CN109438283B - Synthesis method and device of beta-aminopropionitrile - Google Patents
Synthesis method and device of beta-aminopropionitrile Download PDFInfo
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- CN109438283B CN109438283B CN201811595400.6A CN201811595400A CN109438283B CN 109438283 B CN109438283 B CN 109438283B CN 201811595400 A CN201811595400 A CN 201811595400A CN 109438283 B CN109438283 B CN 109438283B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Abstract
The invention relates to the technical field of chemical synthesis processes, in particular to a method and a device for synthesizing beta-aminopropionitrile. The synthesis method of the beta-aminopropionitrile comprises the following steps: (a) after acrylonitrile reacts with ammonia water, beta-aminopropionitrile is distilled and collected; (b) mixing the residual waste liquid after distillation with ammonia water, heating and reacting to obtain a mixed liquid, distilling the mixed liquid to collect beta-aminopropionitrile, and recovering the distilled waste liquid to react with the ammonia water; wherein the distillation conditions in step (b) comprise: and distilling the mixed solution by adopting a steam distillation method to collect the beta-aminopropionitrile, wherein the steam distillation comprises at least two stages of steam distillation, and the steam pressure gradient of the steam distillation of each stage is increased. The invention can effectively control the temperature of a distillation system to be not more than 120 ℃ and prevent the substance components in the waste liquid from being damaged by regulating and controlling the process conditions while ensuring the distillation yield of the product beta-aminopropionitrile, can be used as a raw material for reaction, and improves the yield of the beta-aminopropionitrile.
Description
Technical Field
The invention relates to the technical field of chemical synthesis processes, in particular to a method and a device for synthesizing beta-aminopropionitrile.
Background
Beta-aminopropionitrile is an important organic chemical intermediate, and is prepared by the reaction of ammonia and acrylonitrile in a common preparation method. However, the beta-aminopropionitrile has low yield and high treatment cost of hazardous chemicals due to the side reaction in the preparation process and the by-products can not be directly utilized and can only be treated as the hazardous chemicals.
Therefore, it is important to develop a method and apparatus for synthesizing β -aminopropionitrile with high yield.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for synthesizing beta-aminopropionitrile, which improves the utilization rate of byproducts and the yield of the beta-aminopropionitrile by novel process steps so as to solve the problems of low yield and high treatment cost of hazardous chemicals in the prior art.
The second purpose of the invention is to provide a synthesis device of beta-aminopropionitrile, which has a simple device structure, can realize continuous production, and has high utilization rate of each unit and low energy consumption.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for synthesizing beta-aminopropionitrile comprises the following steps:
(a) after acrylonitrile reacts with ammonia water, beta-aminopropionitrile is distilled and collected;
(b) mixing the residual waste liquid after distillation with ammonia water, heating and reacting to obtain a mixed liquid, distilling the mixed liquid to collect beta-aminopropionitrile, and recovering the distilled waste liquid to react with the ammonia water;
wherein the distillation conditions in step (b) comprise: and distilling the mixed solution by adopting a steam distillation method to collect the beta-aminopropionitrile, wherein the steam distillation comprises at least two stages of steam distillation, and the steam pressure gradient of the steam distillation of each stage is increased. .
According to the invention, a large number of researches show that high-boiling-point substances such as byproduct beta, beta-iminodiacetonitrile and the like can be generated in the synthesis process of the beta-aminopropionitrile, and when the product beta-aminopropionitrile is collected under the common distillation condition, in order to improve the yield of the product beta-aminopropionitrile, the temperature of the residual high-boiling-point substances in a distillation system usually reaches at least 140 ℃ and 150 ℃, and part of beta-aminopropionitrile can be distilled; under the temperature condition, substances such as beta, beta-iminodipropionitrile in high-boiling residues are deteriorated by reaction and can not be used as raw materials to react with ammonia water to prepare the beta-aminopropionitrile, so that the yield of the beta-aminopropionitrile is low, and the treatment cost of the high-boiling residues is high.
The synthesis method provided by the invention can effectively control the temperature in a distillation system to be not more than 120 ℃ and ensure the distillation yield of the product beta-aminopropionitrile under the steam distillation condition by regulating and controlling the process conditions, and the substance components in the waste liquid are not destroyed and can still be used as the raw materials for the reaction in the step (b), so that the yield of the beta-aminopropionitrile is improved, the high-boiling-point substances do not need extra treatment cost, and the production cost is reduced.
