CN109438283A - A kind of synthetic method and device of β-aminopropionitrile - Google Patents
A kind of synthetic method and device of β-aminopropionitrile Download PDFInfo
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- CN109438283A CN109438283A CN201811595400.6A CN201811595400A CN109438283A CN 109438283 A CN109438283 A CN 109438283A CN 201811595400 A CN201811595400 A CN 201811595400A CN 109438283 A CN109438283 A CN 109438283A
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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
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- C07C253/34—Separation; Purification
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Abstract
The present invention relates to chemical synthesis process technical fields, more particularly, to the synthetic method and device of a kind of β-aminopropionitrile.The synthetic method of the β-aminopropionitrile, after including the following steps: (a) acrylonitrile and ammonium hydroxide reaction, β-aminopropionitrile is collected in distillation；(b) waste liquid remaining after distillation is obtained into mixed liquor with ammonium hydroxide mixing temperature reaction, distillation mixed liquor collects β-aminopropionitrile, and recycling slops reacts with ammonia water；Wherein, the distillation condition in step (b) includes: to collect β-aminopropionitrile using vapor distillation method distillation mixed liquor, and steam distillation includes the steam distillation at least two stages, and the water vapor pressure force gradient of the steam distillation in each stage increases.Regulation of the present invention to process conditions, while guaranteeing product β-aminopropionitrile distillation yield, distillation system temperature can be effectively controlled no more than 120 DEG C, the material composition in waste liquid is not destroyed, the raw material that can be used as reaction uses, and improves the yield of β-aminopropionitrile.
Description
Technical field
The present invention relates to chemical synthesis process technical fields, more particularly, to the synthetic method and dress of a kind of β-aminopropionitrile
It sets.
Background technique
β-aminopropionitrile is a kind of important organic chemical industry's intermediate, and more common preparation method is by ammonia and third
The reaction of alkene nitrile, which generates, to be made.But since it has side reaction during the preparation process, and its by-product can not be utilized directly, only
It can be handled as harmful influence, cause the yield of β-aminopropionitrile low, and harmful influence processing cost is high.
Thus, the synthetic method and device for developing a kind of β-aminopropionitrile with high yield are of great significance.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of synthetic method of β-aminopropionitrile, by new processing step, mention
The utilization rate of high by-product, while improving the yield of β-aminopropionitrile, to solve, yield existing in the prior art is low and dangerization
The high problem of product processing cost.
The second object of the present invention is to provide a kind of synthesizer of β-aminopropionitrile, and apparatus structure is simple, Neng Goushi
Existing continuous production, and each unit utilization rate is high, low energy consumption.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of synthetic method of β-aminopropionitrile, includes the following steps:
(a) after acrylonitrile and ammonium hydroxide react, β-aminopropionitrile is collected in distillation；
(b) waste liquid remaining after distillation is obtained into mixed liquor with ammonium hydroxide mixing temperature reaction, distillation mixed liquor collects β-ammonia
Base propionitrile, recycling slops react with ammonia water；
Wherein, the distillation condition in step (b) includes: to collect β-aminopropionitrile using vapor distillation method distillation mixed liquor,
Steam distillation includes the steam distillation at least two stages, and the water vapor pressure force gradient of the steam distillation in each stage increases.
The present invention is had found by numerous studies, can generate by-product β, β-imino-diacetic in the synthesis process of β-aminopropionitrile
The high-boiling components such as propionitrile, when collecting product β-aminopropionitrile under by common distillation condition, in order to improve product beta-amino third
The yield of nitrile, the temperature of remaining high-boiling components will at least reach 140-150 DEG C in usual distillation system, could be by part beta-amino third
Nitrile distills out；And under the conditions of this temperature, β in high-boiling components, the substance reactions such as β-iminobis-propanenitrile are rotten, can not be re-used as
Raw material reacts with ammonia water preparation β-aminopropionitrile, lower so as to cause the yield of β-aminopropionitrile, and the processing cost of high-boiling components
It is higher.
Synthetic method of the invention under the conditions of steam distillation, is guaranteeing product β-ammonia by the regulation to process conditions
It while base propionitrile distillation yield, can effectively control in distillation system, temperature is no more than 120 DEG C, the material composition in waste liquid
It is not destroyed, still can be used as the raw material reacted in step (b) and use, to improve the yield of β-aminopropionitrile, and high boiling
Object is not necessarily to extra process expense, reduces production cost.
