CN103864633A - Method for preparing alpha-aminoisobutyric acid - Google Patents
Method for preparing alpha-aminoisobutyric acid Download PDFInfo
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- CN103864633A CN103864633A CN201410133144.4A CN201410133144A CN103864633A CN 103864633 A CN103864633 A CN 103864633A CN 201410133144 A CN201410133144 A CN 201410133144A CN 103864633 A CN103864633 A CN 103864633A
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Abstract
The invention aims at the field of chemical industry and relates to a method for preparing alpha-aminoisobutyric acid. The method comprises the step of enabling acetone cyanohydrin and ammonium carbonate to be subjected to pressurized and heated reaction in an aqueous medium, thereby synthesizing alpha-aminoisobutyric acid, wherein ammonium carbonate can be replaced with ammonium bicarbonate or ammonia and carbon dioxide. The invention further relates to preparation using an alpha-aminoisobutyric acid production device, wherein a gas stripping device is especially used for recovering carbon dioxide and ammonia gas which are generated during synthesis reaction and are recycled for the synthesis of alpha-aminoisobutyric acid. According to the method disclosed by the invention, the yield is high, the purity of a product is high, and the equipment investment is small; in a whole process, carbon dioxide and ammonia are hardly consumed, no byproduct inorganic salt is produced, and inorganic base is not consumed, so that a very positive effect on the full and comprehensive utilization of resources and environmental protection is exerted; recovered carbon dioxide and ammonia and crystallized mother liquor are sufficiently utilized, so that the problem of pollution to environment caused by waste gases, waste water and waste residues can be excellently solved, and the environmental-friendly and clean production is really achieved.
Description
Technical field
The present invention is directed to chemical field, relate to a kind of method of chemosynthesis α-aminoacid.
Background technology
China has the characteristic fruit of enriching resource, and wherein, lichee, longan, papaya, Kiwifruit etc. are the important characteristic fruit of China.Fruit industry is China's Major agro-industry, in guarantee farmers' income and promotion regional economic development, has very important status and effect.Fresh fruit is fresh goods, has and adopts rear rapid maturation, aging, corruption, and quality is the feature such as bad change very easily, adopts at present rear loss amount quite serious.Every year, because the loss of rotting to cause is all more than hundred billion yuan, transportation and sales circulation and the foreign exchange earning of these famous and high-quality fruits are seriously restricted.
At present, fruits and vegetables storage method mainly contains physical method and chemical process, and wherein physical method is comparatively desirable and safe method as cold chain and controlled atmosphere store, but use cost is higher, and can not control the generation of adopting rear sufferer completely, especially cold-resistant pathogenic bacterium.And traditional Chemical Preservative mainly contains sterilant class and growth regulating class, but the processing of traditional chemical sanitas can cause environmental pollution and food contamination, has become tender subject of human consumer.
α-aminoacid processing can extend the bottle of fresh cutting flower and insert life-span (Onozaki etc. 1998, Journal of the Japanese Society for Horticultural Science, 67(2), 198-203); Patent CN94194928.1 has reported that aminobutyric acid and derivative (α-aminoacid, B-AIB, gamma amino isobutyric acid) thereof can cause plant and avoid fungal infection, and defines the crop scope of use.Patent CN102224840A discloses a kind of α-aminoacid and B-AIB of utilizing in the application of preparing in fruit antistaling agent, can effectively reduce the rotting rate of fruit, keeps fruit quality, improves the commodity rate of fruit, and prolongs storage period.
But at present little about α-aminoacid preparation method's open source literature, published document is mainly again microbe fermentation method.For example, document CN102864190A, a kind of and α-aminoacid analog structure material---the production method of γ-aminobutyric acid are disclosed, it is take glycerine, corn steep liquor, yeast powder, inorganic salt as raw material, add inductor, carry out expression of enzymes, during the fermentation feed supplement through Escherichia coli fermentation, then add substrate to transform, to obtain α-aminoacid.Because fermentation method self exists the features such as equipment requirements is high, condition control is strict, preparation cycle is long, its application is restricted.