The invention obtains the reason of lower yield of the beta-aminopropionitrile in the prior art through research, provides a simple and convenient solution, can greatly improve the yield of the beta-aminopropionitrile, simultaneously reduces the cost for treating high-boiling residues, and greatly reduces the production cost.
Meanwhile, when the initial acrylonitrile is reacted with the ammonia water, the raw materials are mixed and added in proportion, the proportion of the raw materials and the ammonia water does not need to be regulated at any time, the finally obtained distillation waste liquid can be effectively utilized, and the process complexity is reduced.
By adopting a multi-gradient pressure distillation mode, the temperature of the water vapor is gradually increased, excessive boiling after the water vapor is introduced at the beginning is avoided, the safety is improved, and meanwhile, the high-boiling substances in the mixed liquid are prevented from being oxidized and deteriorated under the condition that a large amount of superheated gas is introduced. Meanwhile, the water vapor pressure is increased in a gradient manner, under the condition that the content of the beta-aminopropionitrile is high and the water vapor pressure is low, the beta-aminopropionitrile can be fully contacted and azeotroped, and meanwhile, the water vapor can carry the beta-aminopropionitrile out; along with the reduction of the content of the beta-aminopropionitrile in the mixed solution, the steam pressure is gradually increased, the steam can be ensured to effectively contact the beta-aminopropionitrile in the mixed solution, the beta-aminopropionitrile is effectively distilled, and the condition that the distillation yield is reduced along with the decrease of the residual beta-aminopropionitrile in the mixed solution is avoided, so that the condition that the yield is reduced by adopting a multi-time gradient pressure distillation mode can effectively give consideration to the yield and avoid damaging the components of high-boiling-point substances, the high-boiling-point substances can be further utilized as raw materials, and the cycle yield is improved.
Preferably, step (b) is repeated a plurality of times. More preferably, step (b) is repeated repeatedly 1-3 times, preferably 2 times.
Because the invention adopts the steam distillation mode, under the condition of fully distilling and collecting the product beta-aminopropionitrile, the temperature of high-boiling-point substances in a distillation system is greatly reduced, the reaction deterioration of the high-boiling-point substances is avoided, the beta-aminopropionitrile can be prepared by taking the beta-aminopropionitrile as the raw material and ammonia water again, and the beta-aminopropionitrile can be recycled, thereby improving the yield of the beta-aminopropionitrile and fully utilizing the high-boiling-point substances. The product beta-aminopropionitrile to be collected can be azeotroped with water by adopting steam distillation to carry out product extraction, and the distillation yield of the product is improved.
In the actual production process, under the condition that the step (b) is repeated twice, the yield of the beta-aminopropionitrile can reach more than 99 percent, and the yield is greatly improved; the residual high-boiling substance content is very low, and the reuse can be stopped.
Preferably, in the step (b), the temperature of the mixed solution during distillation is 100-120 ℃, preferably 110-115 ℃.
Preferably, the pressure during the distillation in step (b) is between-0.095 MPa and-0.1 MPa.
Preferably, in the steam distillation process, the flow rate of the steam is from 5 to 15m/s, preferably from 8 to 12 m/s.
By adjusting the steam flow rate within the above range, the steam utilization rate and the distillation yield of the product beta-aminopropionitrile are both improved. The problems that the flow rate of steam is too small, the collection rate is slow, and the problem that beta-aminopropionitrile cannot be effectively distilled and collected due to too large flow rate of steam are avoided.
Preferably, the pressure of the steam during the steam distillation is 0.05 to 0.3 MPa. More preferably, the pressure of the steam during the steam distillation is 0.05 to 0.2 MPa.
Preferably, the steam distillation comprises one-stage steam distillation, two-stage steam distillation, three-stage steam distillation and four-stage steam distillation, wherein the pressure of the steam of the one-stage steam distillation is 0.05-0.08MPa, the pressure of the steam of the two-stage steam distillation is 0.08-0.1MPa, the pressure of the steam of the three-stage steam distillation is 0.1-0.15MPa, and the pressure of the steam of the four-stage steam distillation is 0.15-0.2 MPa. And distilling 40-50% of beta-aminopropionitrile in the mixed solution by adopting one-stage steam distillation, distilling 20-30% of beta-aminopropionitrile in the mixed solution by adopting two-stage steam distillation, distilling 10-20% of beta-aminopropionitrile in the mixed solution by adopting three-stage steam distillation, and distilling the residual beta-aminopropionitrile in the mixed solution by adopting four-stage distillation.
