CN113149850A - Process for continuously preparing N-hydroxyethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor - Google Patents
Process for continuously preparing N-hydroxyethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor Download PDFInfo
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Abstract
The invention discloses a process for continuously preparing N-hydroxyethyl-1, 3-propane diamine by using a micro-mixing and fixed bed reactor, belonging to the technical field of organic chemical industry. The method comprises the steps of taking ethanolamine and acrylonitrile as raw materials, enabling the ethanolamine and the acrylonitrile to continuously pass through a first fixed bed reactor to react to generate an N-hydroxyethyl-3-aminopropionitrile intermediate, enabling the N-hydroxyethyl-3-aminopropionitrile intermediate and a cocatalyst to be subjected to liquid-liquid mixing in a first micro-mixing reactor, enabling the N-hydroxyethyl-3-aminopropionitrile intermediate and the cocatalyst to enter a second micro-mixing reactor together with hydrogen to be subjected to gas-liquid mixing, enabling the intermediate reaction liquid to continuously enter a second fixed bed hydrogenation reactor to be subjected to catalytic hydrogenation to generate N-hydroxyethyl-1, 3-propanediamine, wherein the yield is more than or equal to 98%. The method has the advantages of continuous production, simplicity, less three wastes, energy conservation, environmental protection, low cost and easy realization of industrialization.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a process method for continuously preparing N-hydroxyethyl-1, 3-propane diamine by using a micro-mixing and fixed bed reactor.
Background
N-ethoxyl-1, 3-propane diamine belongs to low-grade aliphatic diamine, is an important organic chemical intermediate and is widely applied in the fields of medicine, feed, food and the like. In the process for preparing the broad-spectrum cell protective agent amifostine, N-ethoxyl-1, 3-propane diamine is an important intermediate for synthesizing the amifostine.
At present, two main synthetic routes of N-hydroxyethyl-1, 3-propane diamine are available, one of the two main synthetic routes is to use 1, 3-propane diamine and ethylene oxide as raw materials to prepare N-hydroxyethyl-1, 3-propane diamine (Eur J Med Chem,30,47,1995; J Med Chem 12,236,1969; US 4814443; pharmaceutical science (4), 302, 1981; CN 1752092A). although the synthetic route is simple, the amino group of N-hydroxyethyl-1, 3-propane diamine is extremely active and is easy to be converted into N, N-dihydroxyethyl-1, 3-propane diamine by addition with ethylene oxide in the preparation process, so that the 1, 3-propane diamine needs to be excessive, and the process has the advantages of low product selectivity, more byproducts, complex process and difficulty in realizing continuous chemical process production. In the other route, ethanolamine and acrylonitrile are used as raw materials to prepare N-hydroxyethyl-1, 3-propanediamine (CN101665440A), acrylonitrile and ethanolamine react to generate an intermediate N-hydroxyethyl-3-aminopropionitrile, and then the N-hydroxyethyl-1, 3-propanediamine is prepared by catalytic hydrogenation, but the preparation in the patent is only carried out by a batch method, so the production efficiency is low.
Disclosure of Invention
The invention solves the problem of providing a preparation process method of N-ethoxyl-1, 3-propane diamine, which has simple process, low cost, high selectivity and easy realization of continuous production.
The technical scheme of the invention is as follows:
a process for continuously preparing N-hydroxyethyl-1, 3-propanediamine by using a micro-mixing and fixed-bed reactor, which comprises continuously catalyzing ethanolamine and acrylonitrile to perform addition reaction in a first fixed-bed reactor filled with a molecular sieve catalyst to obtain a reaction liquid of N-hydroxyethyl-3-aminopropionitrile, mixing an acrylonitrile conversion rate of not less than 99%, then performing liquid-liquid mixing on a cocatalyst and the reaction liquid containing the N-hydroxyethyl-3-aminopropionitrile in a first micro-mixing reactor, then performing gas-liquid mixing on the mixture and hydrogen in a second micro-mixing reactor, continuously catalyzing and hydrogenating the N-hydroxyethyl-3-aminopropionitrile to generate the N-hydroxyethyl-1, 3-propanediamine in a second fixed-bed reactor filled with a Raney-Ni catalyst, the yield of the N-ethoxyl-1, 3-propane diamine is not less than 98 percent.