Document CN102241600A discloses a kind of preparation method of 2-amino-butyric acid, the method is under urotropine catalysis, 2-chloro-butyric acid and liquefied ammonia make the chlorion of the amino 2-of replacement chloro-butyric acid for 2～30 hours 20 ℃～90 ℃ reactions, after being dissolved in water, alcohol is analysed and made 2-amino-butyric acid.The yield of the synthetic 2-amino-butyric acid of the method is only more than 50%, need to improve.
Based on above-mentioned prior art, the present invention has developed a kind of chemical synthesis process of α-aminoacid.
Summary of the invention
In view of this, the invention provides a kind of preparation method of α-aminoacid, the method step is few, and yield and purity are high.
For achieving the above object, technical scheme of the present invention is:
The preparation method of α-aminoacid, comprises step: acetone cyanohydrin and volatile salt are in water medium, and α-aminoacid is synthesized in pressurized, heated reaction; Described volatile salt can replace with bicarbonate of ammonia, or replaces with ammonia and carbonic acid gas;
Described reaction formula is as follows:
The mechanism of described reaction is: acetone cyanohydrin, under the effect of ammonia, first generates 2-aminoisobutyric nitrile, then generates 5,5-T10 with carbonic acid gas effect, and 5,5-T10 is hydrolyzed generation α-aminoacid again.Because 5,5-T10 is unstable under alkaline condition, pressurized, heated is conducive to the hydrolysis of 5,5-T10 and generates α-aminoacid.
Can find out from above-mentioned reaction formula, before and after α-aminoacid preparation, not consume any ammonia and carbonic acid gas, only consume the water of 1 equivalent.Therefore adopt method of the present invention, ammonia and the carbonic acid gas that can further emit reaction reclaim, and are cycled to used in the synthetic of lower batch of α-aminoacid, have both avoided the discharge of waste gas and waste liquid, have reduced again production cost.Described starting raw material acetone cyanohydrin can commercially available purchase or is prepared with acetone prussic acid.
Further, the temperature of described reaction is controlled at 140～180 ℃, and reaction pressure is controlled at 3～6MPa, and the reaction times is controlled at 3～6 hours.According to the analysis of above-mentioned reaction mechanism, this reaction also can be carried out under other heating and pressurizing conditions, and as 100 ℃ of temperature, 120 ℃, 200 ℃ and pressure 1MPa, 2MPa, 8MPa etc., just time and the yield of reaction have difference.Therefore, the selection of numerical range of the present invention is only preferably, does not get rid of the exploitativeness of reacting under other heating and pressurizing conditions.
Further, the molar ratio of described acetone cyanohydrin, volatile salt and water is 1:2～4:35～60, or the molar ratio of acetone cyanohydrin, ammonia, carbonic acid gas and water is 1:4～7:2～4:35～60.This molar ratio is only also of the present invention preferred, does not get rid of the exploitativeness of above-mentioned reaction under other molar ratios.
Further, described reaction feed intake for: the acetone cyanohydrin under room temperature is added in the volatile salt or ammonium bicarbonate aqueous solution that is preheated to 50～80 ℃; Or, the acetone cyanohydrin under room temperature is added in the mixed aqueous solution that is preheated to the ammonia of 50～80 ℃ and carbonic acid gas.Drop into after acetone cyanohydrin like this, then carry out pressurized, heated reaction, thereby obtain α-aminoacid.So greatly shorten the retention time of acetone cyanohydrin under comparatively high temps, reduced the chance of its decomposition and polymerization, effectively avoided the generation of side reaction, well suppressed the generation of detrimental impurity, improved reaction conversion ratio.Described preheating temperature to be to be limited to the temperature that unlikely ammonia and carbonic acid gas overflow in a large number from water medium again higher than room temperature, further preferably 60～70 ℃.
Further, after described synthesizing, also comprise purification step: the α-aminoacid aqueous solution that building-up reactions is obtained, through concentrated, crystallization, separation, obtains α-aminoacid crude product; The Recycling Mother Solution that described crystallization obtains is synthetic for lower batch of α-aminoacid.The α-aminoacid crude product yield making is more than 80%, purity is more than 92%.By the circulation to crystalline mother solution, owing to also containing the material such as dipolymer and trimer, glycolylurea of unconverted hydantoic acid, α-aminoacid in crystalline mother solution, make these materials under the condition of High Temperature High Pressure, continue to be converted into α-aminoacid, can further improve yield.