Through the multi-step gradient distillation mode, the temperature of the water vapor can be gradually increased, excessive boiling after the water vapor is introduced is avoided, the safety is improved, and meanwhile, the high-boiling substances in the mixed liquid are prevented from being oxidized and the like to deteriorate in the heating process.
Meanwhile, different amounts of beta-aminopropionitrile are distilled by adopting different water vapor pressures, the distillation collection amount of the beta-aminopropionitrile is further increased, the water vapor pressure is increased in a gradient manner, under the condition that the content of the beta-aminopropionitrile is higher, the water vapor pressure is lower, the beta-aminopropionitrile can be fully contacted and azeotroped, and meanwhile, the water vapor can carry the beta-aminopropionitrile out; along with the reduction of the content of the beta-aminopropionitrile in the mixed solution, the steam pressure is gradually increased, the steam can be ensured to effectively contact the beta-aminopropionitrile in the mixed solution, the beta-aminopropionitrile is effectively distilled, and the condition that the distillation yield is reduced along with the decrease of the residual beta-aminopropionitrile in the mixed solution is avoided.
In addition, the gradient distillation mode can not only improve the safety, but also minimize the using amount of the water vapor and improve the utilization rate of the water vapor.
Preferably, the concentration of ammonia is 30 to 40%, preferably 34 to 36%, more preferably 35%.
Preferably, in step (b), the temperature for the temperature-raising reaction is 130-150 ℃, preferably 150 ℃. More preferably, in step (b), the reaction time is 2 to 5 hours, preferably 3 to 5 hours, more preferably 5 hours. The distillation waste liquid can be fully utilized through the adjustment of the distillation process, the heat preservation time can be properly prolonged, the reaction degree is improved, and meanwhile, the byproducts can be recycled.
Preferably, in the step (b), the pressure for the temperature-raising reaction is 3 to 4 MPa.
Preferably, in step (b), the mass ratio of waste liquid to ammonia water is 1: 4-7, preferably 1: 4.8-6.4. More preferably, in step (b), the mass ratio of β, β -iminodipropionitrile to ammonia in the waste liquid is 1: 5 to 8, preferably 1: 6.5 to 8, and more preferably 1: 7 to 8.
Preferably, the distillation in step (a) is a steam distillation process. When the steam distillation method is adopted in the step (a), the distillation yield of the product beta-aminopropionitrile can be further ensured, the temperature of the residual waste liquid in a distillation system is effectively controlled not to exceed 120 ℃, and the substance components are prevented from being damaged, so that the yield of the beta-aminopropionitrile is improved.
Preferably, the steam distillation in step (a) comprises at least two stages of steam distillation, the steam distillation of each stage having an increasing water vapour pressure gradient.
Preferably, in step (a), the volume ratio of acrylonitrile to ammonia water is 1: 4-6, preferably 1: 5. More preferably, in step (a), the reaction temperature of acrylonitrile and ammonia water is 100-150 ℃.
Preferably, in step (a), after the reaction, ammonia water is recovered, and β -aminopropionitrile is collected by distillation. More preferably, the ammonia is recovered by flash evaporation. The ammonia water can be recovered under the negative pressure condition and can be reused.
Preferably, the beta-aminopropionitrile is collected by distilling the mixed solution by a steam distillation method, and then the beta-aminopropionitrile is directly hydrolyzed under an alkaline condition as a raw material to obtain the sodium aminopropionate.
After the beta-aminopropionitrile is distilled by the steam distillation method, water vapor can be directly used as a medium to hydrolyze under an alkaline condition, the utilization rate of water is further improved, subsequent treatment on the steam is not needed, and the process cost is reduced.
Preferably, the aminopropionic acid is obtained by neutralizing sodium aminopropionate with hydrochloric acid, concentrating, and recrystallizing with water. Or the amino propionic acid aqueous solution is obtained by passing the amino propionic acid sodium aqueous solution through strong acid styrene cation exchange resin, and the amino propionic acid is obtained by adopting water recrystallization after concentration.