The present invention has obtained the reason that β-aminopropionitrile yield is lower in the prior art by research, and provides simplicity
Solution, can increase substantially the yield of β-aminopropionitrile, while reduce the expense of high-boiling components processing, greatly reduce life
Produce cost.
Meanwhile when initial acrylonitrile reacts with ammonia water, raw material mixes addition in proportion, does not need to regulate and control two at any time
Person's ratio, finally obtained slops can be efficiently used, and process complexity is reduced.
By using the mode that multiple gradient pressure distills, the temperature of water vapour is stepped up, avoids initially being passed through water steaming
Excessive boiling after stripping temperature is excessively high improves safety, while it is logical in a large amount of overheated gas to avoid the high boiling substance in mixed liquor
It is oxidized in the case where entering rotten etc..Meanwhile gradient improves water vapor pressure, in the higher situation of β-aminopropionitrile content,
Water vapor pressure can come into full contact with azeotropic in lesser situation with β-aminopropionitrile, while water vapour can take beta-amino out of
Propionitrile；With the reduction of β-aminopropionitrile content in mixed liquor, water vapor pressure is stepped up, guarantees that water vapour can effectively connect
β-aminopropionitrile in mixed liquor is touched, β-aminopropionitrile is effectively distilled out, is avoided more next with β-aminopropionitrile remaining in mixed liquor
It is fewer, the case where yield reduces is distilled, thus, by the way of the distillation of multiple gradient pressure, it can effectively take into account yield and keep away
Exempt to destroy high-boiling components ingredient, can further be utilized using high-boiling components as raw material, improves cyclic yield.
Preferably, step (b) is iteratively repeated repeatedly.It is furthermore preferred that step (b) is iteratively repeated 1-3 times, preferably 2 times.
Since the present invention is by way of steam distillation, in the case where product β-aminopropionitrile is collected in abundant distillation, pole
The big temperature for reducing high-boiling components in distillation system, the reaction for avoiding high-boiling components is rotten, can be used as raw material and ammonium hydroxide again
β-aminopropionitrile is prepared, and can be reused, to improve the yield of β-aminopropionitrile, and high-boiling components are made full use of.It adopts
It can make product β-aminopropionitrile azeotrope with water to be collected with steam distillation and take product out of, improve the distillation yield of product.
In the actual production process, in the case where step (b) is repeated twice, the yield of β-aminopropionitrile can be made to reach
99% or more, yield is greatly improved；Remaining high-boiling components content is few, can stop reusing.
Preferably, in step (b), the temperature of mixed liquor is 100-120 DEG C, preferably 110-115 DEG C when distillation.
Preferably, the pressure in step (b) when distillation is -0.095MPa~-0.1MPa.
Preferably, in vapor distillation method, the flow velocity of steam is 5-15m/s, preferably 8-12m/s.
Within the above range by adjusting steam flow rate, the steaming for improving steam utilization and product β-aminopropionitrile is taken into account
Evaporate yield.Avoid steam flow rate too small, collection rate is slower, also avoids steam flow rate excessive, and β-aminopropionitrile cannot be had
Effect distillation is collected.
Preferably, during steam distillation, the pressure of water vapour is 0.05-0.3MPa.It is furthermore preferred that steam distillation process
In, the pressure of water vapour is 0.05-0.2MPa.
Preferably, steam distillation includes a stage steam distillation, two-stage steam distillation, the distillation of three stage steams and quadravalence
Section steam distillation, the pressure of the water vapour of a stage steam distillation are 0.05-0.08MPa, the water vapour of two-stage steam distillation
Pressure be 0.08-0.1MPa, three stage steams distillation water vapour pressure be 0.1-0.15MPa, four stage steam distillations
Water vapour pressure be 0.15-0.2MPa.The beta-amino third of 40-50% in mixed liquor is distilled out using a stage steam distillation
Nitrile distills out the β-aminopropionitrile of 20-30% in mixed liquor using two-stage steam distillation, is distilled using three stage steams
Out in mixed liquor 10-20% β-aminopropionitrile, distill out remaining β-aminopropionitrile in mixed liquor using four stages.
In such a way that above-mentioned multi-step gradient is distilled, the temperature of water vapour can be stepped up, is avoided after being passed through water vapour
Excessive boiling improves safety, while avoiding the high boiling substance in mixed liquor the generations such as to be oxidized during heating rotten.