Further, described purification step also comprises: described α-aminoacid crude product, through hot water dissolving, decolouring, recrystallization, separation, dry, obtains highly purified α-aminoacid; The Recycling Mother Solution that described recrystallization obtains is for the recrystallization of lower batch of crude product.The high purity α-aminoacid yield making is more than 50%, purity is more than 99.5%; Recycling of recrystallization mother liquor also further improves yield.
Further, the method that described decolouring adopts comprises: activated carbon decolorizing, film decolouring or resin absorption decolouring.
Further, when described recrystallization, the mass ratio of described α-aminoacid crude product and water is 1:2～4, and the temperature of recrystallization is 0～30 ℃.
The present invention also provides a kind of method of utilizing α-aminoacid production equipment to prepare α-aminoacid, the method environment-protecting clean, and step is few, and yield and purity are high.
For achieving the above object, technical scheme of the present invention is:
Utilize α-aminoacid production equipment to prepare the environment-protecting clean method of α-aminoacid, the air-lift device that described production equipment comprises autoclave and is connected with autoclave; Described preparation method comprises the following steps:
A, in described autoclave, add ammonium carbonate solution, or add ammonium bicarbonate aqueous solution in described autoclave, or add water, carbonic acid gas and ammonia in described autoclave, be preheated to 50～80 ℃, add again acetone cyanohydrin, the synthetic α-aminoacid of pressurized, heated reaction;
After b, described reaction finish, reaction mass cooling down, then pressure release is reclaimed carbonic acid gas and ammonia through air-lift device; The carbonic acid gas of described recovery and ammonia recycle are synthetic for α-aminoacid.
Described air-lift device specifically can be gas stripping column, and the carbonic acid gas of recovery and ammonia can be used for preparing volatile salt or ammonium bicarbonate aqueous solution, or directly passes into the building-up reactions system of α-aminoacid, is cycled to used in synthetic α-aminoacid.
Further, the inwall of described autoclave and connecting piece material are zirconium or Zirconium alloy material.Zirconium material can promote glycolylurea (having another name called glycolylurea, is the intermediate in building-up reactions) to be hydrolyzed into α-aminoacid, shortens hydrolysis time.
Further, described production equipment also comprises purification devices, and described purification devices is provided with synthetic for α-aminoacid of Recycling Mother Solution that pipeline obtains crystallization for the first time, is also provided with pipeline recrystallization mother liquor is cycled to used in the recrystallization of lower batch of crude product; The aqueous solution that described step b reacts the α-aminoacid obtaining by purification devices concentrate, crystallization, separation obtain α-aminoacid crude product, described crude product by purification devices hot water dissolving, decolouring, recrystallization, separation, dry, obtains highly purified α-aminoacid again.Described purification devices comprises crystallization kettle, filtration unit (as whizzer, rejection filter machine, suction filter, plate filter etc.), decolouring still etc., but is not limited to this.
Related parameters optimization and the condition of preparation method of the α-aminoacid of above-mentioned not belting, also be applicable to the environment-protecting clean method of preparing α-aminoacid of this part belting, and described production equipment is also not limited to described autoclave and air-lift device.
Useful technique effect of the present invention is:
Adopt the direct chemosynthesis α-aminoacid of the inventive method, synthesis step is few, facility investment is few, in whole process, consume hardly carbonic acid gas and ammonia, there is no by-product inorganic salt, do not consume any mineral alkali, the protection of abundant utilize resources synthetically and environment is played to very positive effect; The shortcomings such as fermentation method equipment requirements is high, condition control is strict, preparation cycle is long are avoided.In addition, the α-aminoacid crude product yield preparing by the inventive method is more than 80%, purity is more than 92%, after further refining, yield is more than 50%, purity is more than 99.5%, visible its yield and purity obviously exceed much than the method for chemosynthesis α-aminoacid analogue, and in this preparation process, have suppressed the generation of detrimental impurity.Utilize α-aminoacid production equipment to prepare the method for α-aminoacid, the equipment relating to is simple, and operation steps is few, take full advantage of carbonic acid gas and the ammonia of recovery, and crystalline mother solution, can extraordinaryly solving " three wastes " pollution to environment, the real environment-protecting clean of accomplishing is produced.