The invention also provides a synthesis device of the beta-aminopropionitrile, which comprises a reaction unit and a distillation unit;
the reaction unit comprises a reactor and an ammonia recoverer, and the discharge end of the reactor is connected with the ammonia recoverer; the distillation unit comprises a distiller and a water vapor generator, and the water vapor generator is connected with the distiller; the discharge end of the ammonia recoverer is connected to the feed end of the distiller, and the waste liquid discharge end of the distiller is connected to the feed end of the reactor.
According to the device, the water vapor generator is connected with the distiller, water vapor is introduced into the distiller in the distillation process, the distillation yield of the product can be improved by adopting a steam distillation mode, the residual components in the waste liquid cannot be damaged, and the waste liquid is fed into the reactor again from the waste liquid discharge port of the distiller, so that the device can be recycled, and the production cost is reduced. The device has the advantages of simple structure, high utilization rate of the device and low energy consumption.
Preferably, the ammonia outlet of the ammonia recoverer is connected with the inlet of the reactor. The recovered ammonia is used as a raw material for repeated use and is sent into a reactor for reaction.
Preferably, the device also comprises a hydrolysis reactor which is connected with the product discharge end of the distiller. And directly feeding the product of the distiller into a hydrolysis reactor, and carrying out hydrolysis reaction under an alkaline condition to obtain the sodium aminopropionate, thereby realizing continuous operation of the process steps.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the synthesis method, through regulation and control of process conditions, under the steam distillation condition, the distillation yield of the product beta-aminopropionitrile is ensured, the temperature in a distillation system can be effectively controlled to be not more than 120 ℃, the substance components in the waste liquid are not damaged, and the product can still be used as the raw material for the reaction in the step (b), so that the yield of the beta-aminopropionitrile is improved, extra treatment cost is not required for high-boiling-point substances, and the production cost is reduced;
(2) the invention further optimizes the steam distillation process conditions, improves the process safety, simultaneously further avoids the change reactions of oxidation and the like of substances in the mixed solution, simultaneously adopts different water vapor pressures to distill out beta-aminopropionitrile with different quantities, further improves the distillation collection quantity of the beta-aminopropionitrile, and improves the utilization rate of the water vapor;
(3) the device has simple structure, high utilization rate and low energy consumption; the steam generator is connected with the distiller, and in the distillation process, steam is introduced into the distiller, and the mode of steam distillation is adopted, so that the distillation yield of the product can be improved, and the residual components in the waste liquid cannot be destroyed, and can be sent into the reactor again by the distiller, so that the steam generator can be repeatedly used, and the production cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a β -aminopropionitrile synthesis apparatus provided in an embodiment of the present invention.
Reference numerals:
1-a reactor; 2-ammonia recovery; 3-a distiller;
4-a water vapor generator; 5-a hydrolysis reactor; 11-ammonia feed inlet;
12-high boiler feed inlet; 21-discharging the mixed liquid; 22-ammonia outlet;
31-discharge of waste liquid; 32-product outlet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
FIG. 1 is a schematic structural diagram of a β -aminopropionitrile synthesis apparatus provided in an embodiment of the present invention; as shown in fig. 1, the apparatus for synthesizing β -aminopropionitrile provided in this example includes a reaction unit and a distillation unit.
The reaction unit comprises a reactor 1 and an ammonia recoverer 2, and the discharge end of the reactor 1 is connected with the ammonia recoverer 2. The distillation unit comprises a distiller 3 and a water vapor generator 4, the water vapor generator 4 being connected to the distiller. The discharge end of the ammonia recoverer 2 is connected with the feed end of the distiller 3, and the waste liquid discharge port 32 of the distiller 3 is connected with the feed end of the reactor 1.
In a preferred embodiment of the present invention, the feeding end of the reactor 1 is provided with an ammonia water feeding port 11 and a high boiling substance feeding port 12, the ammonia water feeding port 11 is used for proportionally adding ammonia water into the reactor 1, and the high boiling substance feeding port 12 is used for adding raw materials such as residual high boiling substances after distillation into the reactor 1.
In a preferred embodiment of the present invention, the ammonia recovery unit 2 is provided with two discharge ports, i.e., a mixed liquid discharge port 21 and an ammonia discharge port 22. After the reaction in the reactor 1 is finished, the mixture is sent to an ammonia recoverer 2 for recovering ammonia water, the recovered ammonia water is discharged through an ammonia discharge port 22, and the mixed solution after ammonia removal is sent to a distiller 3 through a mixed solution discharge port 21 for the next process.
