material, has potential safety hazards and has higher requirements on experimenters and experimental environments. In view of the problems of safety, environmental protection, efficiency, yield, process difficulty and the like in the preparation of the 3-hydroxypropionitrile, the price of the raw materials is higher, the production cost of the gamma-aminopropanol is increased, and the production of the gamma-aminopropanol is limited due to insufficient supply stability of the raw materials under increasingly strict environmental protection supervision. Therefore, the preparation method of the gamma-aminopropanol, which is simple and convenient to operate, safe and controllable, green and environment-friendly, low in production cost and easy for industrial production, is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a method for preparing gamma-aminopropanol by one-step catalytic hydrogenation, which comprises the following step of carrying out hydrogenation reaction on beta-alanine and hydrogen in a reaction solvent in the presence of a metal catalyst to obtain the gamma-aminopropanol.
In a preferred technical scheme of the present invention, the metal catalyst is a group VIII metal catalyst, preferably any one of a metal binary catalyst, a metal ternary catalyst, and a metal quaternary catalyst, or a combination thereof.
In a preferred embodiment of the present invention, the metal binary catalyst comprises ruthenium and any one selected from rhodium, palladium and platinum.
In a preferred embodiment of the present invention, the molar ratio of ruthenium to any one of rhodium, palladium and platinum in the metal binary catalyst is (0.1-20): 1, preferably (1-15): 1, more preferably (5-10): 1.
in a preferred technical scheme of the invention, the metal three-way catalyst is composed of ruthenium and any two of rhodium, palladium and platinum.
In a preferred technical scheme of the invention, the molar ratio of ruthenium to any two of rhodium, palladium and platinum in the metal three-way catalyst is (1-9): (1-9): (1-9), preferably (1-2): (1-2): (1-2).
In a preferred technical scheme of the invention, the metal quaternary catalyst is composed of a composition of ruthenium, rhodium, palladium and platinum, preferably the composition of ruthenium: rhodium: palladium: the mole ratio of platinum is (1-9): (2-8): (2-8): (2-8), preferably (4-8): (1-2): (1-2): (1-2).
In a preferred technical scheme of the invention, the metal catalyst further comprises a catalyst carrier.
In a preferred technical scheme of the invention, the catalyst carrier is selected from silica sol, aluminosilicate, activated carbon, carbon nano tube and SiO2、Al2O3In (1)Any one or a combination thereof.
In a preferred embodiment of the present invention, the aluminosilicate is selected from any one of sodium aluminosilicate, potassium aluminosilicate, and calcium aluminosilicate, or a combination thereof.
In a preferred embodiment of the present invention, the mass ratio of the catalyst to the catalyst support in the metal catalyst is 0.5 to 10%, preferably 1 to 8%, and more preferably 1.5 to 5%.
In a preferred technical scheme of the invention, the metal catalyst is a metal salt catalyst.
In a preferred embodiment of the present invention, the metal salt is selected from any one of hydrochloride, bromate, carbonate, bicarbonate, sulfate, bisulfate, and phosphate.
In the preferable technical scheme of the invention, in the reaction system, the mass ratio of the beta-alanine to the metal catalyst is 100: (0.1-15), preferably 100: (0.5-5), more preferably 100: (1-3).
In the preferable technical scheme of the invention, the concentration of beta-alanine in the reaction system is less than or equal to 60 percent, and preferably 10-50 percent.
In the preferred technical scheme of the invention, the pH of the reaction system is less than or equal to 6, preferably the pH is 1-5, and more preferably the pH is 3-4.
In a preferred technical scheme of the invention, the pH regulator for regulating the pH of the reaction system is any one or combination of sulfuric acid, nitric acid and hydrochloric acid.
In the preferred technical scheme of the invention, the reaction temperature is more than or equal to 15 ℃, preferably 30-150 ℃, more preferably 50-110 ℃ and further preferably 55-95 ℃.
In the preferred technical scheme of the invention, the reaction pressure P is more than or equal to 0.1MPa, preferably more than or equal to 2MPa, more preferably 5-12MPa, and still more preferably 5-8 MPa.