Accompanying drawing explanation
Fig. 1 utilizes α-aminoacid production equipment to prepare the equipment flowsheet of α-aminoacid;
Fig. 2 is the equipment of Fig. 1 and a kind of structural representation of connection (omitted purification devices in figure, described air-lift device is gas stripping column) thereof.
Embodiment
Referring to accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in preferred embodiment, carries out according to normal condition.
Embodiment 1
In 3L reactor, first add the water of 1800g and the volatile salt of 587.8g98%, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 190.72g that obtains, and the yield of α-aminoacid is that 86%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.5%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
α-aminoacid crude product obtained above is added to the water of 400g, heating for dissolving, then add the gac of 1.5g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 134.7g, and α-aminoacid yield is that 65%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
In 3L reactor, first add the water of 1800g and the bicarbonate of ammonia of 483.7g98%, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation bicarbonate of ammonia.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 137.5g that obtains, and the yield of α-aminoacid is that 62%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.5%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
α-aminoacid crude product obtained above is added to the water of 300g, heating for dissolving, then add the gac of 1.5g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 93.3g, and α-aminoacid yield is that 45%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 3
In 3L reactor, first add the water of 1800g, the volatile salt of 587.8g98% and the crystalline mother solution that embodiment 1 obtains, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 199.51g that obtains, and the yield of α-aminoacid is that 89%(is in acetone cyanohydrin), α-aminoacid content is 92%, moisture 7.0%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 1 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 176.2g, and α-aminoacid yield is that 85%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 4
The crystalline mother solution that first adds water, carbonic acid gas 264g, ammonia 204g and the embodiment 3 of 1800g to obtain in 3L reactor, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 206.24g that obtains, and the yield of α-aminoacid is that 92%(is in acetone cyanohydrin), α-aminoacid content is 92%, moisture 7.0%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 3 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 186.6g, and α-aminoacid yield is that 90%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 5
The crystalline mother solution that first adds water, carbonic acid gas 264g, ammonia 204g and the embodiment 4 of 1800g to obtain in 3L reactor, then be airtightly preheated to 70 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 170 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 5 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 206.24g that obtains, and the yield of α-aminoacid is that 92%(is in acetone cyanohydrin), α-aminoacid content is 92%, moisture 7.0%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 4 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 194.8g, and α-aminoacid yield is that 94%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 6
The crystalline mother solution that first adds water, carbonic acid gas 264g, ammonia 204g and the embodiment 5 of 1800g to obtain in 3L reactor, then be airtightly preheated to 70 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 170 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 5 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 206.24g that obtains, and the yield of α-aminoacid is that 92%(is in acetone cyanohydrin), α-aminoacid content is 92%, moisture 7.0%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 5 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then use while hot the ceramic membrane filter of 50～200nm, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 194.8g, and α-aminoacid yield is that 94%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 7
The crystalline mother solution that first adds water, carbonic acid gas 264g, ammonia 204g and the embodiment 6 of 1800g to obtain in 3L reactor, then be airtightly preheated to 70 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 170 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 5 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99.9%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 206.24g that obtains, and the yield of α-aminoacid is that 92%(is in acetone cyanohydrin), α-aminoacid content is 92%, moisture 7.0%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 6 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then adsorb foreign pigment with resin, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 190.7g, and α-aminoacid yield is that 92%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 8
In 3L reactor, first add the water of 2100g and the volatile salt of 392g98%, then be airtightly preheated to 70 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 140 ℃, pressure in reactor is 4.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 171.7g that obtains, and the yield of α-aminoacid is that 80%(is in acetone cyanohydrin), α-aminoacid content is 96%, moisture 3.8%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