In a preferred embodiment of the present invention, the ammonia outlet 22 of the ammonia recovery unit 2 is connected to the ammonia water inlet of the reactor 1, so that the ammonia water recovered by the ammonia recovery unit 2 is directly used as a raw material and fed into the reactor for reaction, thereby improving the utilization rate of the raw material and avoiding environmental pollution.
In a preferred embodiment of the present invention, the distiller 3 is provided with a product outlet 31 and a waste outlet 32. After the mixed solution after ammonia removal is sent into a distiller 3, water vapor is generated by a water vapor generator 4 and sent into the distiller, preferably sent below the liquid level, for steam distillation, and in the distillation process, a product beta-aminopropionitrile and the water vapor are discharged from a product discharge port 31 of the distiller 3 and collected; and the high-boiling-point substance liquid remained after the distillation is finished is collected by a waste liquid discharge port 32 of the distiller 3 and is sent into the reactor 1 through a high-boiling-point substance feed port 12 of the reactor 1 to be used as a raw material for reaction.
In a preferred embodiment of the invention, the apparatus further comprises a hydrolysis reactor 5. The hydrolysis reactor 5 is connected to a product outlet of the still 3, in this example a product outlet 31. And directly feeding the product of the distiller 3 into a hydrolysis reactor 5, and carrying out hydrolysis reaction under an alkaline condition to obtain the sodium aminopropionate, so as to realize continuous operation of the process steps.
In the embodiments of the invention, the distillation waste liquid is used as a raw material to react with ammonia water to prepare beta-aminopropionitrile, and the method for obtaining the distillation waste liquid comprises the following steps:
adding acrylonitrile and 35% ammonia water into a reaction kettle according to the volume ratio of 5: 1 for reaction, reacting for 2 hours at 150 ℃ and 1.0MPa, reducing the pressure of the reaction kettle to 0.05MPa through a pressure reducing valve for ammonia water recovery, distilling the residual materials after the ammonia water recovery, collecting the fraction at 88-135 ℃ as aminopropionitrile, and distilling the residual distillate at 135 ℃ to obtain the tertiary ammonia structure with the three substituted hydrogens, wherein the content of beta, beta-iminodipropionitrile is 90%, the content of aminopropionitrile is about 8%, and the balance is the tertiary ammonia structure in which the three hydrogens in the structure are substituted. The beta-aminopropionitrile distillation waste liquid is continuously used as a raw material to synthesize the beta-aminopropionitrile.
Example 1
The method for synthesizing beta-aminopropionitrile of the embodiment comprises the following steps:
(1) adding 50g of beta-aminopropionitrile distillation waste liquid (wherein the content of beta, beta-iminodipropionitrile is 90 percent) into an autoclave, adding 320g of 35 percent ammonia water, heating to 150 ℃ under a closed condition, carrying out heat preservation reaction for 5 hours under 3MPa, and cooling to room temperature after heat preservation;
(2) taking out the mixed solution obtained after the reaction, distilling, recovering ammonia water, distilling and recovering ammonia water under reduced pressure of 45-55 ℃, and under reduced pressure of-0.095 MPa, after the ammonia water is recovered, heating the remaining mixed solution until the temperature reaches 100 ℃, starting to introduce water vapor into the remaining mixed solution for steam distillation, dividing the pressure of the water vapor into four stages, controlling the temperature of the mixed solution to be 110-, through one-time reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.9 percent.
Example 2
The method for synthesizing beta-aminopropionitrile of the embodiment comprises the following steps:
(1) adding 50g of beta-aminopropionitrile distillation waste liquid (wherein the content of beta, beta-iminodipropionitrile is 90 percent) into an autoclave, adding 320g of 35 percent ammonia water, heating to 150 ℃ under a closed condition, carrying out heat preservation reaction for 5 hours, and cooling to room temperature after heat preservation;
(2) taking out the mixed solution obtained after the reaction for distillation, recovering ammonia water, after the ammonia water is recovered, heating the remaining mixed solution until the temperature reaches 100 ℃, starting to introduce steam into the remaining mixed solution for steam distillation, dividing the pressure of the steam into four stages, controlling the temperature of the mixed solution to be 110-115 ℃, carrying out reduced pressure distillation at-0.095 MPa, controlling the flow rate of the steam to be 9-11m/s, the initial introduction pressure to be 0.06MPa, adjusting the steam pressure to be 0.09MPa after distilling and collecting 27g of beta-aminopropionitrile, then adjusting the steam pressure to be 0.12MPa after distilling and collecting 15g of beta-aminopropionitrile, continuously distilling and collecting 8g of beta-aminopropionitrile, adjusting the steam pressure to be 0.17MPa, continuously distilling and collecting 5g of beta-aminopropionitrile, jointly collecting 55g of beta-aminopropionitrile, carrying out one-time reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.9 percent;
(3) collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting 0.8g of beta-aminopropionitrile again; repeating the steps again, and collecting 0.3g of the obtained beta-aminopropionitrile; through one-time repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 99.3 percent; through the secondary repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 99.8 percent.