In a preferred embodiment of the present invention, the reaction solvent is a polar solvent, preferably any one or a combination of water, methanol, ethanol, isopropanol, and tetrahydrofuran.
In the preferred technical scheme of the invention, the reaction solution is filtered, and the filtrate is collected and distilled to obtain the catalyst.
In a preferred technical scheme of the invention, the preparation of the metal catalyst comprises the following steps:
(1) dissolving metal salt in water, adding silica sol, stirring and uniformly mixing;
(2) adding an alkali solution, stirring and reacting for a period of time;
(3) filtering, collecting a filter cake, washing and drying to obtain a dried product;
(4) and (4) reacting the dried product with hydrogen to obtain the catalyst.
In the preferred technical scheme of the invention, the preparation of the catalyst comprises the following steps of dissolving metal salt in water, adding silica sol, stirring, reacting at the pH of 8-10 and the temperature of 40-50 ℃ for 2-4 hours, filtering, washing a filter cake with water, drying, reacting the obtained dried product at the temperature of 300-500 ℃ for 5-7 hours in a hydrogen environment, and crushing to obtain the catalyst.
In a preferred technical scheme of the invention, the preparation of the metal catalyst comprises the following steps:
(1) dissolving a metal salt in water to prepare a metal salt solution;
(2) after acid washing and alkali washing, washing the activated carbon with water to a pH value of 6-7;
(3) uniformly mixing the activated carbon obtained in the step (2) with the metal salt solution prepared in the step (1), reacting at the temperature of 40-50 ℃ at the pH of 8-10, filtering, collecting a filter cake, washing with water, drying, and reacting the obtained dried product with hydrogen to obtain the catalyst;
wherein, the steps (1) and (2) are not divided into a sequence.
In a preferred technical scheme of the invention, the preparation of the metal catalyst comprises the following steps:
(1) dissolving a metal salt in water to prepare a metal salt solution;
(2) after acid washing and alkali washing, washing the activated carbon with water to a pH value of 6-7;
(3) and (2) uniformly mixing the activated carbon obtained in the step (2) with the metal salt solution prepared in the step (1), reacting for 2-4 hours at the pH of 8-10 and the temperature of 40-50 ℃, filtering, washing with water, drying, reducing the obtained dried product for 5-7 hours at the temperature of 300-500 ℃ in a hydrogen environment, and crushing to obtain the catalyst.
In a preferred embodiment of the present invention, the metal salt is selected from any one of ruthenium hydrochloride, rhodium hydrochloride, palladium hydrochloride, platinum hydrochloride, or a combination thereof.
In a preferred technical scheme of the invention, the metal salt is selected from any one of ruthenium trichloride, rhodium trichloride, palladium dichloride and platinum tetrachloride or a combination thereof.
In a preferred technical scheme of the invention, the metal salt is a composition of ruthenium trichloride and a second metal salt, and the molar ratio of the ruthenium trichloride to the second metal salt in the composition is (0.1-20): 1, preferably (1-15): 1, more preferably the molar ratio is (5-10): 1, more preferably the second metal salt is selected from any one of rhodium trichloride, palladium dichloride, platinum tetrachloride.
In a preferred technical scheme of the invention, the metal salt is a composition of ruthenium trichloride, a third metal salt and a fourth metal salt, and the molar ratio of the ruthenium trichloride to the third metal salt to the fourth metal salt is (1-9): (1-9): (1-9), preferably (1-2): (1-2): (1-2), more preferably, the third metal salt and the fourth metal salt are selected from any two of rhodium trichloride, palladium dichloride and platinum tetrachloride which are different from each other.
In the preferred technical scheme of the invention, the metal salt is a composition of ruthenium trichloride, rhodium trichloride, palladium dichloride and platinum tetrachloride, and the molar ratio of ruthenium trichloride, rhodium trichloride, palladium dichloride and platinum tetrachloride in the composition is (1-9): (2-8): (2-8): (2-8), preferably (4-8): (1-2): (1-2): (1-2).
In the preferred technical scheme of the invention, the mass ratio of the metal salt to the water is 1: (20-500).