Meanwhile different amounts of β-aminopropionitrile is distilled out using different water vapor pressures, further increase beta-amino third
The distillation collecting amount of nitrile, meanwhile, gradient improves water vapor pressure, in the higher situation of β-aminopropionitrile content, water vapor pressure
Power can come into full contact with azeotropic in lesser situation with β-aminopropionitrile, while water vapour can take β-aminopropionitrile out of；With
The reduction of β-aminopropionitrile content in mixed liquor steps up water vapor pressure, guarantees that water vapour can effectively contact mixed liquor
Middle β-aminopropionitrile, effectively distills out β-aminopropionitrile, avoids, distillation fewer and fewer with β-aminopropionitrile remaining in mixed liquor
The case where yield reduces.
In addition, the mode of gradient distillation, in addition to improving safety, additionally it is possible to minimize the dosage of water vapour, improve water and steam
The utilization rate of vapour.
Preferably, the concentration of ammonium hydroxide is 30-40%, preferably 34-36%, more preferably 35%.
Preferably, in step (b), the temperature of temperature reaction is 130-150 DEG C, preferably 150 DEG C.It is furthermore preferred that step
(b) in, the time of reaction is 2-5h, preferably 3-5h, more preferably 5h.It can due to being adjusted in the present invention by distillation technique
Slops is made full use of, soaking time can be appropriately extended, improves degree of reaction, while by-product recoverable.
Preferably, in step (b), the pressure of temperature reaction is 3-4MPa.
Preferably, in step (b), the mass ratio of waste liquid and ammonium hydroxide is 1 ﹕ (4-7), preferably 1 ﹕ (4.8-6.4).It is more excellent
Choosing, in step (b), the mass ratio of β in waste liquid, β-iminobis-propanenitrile and ammonium hydroxide are 1 ﹕ (5-8), preferably 1 ﹕ (6.5-
8), more preferably 1 ﹕ (7-8).
Preferably, the distillation in step (a) is vapor distillation method.It, can when also using vapor distillation method in step (a)
It is further ensured that product β-aminopropionitrile distillation yield, and effectively controls in distillation system, the temperature of residual waste solution is no more than 120
DEG C, avoid material composition from being destroyed, to improve the yield of β-aminopropionitrile.
Preferably, the steam distillation in step (a) includes the steam distillation at least two stages, the steamed in each stage
The water vapor pressure force gradient evaporated increases.
Preferably, in step (a), the volume ratio of acrylonitrile and ammonium hydroxide is 1 ﹕ (4-6), preferably 1 ﹕ 5.It is furthermore preferred that step
Suddenly in (a), the reaction temperature of acrylonitrile and ammonium hydroxide is 100-150 DEG C.
Preferably, in step (a), after reaction, ammonium hydroxide is recycled, β-aminopropionitrile is collected in redistillation.It is furthermore preferred that using dodging
Steaming method recycles ammonium hydroxide.Condition of negative pressure can recycle ammonium hydroxide, reuse.
Preferably, after collecting β-aminopropionitrile using vapor distillation method distillation mixed liquor, directly as raw material in alkaline item
It is hydrolyzed under part, obtains alanine sodium.
It, can be directly using water vapour as medium in alkalinity after vapor distillation method distillation β-aminopropionitrile through the invention
Under the conditions of hydrolyze, further increase the utilization rate of water, without to steam carry out subsequent processing, reduce process costs.
Preferably, alanine sodium is neutralized through hydrochloric acid, after concentration, alanine is recrystallized to give using water.Or it will
Alanine sodium water solution obtains alanine aqueous solution through strongly acidic styrene's cation exchange resin, after concentration, using water
It is recrystallized to give alanine.
The present invention also provides a kind of synthesizers of β-aminopropionitrile, including reaction member and distillation unit；
Reaction member includes reactor and recovery ammonia device, and the discharge end of reactor is connected to recovery ammonia device；Distillation unit packet
Distiller and steam generator are included, steam generator is connected to distiller；The discharge end of recovery ammonia device is connected to distiller
Feed end, the waste liquid discharge end of distiller is connected to the feed end of reactor.