The step (3) is to verify that the steam distillation of the present example has no influence on the components of the waste liquid, does not cause component change and deterioration, and can be used as a raw material to react to obtain the beta-aminopropionitrile. In actual production, the waste liquid generated by distillation in the step (2) and the beta-aminopropionitrile distillation waste liquid in the step (1) can be mixed and then reacted, so that the production efficiency is improved.
Example 3
The method for synthesizing beta-aminopropionitrile of the embodiment comprises the following steps:
(1) adding 50g of beta-aminopropionitrile distillation waste liquid (wherein the content of beta, beta-iminodipropionitrile is 90 percent) into an autoclave, adding 320g of 35 percent ammonia water, heating to 150 ℃ under a closed condition, carrying out heat preservation reaction for 5 hours, and cooling to room temperature after heat preservation;
(2) taking out the mixed solution obtained after the reaction, distilling, recovering ammonia water, after the ammonia water is recovered, starting to introduce steam into the residual mixed solution for steam distillation when the temperature in the residual mixed solution is heated to 100 ℃, wherein the pressure of the steam is 0.17MPa, the temperature of the mixed solution is controlled to be 110-115 ℃, and the reduced pressure distillation is carried out under the pressure of-0.095 MPa, and the flow rate of the steam is 9-11 m/s; 54.6g of beta-aminopropionitrile is obtained by distillation and collection, and the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.1 percent through one-time reaction;
(3) collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting 0.3g of beta-aminopropionitrile again; repeating the steps again, and collecting 0.2g of the obtained beta-aminopropionitrile; through one-time repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 97.7 percent; after the secondary repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 98 percent.
Example 4
This example refers to the synthesis of example 3, with the only difference that: the pressure of the water vapor in the step (2) is 0.06MPa, 53.2g of beta-aminopropionitrile is obtained by distillation and collection, and the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 94.7 percent through one-time reaction; collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting 0.4g of beta-aminopropionitrile again; repeating the steps again, and collecting 0.3g of the obtained beta-aminopropionitrile; through one-time repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 95.4 percent; through the secondary repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 95.9 percent.
Example 5
This example refers to the synthesis of example 2, with the only difference that: the steam distillation comprises two stages of steam distillation, the flow rate of steam is 9-11m/s, the initial introduction pressure is 0.06MPa, after 27g of beta-aminopropionitrile is distilled and collected, the steam pressure is adjusted to 0.17MPa, after 27.3g of beta-aminopropionitrile is distilled and collected, 54.3g of beta-aminopropionitrile is obtained by co-collection, and through one-time reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 96.7%; collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting 0.4g of beta-aminopropionitrile again; repeating the steps again, and collecting 0.2g of the obtained beta-aminopropionitrile; through one-time repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.3 percent; through the secondary repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.7 percent.
Example 6
This example refers to the synthesis of example 2, with the only difference that: the flow rate of the steam is 5-7 m/s. After the primary reaction, 53.7g of beta-aminopropionitrile was collected by conversion of the distillation waste liquid into beta-aminopropionitrile, and the conversion rate was 95.5%.
Example 7
This example refers to the synthesis of example 2, with the only difference that: the flow rate of the steam is 13-15 m/s. Through the primary reaction, 53.6g of beta-aminopropionitrile collected by the conversion of the distillation waste liquid into the beta-aminopropionitrile and the conversion rate of 95.3 percent were obtained.
Example 8
This example refers to the synthesis of example 2, with the only difference that: the amount of ammonia used was 280 g. After the primary reaction, 53.4g of beta-aminopropionitrile was collected by conversion of the distillation waste liquid into beta-aminopropionitrile, and the conversion rate was 95%.