α-aminoacid crude product obtained above is added to the water of 400g, heating for dissolving, then add the gac of 1.5g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 5 ℃ of crystallizations, centrifugal, dryly obtains α-aminoacid white crystal 123.8g, and α-aminoacid yield is that 60%(is in acetone cyanohydrin), purity is 99.8%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 9
In 3L reactor, first add the water of 1260g and the volatile salt of 784g98%, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 180 ℃, pressure in reactor is 3.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 190.72g that obtains, and the yield of α-aminoacid is that 86%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.8%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 7 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 10 ℃ of crystallizations, centrifugal, dryly obtains α-aminoacid white crystal 134.7g, and α-aminoacid yield is that 65%(is in acetone cyanohydrin), purity is 99.6%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 10
In 3L reactor, first add water, carbonic acid gas 352g and the ammonia 238g of 2160g, then be airtightly preheated to 70 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 180 ℃, pressure in reactor is 6.0MPa, reacts then cooling down under this temperature and pressure 3 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 190.72g that obtains, and the yield of α-aminoacid is that 86%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.8%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 8 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 20 ℃ of crystallizations, centrifugal, dryly obtains α-aminoacid white crystal 115.5g, and α-aminoacid yield is that 56%(is in acetone cyanohydrin), purity is 99.9%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 11
In 3L reactor, first add water, carbonic acid gas 176g and the ammonia 136g of 1260g, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 171.7g that obtains, and the yield of α-aminoacid is that 80%(is in acetone cyanohydrin), α-aminoacid content is 96%, moisture 3.8%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
The recrystallization mother liquor that adds embodiment 9 to obtain α-aminoacid crude product obtained above, heating for dissolving, as do not dissolved completely, can suitably add a small amount of water it is dissolved completely, then add the gac of 2.0g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 30 ℃ of crystallizations, centrifugal, dryly obtains α-aminoacid white crystal 103.1g, and α-aminoacid yield is that 50%(is in acetone cyanohydrin), purity is 99.9%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 12
In 3L reactor, add the water of 1800g and the volatile salt of 587.8g98%, and with High pressure feeding pump to the acetone cyanohydrin that adds 171.9g99% in reactor, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, under this temperature and pressure, react 6 hours, then cooling down, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation volatile salt.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.Reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 190.72g that obtains, and the yield of α-aminoacid is that 86%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.5%.Crystalline mother solution recycled to mixed raw material for α-aminoacid step.
α-aminoacid crude product obtained above is added to the water of 400g, heating for dissolving, then add the gac of 1.5g, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, dryly obtains α-aminoacid white crystal 134.7g, and α-aminoacid yield is that 65%(is in acetone cyanohydrin), purity is 99.5%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Embodiment 13
Utilize α-aminoacid production equipment to prepare α-aminoacid, the described equipment flowsheet of preparing α-aminoacid as shown in Figure 1, a kind of structural representation of its equipment connection as shown in Figure 2, comprises autoclave 1, air-lift device 2(gas stripping column) and purification devices 3; The inwall of described autoclave 1 and connecting piece material are zirconium or Zirconium alloy material; Described purification devices 3 is provided with Recycling Mother Solution that pipeline obtains crystallization for the first time to autoclave 1, is also provided with pipeline recrystallization mother liquor is cycled to used in the recrystallization of lower batch of crude product.
In 3000L autoclave 1, first add the water of 1800kg and the volatile salt of 587.8kg98%, then be airtightly preheated to 60 ℃, again with High pressure feeding pump to the acetone cyanohydrin that adds 171.9kg99% in autoclave 1, be warming up to immediately 160 ℃, pressure in reactor is 5.0MPa, reacts then cooling down under this temperature and pressure 6 hours, then pressure release is reclaimed carbonic acid gas and ammonia through gas stripping column, and the ammonia of recovery and carbonic acid gas are circulated to preparation ammonium carbonate solution.The reaction feed liquid that processing obtains through gas stripping column, the transformation efficiency of acetone cyanohydrin is 99%.In purification devices 3, reaction solution is through concentrating, be cooled to 0 ℃ of crystallization, the centrifugal α-aminoacid crude product 190.8kg that obtains, and the yield of α-aminoacid is that 86%(is in acetone cyanohydrin), α-aminoacid content is 93%, moisture 6.8%.Crystalline mother solution (crystalline mother solution for the first time) is circulated to autoclave 1 to be mixed with raw material, for the preparation of lower batch of α-aminoacid.