The device of the invention, steam generator are connected to distiller, and in distillation process, water vapour is passed through distiller
In, by the way of steam distillation, it can be improved the distillation yield of product, and residual components will not be destroyed in waste liquid, by steaming
It evaporates device waste liquid discharge port and is re-fed into reactor, it is reusable, reduce production cost.The device of the invention structure is simple, dress
Utilization rate height is set, low energy consumption.
Preferably, the ammonia discharge port of recovery ammonia device is connected to the feed inlet of reactor.The ammonia that recycling is obtained is as raw material
It reuses, is sent into reactor and is reacted.
It preferably, further include hydrolysis reactor, hydrolysis reactor is connected to the product discharge end of distiller.By distiller
Product is sent directly into hydrolysis reactor, and hydrolysis obtains alanine sodium under alkaline condition, realizes the company of processing step
It is continuous to carry out.
Compared with prior art, the invention has the benefit that
(1) synthetic method of the invention under the conditions of steam distillation, is guaranteeing product by the regulation to process conditions
It while β-aminopropionitrile distillation yield, can effectively control in distillation system, temperature is no more than 120 DEG C, the substance in waste liquid
Ingredient is not destroyed, still be can be used as the raw material reacted in step (b) and is used, so that the yield of β-aminopropionitrile is improved, and
High-boiling components are not necessarily to extra process expense, reduce production cost；
(2) present invention further optimizes steam distillation process conditions, improves process safety, while further keeping away
Exempt from the substance in mixed liquor and the reacting conditions such as oxidation occur, meanwhile, it is distilled out using different water vapor pressures different amounts of
β-aminopropionitrile further increases the distillation collecting amount of β-aminopropionitrile, improves the utilization rate of water vapour；
(3) the device of the invention structure is simple, and utilization ratio of device is high, and low energy consumption；Steam generator is connected to distiller,
In distillation process, water vapour is passed through in distiller, by the way of steam distillation, can be improved the distillation yield of product,
And residual components will not be destroyed in waste liquid, be re-fed into reactor by distiller, and it is reusable, reduce production cost.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of the synthesizer of β-aminopropionitrile provided in an embodiment of the present invention.
Appended drawing reference:
1- reactor；2- recovery ammonia device；3- distiller；
4- steam generator；5- hydrolysis reactor；11- ammonium hydroxide feed inlet；
12- high-boiling components feed inlet；21- mixed liquor discharge port；22- ammonia discharge port；
31- waste liquid discharge port；32- product discharge mouth.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
Fig. 1 is the structural schematic diagram of the synthesizer of β-aminopropionitrile provided in an embodiment of the present invention；As shown in Figure 1, this
The synthesizer for the β-aminopropionitrile that embodiment provides, including reaction member and distillation unit.
Reaction member includes reactor 1 and recovery ammonia device 2, and the discharge end of reactor 1 is connected to recovery ammonia device 2.Distillation is single
Member includes distiller 3 and steam generator 4, and steam generator 4 is connected to distiller.The discharge end of recovery ammonia device 2 connects
In the feed end of distiller 3, the waste liquid discharge port 32 of distiller 3 is connected to the feed end of reactor 1.
In an of the invention preferred embodiment, the feed end of reactor 1 be provided with ammonium hydroxide feed inlet 11 and high-boiling components into
Material mouth 12, ammonium hydroxide feed inlet 11 are used for for being proportionally added into ammonium hydroxide, high-boiling components feed inlet 12 into reactor 1 to reactor 1
The raw materials such as remaining high-boiling components are distilled in middle addition.
In a preferred embodiment of the invention, it is mixed liquor discharge port respectively that there are two discharge ports for the setting of recovery ammonia device 2
21 and ammonia discharge port 22.Carry out being sent into the recycling that ammonium hydroxide is carried out in recovery ammonia device 2 in reactor 1 after reaction, after recycling
Ammonium hydroxide be discharged through ammonia discharge port 22, is carried out down through except the mixed liquor after ammonia is sent by mixed liquor discharge port 21 into distiller 3
One process.
In a preferred embodiment of the invention, the ammonia discharge port 22 of recovery ammonia device 2 is connected to the ammonium hydroxide charging of reactor 1
Mouthful, it is reacted to obtained ammonium hydroxide will be recycled through recovery ammonia device 2 and be sent into reactor directly as raw material, improves the benefit of raw material
With rate, while avoiding pollution environment.