Example 9
This example refers to the synthesis of example 2, with the only difference that: the amount of ammonia used was 240 g. After the primary reaction, 53.0g of beta-aminopropionitrile was collected by conversion of the distillation waste liquid into beta-aminopropionitrile, and the conversion rate was 94.3%.
Example 10
This example refers to the synthesis of example 2, with the only difference that: the pressure of the water vapor in the step (2) is 0.2MPa, 54.3g of beta-aminopropionitrile is obtained by distillation and collection, and the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 96.7 percent through one-time reaction; collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting 0.2g of beta-aminopropionitrile again; repeating the operation again, wherein the beta-aminopropionitrile is not collected; after one-time repeated reaction, the conversion rate of the distillation waste liquid to the beta-aminopropionitrile can reach 97.0 percent.
Example 11
This example refers to the synthesis of example 2, with the only difference that: the pressure of the water vapor in the step (2) is 0.3MPa, 54.0g of beta-aminopropionitrile is obtained by distillation and collection, and the conversion rate of the distillation waste liquid to the beta-aminopropionitrile is 96.1 percent through one-time reaction; and (3) collecting the waste liquid obtained after distillation in the step (2), repeating the steps (1) and (2) once, and collecting no beta-aminopropionitrile.
Example 12
This example provides, with reference to example 2, a process for the preparation of aminopropionic acid comprising the steps of:
a first group:
hydrolyzing the beta-aminopropionitrile prepared in each of examples 1 to 11 as a raw material at 90 to 95 ℃ under an alkaline (sodium hydroxide) condition, preserving heat for 1 to 2 hours to obtain aminopropionic acid sodium, adding a proper amount of water, and dropwise adding hydrochloric acid until the pH value is 7 to 7.2; filtering to remove a small amount of insoluble impurities, collecting filtrate, concentrating under reduced pressure until a large amount of solid is separated out, and recrystallizing with water to obtain aminopropionic acid with yield of 92%.
Second group: beta-aminopropionic acid obtained in each of examples 1 to 11 was hydrolyzed at 90 to 95 ℃ under an alkaline condition (sodium hydroxide), and the resulting product was reacted at an elevated temperature for 1 to 2 hours to give an aqueous solution of sodium aminopropionate, which was then exchanged with a strongly acidic styrene cation exchange resin to give an aqueous solution of aminopropionic acid, which was concentrated until a large amount of solid precipitated, and recrystallized with water to give aminopropionic acid at a yield of 94%.
Comparative example 1
Comparative example 1 the synthesis of example 1 was referenced, with the following differences: in the step (2), the normal distillation mode is adopted, the distillation is carried out at-0.095 MPa and the distillation temperature of 110 ℃ and 115 ℃, 42.5g of beta-aminopropionitrile can be collected by distillation, and the yield is 75.6%.
Comparative example 2
Comparative example 2 the synthesis of example 1 was referenced, with the following differences: in the step (2), the distillation is carried out in a common distillation mode at-0.095 MPa and the distillation temperature of 140 ℃ and 145 ℃, and only 45.3g of beta-aminopropionitrile can be collected by distillation, wherein the yield is 80.6%. And (3) collecting the waste liquid obtained after distillation in the step (2), and repeating the steps (1) and (2) once, wherein the beta-aminopropionitrile is not collected.
Experimental example 1
To further illustrate the differences between the examples of the present invention and the comparative examples, the distillation waste liquid obtained in the step (2) of each process was tested, and the steam utilization rate was also tested, and the test results are shown in table 1.
TABLE 1 test results of composition of distilled waste liquid and steam utilization ratio of different treatments
Note: wherein m is the mass of deteriorated components in the distillation waste liquid, m is0Is the total mass of the waste liquid; x is the mass amount of steam, X0The mass amount of steam used in example 1.