The method comprises the following specific steps:
(1) purging the whole set of experimental device by using inert gas, and discharging air; setting the pressure and temperature of a first fixed bed reactor; the pressure and temperature of the second fixed bed reactor were set.
(2) Respectively conveying an ethanolamine solution with the mass concentration of 40-100% and an acrylonitrile solution with the mass concentration of 40-100% to a first fixed bed reactor filled with a molecular sieve catalyst for addition reaction to obtain a reaction liquid containing an intermediate N-hydroxyethyl-3-aminopropionitrile, wherein the reaction airspeed is 0.2-4h-1Wherein the addition amount of the ethanolamine and the acrylonitrile is as follows: ethanolamine and acrylonitrile according to the molar ratio: 4-1: 1, the solvent is: one or more of methanol, ethanol, isopropanol and tert-butanol.
(3) Conveying the reaction liquid of the N-hydroxyethyl-3-aminopropionitrile generated by the first fixed bed reactor and the hydrogenation-assisting catalyst solution to a first micro-mixing reactor for liquid-liquid mixing, uniformly mixing to obtain a mixed liquid, and feeding the mixed liquid and hydrogen into a second micro-mixing reactor to form a gas-liquid mixed liquid, wherein the molar ratio of the hydrogen to the N-hydroxyethyl-3-aminopropionitrile is 10-200: 1, at a reaction space velocity of 0.2-3h-1Under the condition of (1), the obtained product is conveyed to a second fixed bed reactor filled with Raney Ni catalyst together to carry out continuous catalytic hydrogenation reaction, and the N-hydroxyethyl-1, 3-propane diamine is obtained.
Preferably, the first fixed bed reactor pressure is: 0.1-8MPa, temperature: 10-90 ℃.
Preferably, the pressure of the second fixed bed reactor is: 2-8MPa, temperature: 30-150 ℃.
Preferably, when the first fixed bed reactor is used for preparing the N-hydroxyethyl-3-aminopropionitrile, the used molecular sieve catalyst is a silicon-aluminum molecular sieve.
Preferably, the silicon-aluminum molecular sieve is an A-type molecular sieve and an X-type molecular sieve.
Preferably, the hydrogenation-promoting catalyst is NaOH, KOH, LiOH, Na2CO3One kind of (1). Preferably, theThe concentration of the hydrogenation catalyst is 0.1-40%; the solvent is selected from methanol, ethanol or water solution.
Preferably, the mass fraction of the hydrogenation-promoting catalyst in the mixed liquid in the step (3) is 0.1-8%, and the mass fraction of the N-hydroxyethyl-3-aminopropionitrile is 10-80%.
The invention has the beneficial effects that: the method adopts a mode of serially connecting a micro-mixing reactor and a fixed bed reactor, takes ethanolamine and acrylonitrile as raw materials, and continuously prepares the N-hydroxyethyl-1, 3-propane diamine, and adopts the micro-mixing reactor, so that the mixing of the N- (hydroxyethyl) -3-aminopropionitrile and a cocatalyst is more uniform, and the mass transfer and heat transfer of the N- (hydroxyethyl) -3-aminopropionitrile and hydrogen are greatly improved, thereby improving the hydrogenation efficiency, and ensuring that the yield of the prepared N-hydroxyethyl-1, 3-propane diamine is more than or equal to 98 percent and the conversion rate of acrylonitrile is more than or equal to 99 percent. And the process method is easy to realize continuous production, low in cost, green and environment-friendly and suitable for industrial production.
Drawings
FIG. 1 is a schematic view of the structure of a fixed bed reactor used in the present invention.
In the figure: 1-steel cylinder (nitrogen); 2-a ball valve; 3-a pressure gauge; 4-a non-return valve; 5-raw material emptying valve; 6-liquid micro mixer; 7 double-plunger pump; 8-methylamine solution; 9-acrylonitrile; 10-an alkaline auxiliary agent; 11-methanaminating reactor; 12-a gas-liquid separator; 13-a sampling valve; 14-a constant pressure valve; 15-back pressure valve; 16-temperature control instrument; 17-a hydrogenation reactor; 18-a mass flow meter; 19-cylinders (hydrogen); 20-gas-liquid micromixer.