In a preferred embodiment of the invention, distiller 3 is provided with product discharge mouth 31 and waste liquid discharge port 32.Through removing
After mixed liquor after ammonia is sent into distiller 3, water vapour is generated by steam generator 4 and is sent into distiller, is preferably sent to
Under liquid level, steam distillation, in distillation process, the product discharge mouth 31 of product β-aminopropionitrile and vapor through distiller 3 are carried out
Discharge, is collected；Remaining high-boiling components liquid is collected through the waste liquid discharge port 32 of distiller 3 after distillation, and by anti-
It answers the high-boiling components feed inlet 12 of device 1 to be sent into reactor 1, is reacted as raw material.
In a preferred embodiment of the invention, device further includes hydrolysis reactor 5.Hydrolysis reactor 5 is connected to distillation
The product discharge mouth of device 3 is such as product discharge mouth 31 in the present embodiment.The product of distiller 3 is sent directly into hydrolysis
In device 5, hydrolysis obtains alanine sodium under alkaline condition, realizes being carried out continuously for processing step.
Preparation β-aminopropionitrile is reacted with ammonia water in various embodiments of the present invention using slops as raw material, slops
Acquisition methods include the following steps:
Ammonium hydroxide by acrylonitrile and 35% is to react in 5 ﹕ 1 addition reaction kettle by volume, in 150 DEG C, 1.0MPa
Under conditions of react 2h, be decompressed under the conditions of 0.05MPa through pressure reducing valve and carry out ammonium hydroxide recycling, recycle after ammonium hydroxide remaining material into
Row distillation, the fraction for collecting 88-135 DEG C is aminopropionitrile, after 135 DEG C of distillations in remaining slops, β, β-imino-diacetic
The content of propionitrile is 90%, aminopropionitrile content about 8%, and surplus is the substituted tertiary ammonia structure of three hydrogen in structure.It adopts
This β-aminopropionitrile slops is used to continue as Material synthesis β-aminopropionitrile.
Embodiment 1
The synthetic method of the β-aminopropionitrile of the present embodiment, includes the following steps:
(1) β-aminopropionitrile slops 50g (wherein β, β-iminobis-propanenitrile content is added in autoclave
90%) 35% ammonium hydroxide 320g, is added, is warming up to 150 DEG C under confined conditions, in 3MPa insulation reaction 5h, after heat preservation, is down to
Room temperature；
(2) the mixed liquor distillation obtained after reaction is taken out, ammonium hydroxide is recycled, is evaporated under reduced pressure back in 45-55 DEG C, -0.095MPa
Ammonium hydroxide is received, after ammonium hydroxide recycles, when temperature reaches 100 DEG C in heating residual mixed liquor, starts to be passed through into residual mixed liquor
Water vapour carries out steam distillation, and it is 110-115 DEG C that the pressure of water vapour, which is divided into four-stage and controls the temperature of mixed liquor ,-
0.095MPa vacuum distillation, the flow velocity of steam are 9-11m/s, and being initially passed through pressure is 0.06MPa, and 27g beta-amino is collected in distillation
After propionitrile, adjustment water vapor pressure to 0.09MPa, after 15g β-aminopropionitrile is collected in redistillation, adjustment water vapor pressure is extremely
0.12MPa, after continuing distillation collection 8g β-aminopropionitrile, adjustment water vapor pressure to 0.17MPa continues distillation and collects 5g β-ammonia
Base propionitrile is collected obtain β-aminopropionitrile 55g altogether, by primary first-order equation, conversion ratio of the slops to β-aminopropionitrile
Reach 97.9%.
Embodiment 2
The synthetic method of the β-aminopropionitrile of the present embodiment, includes the following steps:
(1) β-aminopropionitrile slops 50g (wherein β, β-iminobis-propanenitrile content is added in autoclave
90%) 35% ammonium hydroxide 320g, is added, is warming up to 150 DEG C under confined conditions, insulation reaction 5h after heat preservation, is down to room temperature；
(2) the mixed liquor distillation obtained after reaction is taken out, ammonium hydroxide is recycled, after ammonium hydroxide recycles, heats residual mixed liquor
When middle temperature reaches 100 DEG C, start to be passed through water vapour progress steam distillation into residual mixed liquor, the pressure of water vapour is divided into four
A stage and the temperature for controlling mixed liquor are 110-115 DEG C, and -0.095MPa vacuum distillation, the flow velocity of steam is 9-11m/s, just
It is 0.06MPa that beginning, which is passed through pressure, and after 27g β-aminopropionitrile is collected in distillation, adjustment water vapor pressure to 0.09MPa, redistillation is received
After collecting 15g β-aminopropionitrile, adjustment water vapor pressure to 0.12MPa, after continuing distillation collection 8g β-aminopropionitrile, adjustment water steams
Steam pressure continues distillation and collects 5g β-aminopropionitrile, collect obtain β-aminopropionitrile 55g altogether, by primary anti-to 0.17MPa
It answers, slops can reach 97.9% to the conversion ratio of β-aminopropionitrile；
(3) waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, collects again
To β-aminopropionitrile 0.8g；It is repeated again, the β-aminopropionitrile 0.3g collected；By once repeating to react, distillation
Waste liquid can reach 99.3% to the conversion ratio of β-aminopropionitrile；It repeats to react by secondary, slops is to β-aminopropionitrile
Conversion ratio can reach 99.8%.