From the above table, it can be seen that the synthesis method of the present invention, by controlling the process conditions, can effectively control the temperature in the distillation system to not exceed 120 ℃ and the material components in the waste liquid are not destroyed while ensuring the distillation yield of the product β -aminopropionitrile under the steam distillation condition, and can still be used as the raw material for the reaction in step (b), thereby increasing the yield of β -aminopropionitrile, and the high boiling substance does not need additional treatment cost, and at the same time, the steam utilization rate is high, and the distillation efficiency is high, and the production cost is reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (18)
1. A method for synthesizing beta-aminopropionitrile is characterized by comprising the following steps:
(a) after acrylonitrile reacts with ammonia water, beta-aminopropionitrile is distilled and collected;
(b) mixing the residual waste liquid after distillation with ammonia water, heating and reacting to obtain a mixed liquid, distilling the mixed liquid to collect beta-aminopropionitrile, and recovering the distilled waste liquid to react with the ammonia water;
wherein the distillation conditions in step (b) comprise: distilling the mixed solution by adopting a steam distillation method to collect beta-aminopropionitrile; the steam distillation comprises one-stage steam distillation, two-stage steam distillation, three-stage steam distillation and four-stage steam distillation, and the steam pressure gradient of the steam distillation of each stage is increased; the pressure of the water vapor of the first-stage steam distillation is 0.05-0.08MPa, the pressure of the water vapor of the second-stage steam distillation is 0.08-0.1MPa, the pressure of the water vapor of the third-stage steam distillation is 0.1-0.15MPa, and the pressure of the water vapor of the fourth-stage steam distillation is 0.15-0.2 MPa;
in the step (b), the temperature of the mixed solution during distillation is 100-115 ℃.
2. The method according to claim 1, wherein the step (b) is repeated a plurality of times.
3. The method of synthesizing β -aminopropionitrile according to claim 2, wherein the step (b) is repeated 1 to 3 times.
4. The method as claimed in claim 1, wherein the temperature of the mixed solution during distillation in step (b) is 110-115 ℃.
5. The method of synthesizing β -aminopropionitrile according to claim 1, wherein the flow rate of steam in the steam distillation method is 5 to 15 m/s.
6. The method of synthesizing β -aminopropionitrile according to claim 5, wherein the flow rate of steam in the steam distillation method is 8 to 12 m/s.
7. The method as claimed in claim 1, wherein the temperature of the temperature-raising reaction in step (b) is 130-150 ℃.
8. The method according to claim 7, wherein the temperature of the temperature-raising reaction is 150 ℃ and the time of the temperature-raising reaction is 2 to 5 hours in the step (b).
9. The method for synthesizing β -aminopropionitrile according to claim 8, wherein in the step (b), the reaction time for raising the temperature is 3 to 5 hours.
10. The method according to claim 9, wherein the reaction time for raising the temperature in step (b) is 5 hours.
11. The method according to claim 1, wherein the mass ratio of β, β -iminodipropionitrile to ammonia in the waste liquid in the step (b) is 1: 5-8.
12. The method according to claim 11, wherein the mass ratio of β, β -iminodipropionitrile to ammonia in the waste liquid in step (b) is 1: 6.5-8.
13. The method according to claim 12, wherein the mass ratio of β, β -iminodipropionitrile to ammonia in the waste liquid in the step (b) is 1: 7-8.
14. The method of claim 1, wherein the beta-aminopropionitrile is obtained by distilling the mixed solution by steam distillation, collecting the beta-aminopropionitrile, and hydrolyzing the beta-aminopropionitrile directly as a raw material under an alkaline condition.
15. The method of synthesizing β -aminopropionitrile according to claim 14, wherein the sodium aminopropionate is neutralized with hydrochloric acid, concentrated, and recrystallized with water to obtain aminopropionic acid; or the amino propionic acid aqueous solution is obtained by passing the amino propionic acid sodium aqueous solution through strong acid styrene cation exchange resin, and the amino propionic acid is obtained by adopting water recrystallization after concentration.
16. The method of synthesizing β -aminopropionitrile according to claim 1, wherein an apparatus for carrying out the method comprises a reaction unit and a distillation unit;
the reaction unit comprises a reactor and an ammonia recoverer, and the discharge end of the reactor is connected with the ammonia recoverer; the distillation unit comprises a distiller and a water vapor generator, and the water vapor generator is connected with the distiller; the discharge end of the ammonia recoverer is connected to the feed end of the distiller, and the waste liquid discharge end of the distiller is connected to the feed end of the reactor.
17. The method of synthesizing β -aminopropionitrile of claim 16, wherein an ammonia outlet of the ammonia recoverer is connected to an inlet of the reactor.
18. The method of synthesizing β -aminopropionitrile according to claim 17, wherein said apparatus further comprises a hydrolysis reactor connected to a product take-off end of said distiller.
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