Detailed description of the invention
The following describes an embodiment of the present invention in detail with reference to fig. 1 and technical solutions.
Example 1:
(1) first, reactor 11 and reactor 17 are filled with catalyst 4A type molecular sieve and Raney-Ni, respectively. (2) The nitrogen cylinder 1 is opened, the whole system is purged, air is exhausted, and the fixed bed reactor 11 is set with pressure by the nitrogen pressure reducing valve 14: 3MPa, temperature set by the temperature controller 16: 35 ℃ is carried out. The pressure of the fixed bed reactor 17 is set by the hydrogen cylinder 19 via the pressure reducing valve 14: 3MPa and is prepared fromThe mass flow controller 18 controls the hydrogen flow rate, and the temperature is set to 65 ℃ by the temperature controller 16. (3) Two double-plunger micro pumps 7 are respectively used for mixing according to the mol ratio of 1.1: 1 ethanolamine (99%) and acrylonitrile (99%) are conveyed to a fixed bed reactor 11 filled with a 4A type molecular sieve catalyst for reaction at a space velocity of 0.75h-1Under the condition of (1), continuously reacting to obtain a reaction solution containing N-hydroxyethyl-3-aminopropionitrile, wherein the mass fraction of the N-hydroxyethyl-3-aminopropionitrile in the reaction solution is 80% (4), and then uniformly mixing the reaction solution and a hydrogenation-assisting catalyst solution (1.5% NaOH ethanol solution) delivered by a double-plunger micro pump in a liquid-liquid micro mixer 6, wherein the mass fraction of NaOH in the mixed solution is 1%. Meanwhile, the hydrogen flow rate is controlled by a mass flow controller 18, so that the molar ratio of the hydrogen to the N-hydroxyethyl-3-aminopropionitrile in the mixed solution is 20: 1, gas-liquid mixing in a micro-mixing reactor 20, and uniformly mixing the reaction liquid at the airspeed of 0.7h-1Under the reaction conditions of (1), the raw materials are put into a fixed bed reactor 17 filled with Raney-Ni catalyst together to carry out continuous catalytic hydrogenation reaction to prepare the N-ethoxyl-1, 3-propane diamine. After the whole device is continuously operated for 3 hours, the reaction liquid is cooled by the gas-liquid separator 12, a small amount of liquid is taken through the sampling valve 13 for gas phase analysis, the conversion rate of acrylonitrile is 99.9 percent, and the yield of the N-ethoxyl-1, 3-propane diamine is 98.9 percent.
Example 2:
the production method of example 1 was employed except that an ethanol solution of ethanolamine having a concentration of 80% was used, the acrylonitrile concentration was 99%, the molar ratio of ethanolamine to acrylonitrile was 2: 1, the reaction temperature is 50 ℃, the reaction pressure is 4MPa, and the space velocity is 1h-1The catalyst is a 3A molecular sieve, and the hydrogenation-assisting catalyst is as follows: 5 percent of NaOH ethanol solution, the content of N-ethoxyl-3-aminopropionitrile in the hydrogenation raw material is 30 percent, and the content of NaOH is 0.5 percent; the molar ratio of hydrogen to N-hydroxyethyl-3-aminopropionitrile is 10: 1, the reaction temperature is 70 ℃, the reaction pressure is 4MPa, and the space velocity is 0.8h-1The hydrogenation catalyst is Raney Ni acrylonitrile conversion rate of 99.8%, and the yield of N-hydroxyethyl-1, 3-propane diamine is 99.2%.
Example 3:
the production method of example 1 was adopted except that the use concentration was 60%The concentration of acrylonitrile in the ethanolamine methanol solution is 99%, and the molar ratio of ethanolamine to acrylonitrile is 1.2: 1, the reaction temperature is 25 ℃, the reaction pressure is 2MPa, and the retention time is 1.2h-1The catalyst is a 5A molecular sieve, and the hydrogenation-assisting catalyst is as follows: 10% NaOH, the content of N-hydroxyethyl-3-aminopropionitrile in the hydrogenation raw material is 50%, the content of NaOH is 2%, and the molar ratio of hydrogen to N-hydroxyethyl-3-aminopropionitrile is 15: 1, the reaction temperature is 55 ℃, the reaction pressure is 3MPa, and the space velocity is 1.1h-1The hydrogenation catalyst is Raney Ni, the conversion rate of acrylonitrile is 99.8 percent, and the yield of N-hydroxyethyl-1, 3-propane diamine is 98.5 percent.