In a preferred technical scheme of the invention, the mass ratio of the metal salt to the silica sol or the activated carbon is 1-20%, preferably 2-15%, and further preferably 3-10%.
In the preferable technical scheme of the invention, the acid washing method comprises the following steps of soaking the activated carbon in 8-9% nitric acid solution for 2 hours at the temperature of 45 ℃.
In a preferred technical scheme of the invention, the alkali washing method comprises the following steps of soaking activated carbon in a 10% sodium hydroxide solution for 2 hours at 45 ℃.
In a preferred technical scheme of the invention, the pH adjusting agent for adjusting pH is selected from any one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and potassium carbonate solution or a combination thereof.
In a preferred embodiment of the present invention, the drying is selected from any one or a combination of vacuum drying, atmospheric drying, and pneumatic drying.
In a preferred technical scheme of the invention, the drying mode is any one or combination of microwave drying and tubular oven drying.
In the preferred technical scheme of the invention, the drying temperature is 90-120 ℃, and preferably 100-110 ℃.
In the preferred technical scheme of the invention, the drying time is more than or equal to 1 hour, and preferably 5-7 hours.
In a preferred embodiment of the invention, the purity of the prepared gamma-aminopropanol is more than 95%, preferably more than 98%, more preferably more than 99%.
Still another object of the present invention is to provide a high-purity γ -aminopropanol for use in the preparation of any one of pharmaceuticals, daily chemicals and foods, preferably in the preparation of any one of panthenol, acamprosate, chloropropamphetamine, domperidone, ifosfamide, urapidil, cyclophosphamide and meclol.
Unless otherwise indicated, when the present invention relates to percentages between liquids, said percentages are volume/volume percentages; the invention relates to the percentage between liquid and solid, said percentage being volume/weight percentage; the invention relates to the percentages between solid and liquid, said percentages being weight/volume percentages; the balance being weight/weight percent.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the gamma-aminopropanol by one-step catalytic hydrogenation has the advantages of high yield, high purity of the prepared gamma-aminopropanol, simple and convenient operation, cheap and easily obtained raw materials, safety, controllability, environmental protection, higher cost, suitability for industrial production and the like, and obviously improves the quality, yield, effectiveness and safety of products prepared from the gamma-aminopropanol.
Detailed Description
The present invention is further illustrated in detail by the following examples and experimental examples. These examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Examples 1 to 4Preparation of the Metal catalyst of the invention
Examples 1-4 the preparation of the metal catalyst comprises the following steps:
respectively weighing 2g of the starting material shown in the table 1, dissolving the starting material in 500g of water, adding 50g of silica sol, stirring to uniformly mix the starting material and the silica sol, dropwise adding 100ml of sodium hydroxide solution (1mol/L), reacting for 3 hours at 45 ℃, filtering, washing a filter cake for 2 times by using 500ml of deionized water, placing the filter cake at 100 ℃ for microwave drying for 6 hours, reducing the dried product for 6 hours at 400 ℃ in a hydrogen environment, and crushing to obtain the catalyst 1-4.
Examples 5 to 10Preparation of the Metal catalyst of the invention
Examples 5-10 preparation of metal catalysts comprising the following steps:
(1) weighing 2g of the starting materials in the table 1 respectively, and dissolving the starting materials in 500g of water to prepare a starting material solution;
(2) weighing 50g of activated carbon, soaking the activated carbon in a nitric acid solution with the concentration of 8-9% at 45 ℃ for 2h, filtering, collecting a filter cake, washing with pure water, transferring the filter cake to a 10% sodium hydroxide solution, soaking at 45 ℃ for 2h, filtering, collecting the filter cake, washing with pure water, adding the filter cake into the nitric acid solution with the concentration of 8-9%, soaking at 45 ℃ for 2h, filtering, collecting the filter cake, and washing with pure water to the pH of 6-7;
(3) adding the filter cake into the aqueous solution of the initial raw material prepared in the step (1), stirring, uniformly mixing, dropwise adding 150ml of sodium carbonate solution (1mol/L), reacting for 3h at 45 ℃, filtering, washing the filter cake with 500ml of deionized water for 2 times, then performing microwave drying for 6h at 100 ℃, reducing the dried product for 6h at 400 ℃ in a hydrogen environment, and crushing to obtain the catalyst 5-10.