Again in purification devices 3, α-aminoacid crude product obtained above is added to the water of 400kg, heating for dissolving, then add the gac of 1.5kg, insulated and stirred 1 hour, then filtered while hot gac, filtrate is cooled to 0 ℃ of crystallization, centrifugal, the dry α-aminoacid white crystal 134.2kg that obtains, α-aminoacid yield is that 65%(is in acetone cyanohydrin), purity is 99.8%.Recrystallization mother liquor recycled is to the re-crystallization step of lower batch of α-aminoacid crude product.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (11)
1. the preparation method of α-aminoacid, is characterized in that, comprises step: acetone cyanohydrin and volatile salt are in water medium, and α-aminoacid is synthesized in pressurized, heated reaction; Described volatile salt can replace with bicarbonate of ammonia, or replaces with ammonia and carbonic acid gas;
Described reaction formula is as follows:
2. the preparation method of α-aminoacid according to claim 1, is characterized in that: ammonia and carbonic acid gas that described reaction is emitted reclaim, and is cycled to used in the synthetic of lower batch of α-aminoacid.
3. the preparation method of α-aminoacid according to claim 1, is characterized in that: the temperature of described reaction is controlled at 140～180 ℃, and reaction pressure is controlled at 3～6MPa, and the reaction times is controlled at 3～6 hours.
4. the preparation method of α-aminoacid according to claim 1, is characterized in that: the molar ratio of described acetone cyanohydrin, volatile salt and water is 1:2～4:35～60; Or the molar ratio of described acetone cyanohydrin, ammonia, carbonic acid gas and water is 1:4～7:2～4:35～60.
5. the preparation method of α-aminoacid according to claim 1, is characterized in that: described reaction feed intake for: the acetone cyanohydrin under room temperature is added in the volatile salt or ammonium bicarbonate aqueous solution that is preheated to 50～80 ℃; Or, the acetone cyanohydrin under room temperature is added in the mixed aqueous solution that is preheated to the ammonia of 50～80 ℃ and carbonic acid gas.
6. according to the preparation method of the α-aminoacid described in claim 1 to 5 any one, it is characterized in that, after described synthesizing, also comprise purification step: the α-aminoacid aqueous solution that building-up reactions is obtained, through concentrated, crystallization, separation, obtains α-aminoacid crude product; The Recycling Mother Solution that described crystallization obtains is synthetic for lower batch of α-aminoacid.
7. the preparation method of α-aminoacid according to claim 6, it is characterized in that, described purification step also comprises: described α-aminoacid crude product, through hot water dissolving, decolouring, recrystallization, separation, dry, obtains highly purified α-aminoacid; The Recycling Mother Solution that described recrystallization obtains is for the recrystallization of lower batch of crude product.
8. the preparation method of α-aminoacid according to claim 7, is characterized in that: when described recrystallization, the mass ratio of described α-aminoacid crude product and water is 1:2～4, and the temperature of recrystallization is 0～30 ℃.
9. utilize α-aminoacid production equipment to prepare the environment-protecting clean method of α-aminoacid, it is characterized in that: the air-lift device (2) that described production equipment comprises autoclave (1) and is connected with autoclave (1); Described preparation method comprises the following steps:
A, in described autoclave (1), add ammonium carbonate solution, or add ammonium bicarbonate aqueous solution in described autoclave (1), or add water, carbonic acid gas and ammonia in described autoclave (1), be preheated to 50～80 ℃, add again acetone cyanohydrin, the synthetic α-aminoacid of pressurized, heated reaction;
After b, described reaction finish, reaction mass cooling down, then pressure release is reclaimed carbonic acid gas and ammonia through air-lift device (2); The carbonic acid gas of described recovery and ammonia recycle are synthetic for α-aminoacid.
10. the environment-protecting clean method of preparing α-aminoacid according to claim 9, is characterized in that: the inwall of described autoclave (1) and connecting piece material are zirconium or Zirconium alloy material.
11. according to the environment-protecting clean method of preparing α-aminoacid described in claim 9 or 10, it is characterized in that: described production equipment also comprises purification devices (3), described purification devices (3) is provided with synthetic for α-aminoacid of Recycling Mother Solution that pipeline obtains crystallization for the first time, is also provided with pipeline recrystallization mother liquor is cycled to used in the recrystallization of lower batch of crude product;
The aqueous solution that described step b reacts the α-aminoacid obtaining by purification devices (3) concentrate, crystallization, separation obtain α-aminoacid crude product, described crude product by purification devices (3) hot water dissolving, decolouring, recrystallization, separation, dry, obtains highly purified α-aminoacid again.
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| CN104892521A (en) * | 2015-03-16 | 2015-09-09 | 河北威远生化农药有限公司 | Synthesis and purification method for alpha-amino acid compound |
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