Example 4:
the production method of example 1 was employed except that a 70% ethanolamine methanol solution was used, the acrylonitrile concentration was 99%, and the molar ratio of ethanolamine to acrylonitrile was 1.5: 1, the reaction temperature is 20 ℃, the reaction pressure is 5MPa, and the space velocity is 0.65h-1The catalyst is 13X molecular sieve, and the hydrogenation-assisting catalyst is as follows: the methanol solution of 3 percent NaOH contains 35 percent of N-ethoxyl-3-aminopropionitrile and 1 percent of NaOH in the hydrogenation raw material, and the molar ratio of hydrogen to N-ethoxyl-3-aminopropionitrile is 10: 1, the reaction temperature is 65 ℃, the reaction pressure is 5MPa, and the space velocity is 0.52h-1The hydrogenation catalyst is Raney Ni, the conversion rate of acrylonitrile is 99.8 percent, and the yield of N-hydroxyethyl-1, 3-propane diamine is 99.3 percent.
Example 5:
the production method of example 1 was employed except that an ethanolamine solution having a concentration of 99% was used, the acrylonitrile concentration was 99%, and the molar ratio of ethanolamine to acrylonitrile was 3: 1, the reaction temperature is 40 ℃, the reaction pressure is 1MPa, and the retention time is 2h-1The catalyst is a 4A molecular sieve, and the hydrogenation-assisting catalyst is as follows: 6% NaOH ethanol solution, wherein the content of N-hydroxyethyl-3-aminopropionitrile in the hydrogenation raw material is 45%, the content of NaOH is 1%, and the molar ratio of hydrogen to N-hydroxyethyl-3-aminopropionitrile is 10: 1, the reaction temperature is 65 ℃, the reaction pressure is 5MPa, and the space velocity is 1.78h-1The hydrogenation catalyst is Raney Ni, the conversion rate of acrylonitrile is 99.5 percent, and the yield of N-hydroxyethyl-1, 3-propane diamine is 98.1 percent.
Comparative example 6:
the production method of example 1 was adopted, exceptAn ethanolamine solution with a concentration of 99% is used, the acrylonitrile concentration is 99%, and the molar ratio of ethanolamine to acrylonitrile is 4: 1, the reaction temperature is 50 ℃, the reaction pressure is 1MPa, the airspeed is 0.8h < -1 >, no molecular sieve catalyst is added, quartz sand is used as a filler, and the hydrogenation-assisting catalyst is as follows: 5% NaOH ethanol solution, wherein the content of N-hydroxyethyl-3-aminopropionitrile in the hydrogenation raw material is 20%, the content of NaOH is 1%, and the molar ratio of hydrogen to N-hydroxyethyl-3-aminopropionitrile is 5: 1, the reaction temperature is 75 ℃, the reaction pressure is 3MPa, and the space velocity is 0.75h-1The hydrogenation catalyst is Raney Ni, the conversion rate of acrylonitrile is 99.5 percent, and the yield of N-hydroxyethyl-1, 3-propane diamine is 95.4 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and those skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A process for the continuous preparation of N-hydroxyethyl-1, 3-propanediamine using a micromixing and fixed bed reactor, characterized in that:
continuously catalyzing the addition reaction of ethanolamine and acrylonitrile by a first fixed bed reactor filled with a molecular sieve catalyst to prepare a reaction solution of N-hydroxyethyl-3-aminopropionitrile; then the cocatalyst and reaction liquid containing N-ethoxyl-3-aminopropionitrile are subjected to liquid-liquid mixing in a first micro-mixing reactor, then the reaction liquid is subjected to gas-liquid mixing with hydrogen in a second micro-mixing reactor, and the evenly mixed reaction liquid is subjected to continuous catalytic hydrogenation on the N-ethoxyl-3-aminopropionitrile in a second fixed bed reactor filled with Raney-Ni catalyst to generate the N-ethoxyl-1, 3-propane diamine.