Above-mentioned steps (3) are not will lead to ingredient to verify the steam distillation of the present embodiment to component of effluent without influence
Change and go bad, can be used as raw material and react to obtain β-aminopropionitrile.In actual production, distillation in step (2) can be generated
It is reacted again after waste liquid and the β-aminopropionitrile slops mixing in step (1), improves production efficiency.
Embodiment 3
The synthetic method of the β-aminopropionitrile of the present embodiment, includes the following steps:
(1) β-aminopropionitrile slops 50g (wherein β, β-iminobis-propanenitrile content is added in autoclave
90%) 35% ammonium hydroxide 320g, is added, is warming up to 150 DEG C under confined conditions, insulation reaction 5h after heat preservation, is down to room temperature；
(2) the mixed liquor distillation obtained after reaction is taken out, ammonium hydroxide is recycled, after ammonium hydroxide recycles, heats residual mixed liquor
When middle temperature reaches 100 DEG C, start to be passed through water vapour progress steam distillation into residual mixed liquor, the pressure of water vapour is
0.17MPa, and the temperature for controlling mixed liquor is 110-115 DEG C, -0.095MPa vacuum distillation, the flow velocity of steam is 9-11m/s；
Distillation collects and obtains β-aminopropionitrile 54.6g, and by primary first-order equation, slops can reach to the conversion ratio of β-aminopropionitrile
97.1%；
(3) waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, collects again
To β-aminopropionitrile 0.3g；It is repeated again, the β-aminopropionitrile 0.2g collected；By once repeating to react, distillation
Waste liquid to the conversion ratio of β-aminopropionitrile be 97.7%；It repeats to react by secondary, conversion of the slops to β-aminopropionitrile
Rate is 98%.
Embodiment 4
The synthetic method of the present embodiment reference implementation example 3, difference are only that: the pressure of water vapour is in step (2)
0.06MPa, distillation collects and obtains β-aminopropionitrile 53.2g, by primary first-order equation, conversion ratio of the slops to β-aminopropionitrile
It is 94.7%；The waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, collects obtain again
β-aminopropionitrile 0.4g；It is repeated again, the β-aminopropionitrile 0.3g collected；By once repeating to react, distillation is useless
Liquid can reach 95.4% to the conversion ratio of β-aminopropionitrile；It repeats to react by secondary, slops turns to β-aminopropionitrile
Rate can reach 95.9%.
Embodiment 5
The synthetic method of the present embodiment reference implementation example 2, difference are only that: steam distillation includes the steamed in two stages
It evaporates, the flow velocity of steam is 9-11m/s, and being initially passed through pressure is 0.06MPa, and after 27g β-aminopropionitrile is collected in distillation, adjustment water steams
Steam pressure after 27.3g β-aminopropionitrile is collected in distillation, is collected obtain β-aminopropionitrile 54.3g altogether, by primary to 0.17MPa
Reaction, slops to the conversion ratio of β-aminopropionitrile be 96.7%；The waste liquid obtained after distillation in collection step (2) repeats
It carries out step (1) and (2) once, collects obtain β-aminopropionitrile 0.4g again；It is repeated again, the beta-amino collected
Propionitrile 0.2g；By once repeating to react, slops can reach 97.3% to the conversion ratio of β-aminopropionitrile；By secondary heavy
Multiple reaction, slops can reach 97.7% to the conversion ratio of β-aminopropionitrile.