Catalysts 1-10 were prepared from examples 1-10, respectively.
TABLE 1
Numbering Starting materials
Example 1 Ruthenium trichloride (RuCl)3)
Example 2 RuCl3：PdCl2＝6:1(mol/mol)
Example 3 RhCl3：PdCl2：RuCl3＝1:2:2(mol/mol/mol)
Example 4 RhCl3：PdCl2：RuCl3：PtCl4＝1:2:4:1(mol/mol/mol/mol)
Example 5 Ruthenium trichloride (RuCl)3)
Example 6 RuCl3：PdCl2＝6:1(mol/mol)
Example 7 RhCl3：PdCl2：RuCl3＝1:2:2(mol/mol/mol)
Example 8 RhCl3：PdCl2：RuCl3：PtCl4＝1:2:4:1(mol/mol/mol/mol)
Example 9 RhCl3：PdCl2：RuCl3：PtCl4＝1:1:2:1(mol/mol/mol/mol)
Example 10 RhCl3：PdCl2：RuCl3：PtCl4＝1:1:8:1(mol/mol/mol/mol)
Example 11Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 1 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 369.2g of gamma-aminopropanol, wherein the yield is 87.60% and the purity is 99.85%.
Example 12Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 2 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction, the mixture is filtered, washed by water, a filter cake is recycled, and the filtrate is collected and distilled to obtain 362.4g of gamma-aminopropanol, wherein the yield is 85.98 percent, and the purity is 99.79 percent.
Example 13Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 3 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction, the mixture was filtered, washed with water, the filter cake was recovered and reused, and the filtrate was collected and distilled to obtain 363.6g of γ -aminopropanol, yield 86.27%, purity 99.69%.
Example 14Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 4 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 356.3g of gamma-aminopropanol, wherein the yield is 84.54% and the purity is 99.75%.
Example 15Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 10g of catalyst 1 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction, the reaction solution was filtered, washed with water, the filter cake was recovered and reused, and the filtrate was collected and distilled to obtain 364.9g of γ -aminopropanol, with a yield of 86.58% and a purity of 99.56%.
Example 16Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 1 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 366.7g of gamma-aminopropanol, wherein the yield is 87.00 percent and the purity is 99.78 percent.
Example 17Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 1 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 95 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 369.0g of gamma-aminopropanol, wherein the yield is 87.55% and the purity is 99.93%.
Example 18Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 1 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 95 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 8 Mpa. After the reaction, the mixture is filtered, washed by water, a filter cake is recycled, filtrate is collected and distilled to obtain 366.2g of gamma-aminopropanol, the yield is 86.88%, and the purity is 99.91%.
Example 19Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 5 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 369.6g of gamma-aminopropanol, wherein the yield is 87.69% and the purity is 99.75%.
Example 20Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 6 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 362.3g of gamma-aminopropanol, wherein the yield is 85.96 percent, and the purity is 99.69 percent.
Example 21Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 7 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction, the mixture is filtered, washed by water, filter cakes are recycled, filtrate is collected and distilled to obtain 363.6g of gamma-aminopropanol, the yield is 86.27 percent, and the purity is 99.81 percent.
Example 22Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 8 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 358.0g of gamma-aminopropanol, wherein the yield is 84.94% and the purity is 99.75%.
Example 23Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 10g of catalyst 5 into a high-pressure reaction kettle, adjusting the pH value of the solution to 3 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 362.8g of gamma-aminopropanol, wherein the yield is 86.08% and the purity is 99.76%.
Example 24Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 5 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 110 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction is finished, filtering, washing with water, recycling a filter cake, collecting filtrate, and distilling to obtain 358.4g of gamma-aminopropanol, wherein the yield is 85.03 percent, and the purity is 99.72 percent.
Example 25Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 5 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 95 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 6 Mpa. After the reaction, the reaction solution was filtered, washed with water, the filter cake was recovered and reused, and the filtrate was collected and distilled to obtain 364.4g of γ -aminopropanol, with a yield of 86.46% and a purity of 99.89%.