2. The process of claim 1 for the continuous preparation of N-hydroxyethyl-1, 3-propanediamine using a micromixing and fixed bed reactor, characterized by the steps of:
(1) purging the whole set of reaction device by using inert gas, and discharging air; respectively setting the pressure and the temperature of a first fixed bed reactor and a second fixed bed reactor;
(2) respectively conveying the ethanolamine solution with the mass concentration of 40-100% and the acrylonitrile solution with the mass concentration of 40-100% to a first micro-mixing reactor for addition reaction to obtain a reaction solution containing an intermediate N-hydroxyethyl-3-aminopropionitrile, wherein the space velocity is 0.2-4h-1Wherein the addition molar ratio of the ethanolamine to the acrylonitrile is 4-1: 1, the solvent is one or more than two of methanol, ethanol, isopropanol or tert-butanol;
(3) conveying the reaction liquid of the N-hydroxyethyl-3-aminopropionitrile generated by the first fixed bed reactor and the hydrogenation-assisting catalyst solution to a first micro-mixing reactor for liquid-liquid mixing, uniformly mixing to obtain a mixed liquid, and feeding the mixed liquid and hydrogen into a second micro-mixing reactor to form a gas-liquid mixed liquid, wherein the molar ratio of the hydrogen to the N-hydroxyethyl-3-aminopropionitrile is 10-200: 1, at a reaction space velocity of 0.2-3h-1Under the condition of (1), the obtained product is conveyed to a second fixed bed reactor filled with Raney Ni catalyst together to carry out continuous catalytic hydrogenation reaction, and the N-hydroxyethyl-1, 3-propane diamine is obtained.
3. The process for continuously preparing N-hydroxyethyl-1, 3-propanediamine using a micromixing and fixed-bed reactor as set forth in claim 1, characterized in that the first fixed-bed reactor is set at a pressure of 0.1 to 8MPa and a temperature of 10 to 90 ℃.
4. The process for the continuous preparation of N-hydroxyethyl-1, 3-propanediamine using a micromixing and fixed-bed reactor as claimed in claim 1, characterized in that the pressure in the second fixed-bed reactor is set: 2-8MPa and the temperature is 30-150 ℃.
5. The process for continuously preparing N-hydroxyethyl-1, 3-propanediamine by using a micro-mixing and fixed bed reactor as claimed in claim 1, wherein when the first fixed bed reactor is used for preparing N-hydroxyethyl-3-aminopropionitrile, the mass concentration of the adopted ethanolamine solution is 40-100%, and the mass concentration of the adopted acrylonitrile solution is 40-100%; the solvent of the ethanolamine solution is water or an alcohol solvent, and the alcohol solvent is one or a mixture of more than two of methanol, ethanol, isopropanol or tert-butanol.
6. The process of claim 1, wherein the molecular sieve catalyst in the first fixed bed reactor is a silicoaluminophosphate molecular sieve when the first fixed bed reactor is used to prepare N-hydroxyethyl-3-aminopropionitrile.
7. The process of claim 6, wherein the silicoaluminophosphate molecular sieves are type A molecular sieves and type X molecular sieves.
8. The process of claim 2, wherein the hydrogenation promoter is NaOH, KOH, LiOH, Na2CO3One kind of (1).
9. The process for continuously preparing N-hydroxyethyl-1, 3-propanediamine using a micro-hybrid and fixed bed reactor as claimed in claim 8, characterized in that said hydrogenation-promoting catalyst is present in a concentration of 0.1-40%; the solvent is selected from methanol, ethanol or water solution.
10. The process for continuously preparing N-hydroxyethyl-1, 3-propanediamine by using a micro-mixing and fixed bed reactor as claimed in claim 2, characterized in that the mass fraction of the hydrogenation-promoting catalyst in the mixed feed liquid in step (3) is 0.1-8%, and the mass fraction of N-hydroxyethyl-3-aminopropionitrile is 10-80%.
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| CN114702397A (en) * | 2022-04-28 | 2022-07-05 | 北京化工大学 | Synthesis method and application of carbon dioxide absorbent |
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| CN116199588A (en) * | 2023-01-10 | 2023-06-02 | 大连理工大学 | Method for preparing N- (2-hydroxyethyl) -1, 3-propanediamine in semi-continuous mode by combining Y-type micro-mixing reactor and high-pressure reaction kettle |
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