Embodiment 6
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the flow velocity of steam is 5-7m/s.By primary
Reaction, the β-aminopropionitrile that conversion of the slops to β-aminopropionitrile is collected into are 53.7g, conversion ratio 95.5%.
Embodiment 7
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the flow velocity of steam is 13-15m/s.By one
Secondary response, the β-aminopropionitrile that conversion of the slops to β-aminopropionitrile is collected into are 53.6g, conversion ratio 95.3%.
Embodiment 8
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the dosage of ammonium hydroxide is 280g.By primary anti-
It answers, the β-aminopropionitrile that conversion of the slops to β-aminopropionitrile is collected into is 53.4g, conversion ratio 95%.
Embodiment 9
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the dosage of ammonium hydroxide is 240g.By primary anti-
It answers, the β-aminopropionitrile that conversion of the slops to β-aminopropionitrile is collected into is 53.0g, conversion ratio 94.3%.
Embodiment 10
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the pressure of water vapour is in step (2)
0.2MPa, distillation collects and obtains β-aminopropionitrile 54.3g, by primary first-order equation, conversion ratio of the slops to β-aminopropionitrile
It is 96.7%；The waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, collects obtain again
β-aminopropionitrile 0.2g；It is repeated again, the β-aminopropionitrile not being collected into；By once repeat react, slops to
The conversion ratio of β-aminopropionitrile can reach 97.0%.
Embodiment 11
The synthetic method of the present embodiment reference implementation example 2, difference are only that: the pressure of water vapour is in step (2)
0.3MPa, distillation collects and obtains β-aminopropionitrile 54.0g, by primary first-order equation, conversion ratio of the slops to β-aminopropionitrile
It is 96.1%；The waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, is not collected into β-ammonia
Base propionitrile.
Embodiment 12
The present embodiment reference implementation example 2 provides the preparation method of alanine, includes the following steps:
First group:
The β-aminopropionitrile that each embodiment of embodiment 1-11 is prepared is as raw material, in alkaline (sodium hydroxide) condition
Under hydrolyzed in 90-95 DEG C, insulation reaction 1-2h obtains alanine sodium, adds suitable quantity of water, be added dropwise hydrochloric acid to pH be 7-7.2；It crosses
Filter removes a small amount of insoluble impurity, collects filtrate decompression and has been concentrated into a large amount of solids precipitations, is recrystallized using water, obtain aminopropan
Acid, yield 92%.
Second group: the Beta-alanine that each embodiment of embodiment 1-11 is prepared is as raw material, in alkaline (hydroxide
Sodium) under the conditions of hydrolyzed in 90-95 DEG C, insulation reaction 1-2h obtains alanine sodium water solution, by strongly acidic styrene's sun from
Sub-exchange resin exchanges to obtain alanine aqueous solution, has been concentrated into a large amount of solids and has been precipitated, has been recrystallized using water, obtain aminopropan
Acid, yield 94%.
Comparative example 1
The synthetic method of 1 reference implementation example 1 of comparative example, difference are: in step (2), by the way of commonly distilling,
It is 110-115 DEG C in -0.095MPa, vapo(u)rizing temperature to distill, it is retortable to be collected into β-aminopropionitrile 42.5g, yield 75.6%.
Comparative example 2
The synthetic method of 2 reference implementation example 1 of comparative example, difference are: in step (2), by the way of commonly distilling,
It is 140-145 DEG C of distillation in -0.095MPa, vapo(u)rizing temperature, only retortable to be collected into β-aminopropionitrile 45.3g, yield is
80.6%.The waste liquid obtained after distillation in collection step (2), repeats step (1) and (2) once, is not collected into β-ammonia
Base propionitrile.
Experimental example 1
For the difference of further comparative illustration various embodiments of the present invention and comparative example, in each method in step (2)
Obtained slops is tested, and is tested steam utilization, and test result is shown in Table 1.
The slops ingredient and steam utilization test result of 1 different disposal of table
Note: wherein m refers to the quality of slops mesometamorphism ingredient, m0For the gross mass of waste liquid；X is that the quality of steam is used
Amount, X0For the quality dosage of steam in embodiment 1.