Example 26Preparation of the inventive gamma-aminopropanols
The preparation of gamma-aminopropanol comprises the following steps:
adding 500ml of water, 500g of beta-alanine (the purity is more than or equal to 99%) and 7g of catalyst 5 into a high-pressure reaction kettle, adjusting the pH value of the solution to 4 by using concentrated sulfuric acid, introducing hydrogen into the kettle, replacing air in the kettle, continuously introducing the hydrogen to adjust the pressure of the kettle, heating to 95 ℃, carrying out heat preservation reaction for 10 hours, intermittently replenishing the hydrogen in the reaction process, and maintaining the pressure of the kettle to be 8 Mpa. After the reaction was completed, filtration was carried out, washing was carried out with water, the filter cake was recovered and reused, and the filtrate was collected and distilled to obtain 371.3g of γ -aminopropanol, the yield was 88.09%, and the purity was 99.92%.
The above description of the specific embodiments of the present invention is not intended to limit the present invention, and those skilled in the art may make various changes and modifications according to the present invention without departing from the spirit of the present invention, which is defined in the appended claims.

Claims (10)

1. A method for preparing gamma-aminopropanol by one-step catalytic hydrogenation comprises the following steps of carrying out hydrogenation reaction on beta-alanine and hydrogen in a reaction solvent in the presence of a metal catalyst to obtain the gamma-aminopropanol.
2. The process of claim 1, the metal catalyst is a group VIII metal catalyst, preferably any one of a metal binary catalyst, a metal ternary catalyst, a metal quaternary catalyst, or a combination thereof.
3. The method according to any one of claims 1 to 2, wherein the metal binary catalyst consists of ruthenium and any one selected from rhodium, palladium and platinum.
4. The process of any of claims 1-2, wherein the metal three-way catalyst is comprised of ruthenium and any two selected from rhodium, palladium, and platinum.
5. The process according to any one of claims 1-2, wherein the metal quaternary catalyst is a catalyst consisting of a combination of ruthenium, rhodium, palladium, platinum, preferably ruthenium: rhodium: palladium: the mole ratio of platinum is (1-9): (2-8): (2-8): (2-8), preferably (4-8): (1-2): (1-2): (1-2).
6. The process according to any one of claims 1 to 5, further comprising a catalyst support, preferably the metal catalyst is a metal salt catalyst.
7. The method according to any one of claims 1 to 6, wherein the mass ratio of the beta-alanine to the metal catalyst in the reaction system is 100: (0.1-15), preferably 100: (0.5-5), more preferably 100: (1-3).
8. The method according to any one of claims 1 to 7, wherein the preparation of the metal catalyst comprises the steps of:
(1) dissolving metal salt in water, adding silica sol, stirring and uniformly mixing;
(2) adding an alkali solution, stirring and reacting for a period of time;
(3) filtering, collecting a filter cake, washing and drying to obtain a dried product;
(4) and (4) reacting the dried product with hydrogen to obtain the catalyst.
9. The method according to any one of claims 1 to 7, wherein the preparation of the metal catalyst comprises the steps of:
(1) dissolving a metal salt in water to prepare a metal salt solution;
(2) after acid washing and alkali washing, washing the activated carbon with water to a pH value of 6-7;
(3) uniformly mixing the activated carbon obtained in the step (2) with the metal salt solution prepared in the step (1), reacting at the temperature of 40-50 ℃ at the pH of 8-10, filtering, collecting a filter cake, washing with water, drying, and reacting the obtained dried product with hydrogen to obtain the catalyst;
wherein, the steps (1) and (2) are not divided into a sequence.
10. A high-purity gamma-aminopropanol is used for preparing any one of medicines, daily chemical products and foods, preferably any one of panthenol, acamprosate, chloropropamphetamine, domperidone, ifosfamide, urapidil, cyclophosphamide and perhexazol.
CN202110562414.3A 2021-03-29 2021-05-24 Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof Pending CN113121368A (en)

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