It is found that synthetic method of the invention from upper table, by the regulation to process conditions, under the conditions of steam distillation,
It while guaranteeing product β-aminopropionitrile distillation yield, can effectively control in distillation system, temperature is no more than 120 DEG C, gives up
Material composition in liquid is not destroyed, still be can be used as the raw material reacted in step (b) and is used, to improve β-aminopropionitrile
Yield, and high-boiling components are not necessarily to extra process expense, while steam utilization is high, and distillation efficiency is high, reduces and is produced into
This.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of synthetic method of β-aminopropionitrile, which comprises the steps of:
(a) after acrylonitrile and ammonium hydroxide react, β-aminopropionitrile is collected in distillation；
(b) waste liquid remaining after distillation is obtained into mixed liquor with ammonium hydroxide mixing temperature reaction, distillation mixed liquor collects beta-amino third
Nitrile, recycling slops react with ammonia water；
Wherein, the distillation condition in the step (b) includes: to collect β-aminopropionitrile using vapor distillation method distillation mixed liquor；
The steam distillation includes the steam distillation at least two stages, and the water vapor pressure force gradient of the steam distillation in each stage increases
Add.
2. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that the step (b) is iteratively repeated
Repeatedly；
Preferably, the step (b) is iteratively repeated 1-3 times.
3. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that in the step (b), when distillation
The temperature of the mixed liquor is 100-120 DEG C；
Preferably, in the step (b), when distillation the temperature of the mixed liquor be 110-115 DEG C.
4. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that in the vapor distillation method, steam
The flow velocity of vapour is 5-15m/s；
Preferably, in the vapor distillation method, the flow velocity of steam is 8-12m/s.
5. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that during the steam distillation,
The pressure of water vapour is 0.05-0.3MPa；
Preferably, during the steam distillation, the pressure of water vapour is 0.05-0.2MPa.
6. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that the steam distillation includes single order
Section steam distillation, two-stage steam distillation, the distillation of three stage steams and four stage steam distillations；The one stage steam distillation
The pressure of water vapour is 0.05-0.08MPa, and the pressure of the water vapour of the two-stage steam distillation is 0.08-0.1MPa, described
The pressure of the water vapour of three stage steams distillation is 0.1-0.15MPa, and the pressure of the water vapour of the four stages steam distillation is
0.15-0.2MPa。
7. the synthetic method of β-aminopropionitrile according to claim 6, which is characterized in that in the step (b), heating is anti-
The temperature answered is 130-150 DEG C；
Preferably, in the step (b), the temperature of temperature reaction is 150 DEG C；
Preferably, in the step (b), the time of temperature reaction is 2-5h；
It is furthermore preferred that the time of temperature reaction is 3-5h in the step (b)；
It is furthermore preferred that the time of temperature reaction is 5h in the step (b).
8. the synthetic method of β-aminopropionitrile according to claim 1, which is characterized in that in the step (b), in waste liquid
β, the mass ratio of β-iminobis-propanenitrile and ammonium hydroxide is 1 ﹕ (5-8)；
Preferably, in the step (b), the β in waste liquid, the mass ratio of β-iminobis-propanenitrile and ammonium hydroxide is 1 ﹕ (6.5-8)；
Preferably, in the step (b), the β in waste liquid, the mass ratio of β-iminobis-propanenitrile and ammonium hydroxide is 1 ﹕ (7-8)；
Preferably, after collecting β-aminopropionitrile using vapor distillation method distillation mixed liquor, under alkaline condition directly as raw material
Hydrolysis, obtains alanine sodium；
It is furthermore preferred that alanine sodium is neutralized through hydrochloric acid, after concentration, alanine is recrystallized to give using water；Or by ammonia
Base propionic acid sodium water solution obtains alanine aqueous solution through strongly acidic styrene's cation exchange resin, after concentration, using water weight
Crystallization obtains alanine.
9. a kind of synthesizer of β-aminopropionitrile, which is characterized in that including reaction member and distillation unit；
Reaction member includes reactor and recovery ammonia device, and the discharge end of reactor is connected to recovery ammonia device；Distillation unit includes steaming
Device and steam generator are evaporated, steam generator is connected to distiller；The discharge end of recovery ammonia device be connected to distiller into
Expect end, the waste liquid discharge end of distiller is connected to the feed end of reactor.
10. the synthesizer of β-aminopropionitrile according to claim 9, which is characterized in that the ammonia of the recovery ammonia device goes out
Material mouth is connected to the feed inlet of the reactor；
Preferably, described device further includes hydrolysis reactor, and the hydrolysis reactor is connected to the product discharge of the distiller
End.
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