CN109232338A - A kind of isolation and purification method of methionine hydroxy analog - Google Patents
A kind of isolation and purification method of methionine hydroxy analog Download PDFInfo
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- CN109232338A CN109232338A CN201811329505.7A CN201811329505A CN109232338A CN 109232338 A CN109232338 A CN 109232338A CN 201811329505 A CN201811329505 A CN 201811329505A CN 109232338 A CN109232338 A CN 109232338A
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- methionine hydroxy
- methionine
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- hydroxy analog
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Abstract
The invention discloses a kind of isolation and purification methods of methionine hydroxy analog, the method provided by the invention for isolating and purifying methionine hydroxy analog and inorganic ammonium salt be by homogeneous membrane and different homogeneous membrane electrodialysis combine in the way of solve the problems, such as that methionine hydroxy analog separates difficulty with inorganic ammonium salt in traditional processing technology, and lead to waste water COD height containing methionine hydroxy analog in the inorganic ammonium salt waste water of discharge, reluctant problem, compared with single use homogeneous membrane or different homogeneous membrane electrodialysis, the combination of the two, which carries out desalination, can overcome the applied defect of the two itself.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of isolation and purification method of methionine hydroxy analog.
Background technique
Methionine hydroxy analog (Methionine Hydroxy Analogue, MHA) is a kind of very strong liquid of acidity
Body organic acid, water content 12wt%, the 88wt%(of hydroxy analogs containing active methionine include the 2- hydroxyl that content is at least 65wt%
Base -4- methylmercapto butyric acid monomer and content are no more than the 2-Hydroxy-4-methylthiobutyric acid dimer and polymer of 23wt%).
In home poultry raising, methionine hydroxy analog shows the property for being similar to the known amino acid for playing stimulating growth,
Therefore become the important additives of animal feed.
One of synthetic method of methionine hydroxy analog is initial cyanohydrin hydrolyis method, is to react methylthiopropionaldehyde with hydrogen cyanide
2- 2-hydroxy-4-methylthio butyronitrile is obtained, the latter is lauched symphysis into 2- 2-hydroxy-4-methylthio butyramide in effect of sulfuric acid, then into
One step is lauched solution in effect of sulfuric acid and obtains the hydrolyzate comprising methionine hydroxy analog, ammonium sulfate and ammonium hydrogen sulfate.From 2- hydroxyl
The existing many reports of method of methionine hydroxy analog are isolated and purified in base -4- methylthio butanenitrile hydrolyzate.Such as:
A kind of method be 2- 2-hydroxy-4-methylthio butyronitrile hydrolyzate is added organic solvent such as ketone, ether unmixing with water etc. into
Row extraction, methionine hydroxy analog is extracted into organic solvent, organic solvent is then evaporated off, it is similar to obtain methionine hydroxy
Object, and the water phase of liquid containing ammonium sulfate is by being concentrated under reduced pressure, crystallisation by cooling, obtains ammonium sulfate.The problem of this method, is using organic
Not only there is the loss of organic solvent in solvent extraction, increase the production cost of methionine hydroxy analog, and organic solvent and
Methionine hydroxy analog can remain in water phase, and the COD so as to cause outer draining is higher, and biochemistry is difficult to handle；It obtains
Also it can contain organic solvent in methionine hydroxy analog, it is necessary to which it is distilled under high vacuum state or is passed through thereto steam
To reduce the content of organic solvent, these result in the cost of this method and energy consumption is higher；It furthermore is due to methionine hydroxy class
Like object, solubility is bigger in water, thus using organic solvent carry out extraction can not completely by methionine hydroxy analog from
It is extracted in water phase, therefore, a certain amount of methionine hydroxy analog is necessarily remained in water phase, lead to the ammonium sulfate of by-product
It carries a small amount of methionine hydroxy analog secretly, with certain stink, influences the sale of ammonium sulfate.
A kind of method is layered in a heated condition after neutralizing the ammonification of 2- 2-hydroxy-4-methylthio butyronitrile hydrolyzate, is obtained
Organic layer and water layer；Organic layer is concentrated into almost anhydrous, centrifugation, supernatant liquid is diluted with water to obtain methionine hydroxy similar
Object, lower layer's solid through organic solvent washing, be dried to obtain ammonium sulfate；By water layer concentration, crystallisation by cooling, filtering, solid is through organic
Solvent washing is dried to obtain ammonium sulfate；The organic solvent washing liquid of solid merges twice, is diluted with water after organic solvent is evaporated off
To methionine hydroxy analog.The problem of this method is to have used organic solvent, when organic solvent is evaporated off, recycling it is organic molten
Agent can all lead to the loss of organic solvent when carrying out except crystal evaporate, in solid ammonium sulfate also can entrainment portions organic solvent, these
Result in the higher cost of this method；Likewise, can also contain in the methionine hydroxy analog obtained after organic solvent is evaporated off
Organic solvent, it is necessary to methionine hydroxy analog be distilled under high vacuum state or to be passed through steam thereto organic molten to reduce
The content of agent, the energy consumption that these result in this method are higher；In addition, this method needs to configure the water removal rectifying device of organic solvent
Deng equipment investment is also larger, and this method can not be such that the methionine hydroxy analog in its water phase completely removes completely, You Jirong
Agent aqueous phase extracted necessarily leads to the residual of organic matter in water phase, and water phase either evaporates the condensed water of recycling, or crystallization obtains
Ammonium sulfate, all more or less entrainment organic matter, especially condensed water COD it is very high.
A kind of method be added ammonium sulfate into 2- 2-hydroxy-4-methylthio butyronitrile hydrolyzate or ammonium hydrogen sulfate make to be layered it is bright
It is aobvious, respectively obtain organic layer and water layer；Water layer is concentrated, crystallisation by cooling, obtains ammonium sulfate；Organic layer is neutralized through ammonification, is concentrated
To almost anhydrous, sulfate precipitate ammonium, methionine hydroxy analog is obtained.The problem of this method, is: obtained ammonium sulfate entrainment
The amount of methionine hydroxy analog is larger, the ammonium sulfate especially isolated and purified from organic layer, methionine hydroxy class
Reach 10% or so like the content of object, such ammonium sulfate has niff, and has and be a bit sticky, it is difficult to
Dry, almost without value, the loss for also resulting in methionine hydroxy analog is larger, yield is lower.
A kind of method is that ammonium hydrogen sulfate is added in the hydrolysis of 2- 2-hydroxy-4-methylthio butyronitrile, and gained hydrolyzate passes through layering
Organic layer and water layer are obtained, organic layer respectively obtains methionine hydroxy analog and ammonium hydrogen sulfate, ammonium sulfate, gained by concentration
After ammonium hydrogen sulfate and ammonium sulfate are mixed with water layer, organic solvent miscible with water is added to deposit ammonium sulfate, and then isolated
Ammonium sulfate and solution containing ammonium hydrogen sulfate.Although this method can obtain purer ammonium sulfate, and can be with recycling and reusing
Ammonium hydrogen sulfate, but it uses organic solvent miscible with water such as methanol etc., so as to cause the organic solvent recycling it is difficult,
The problems such as usage amount and larger loss amount.Furthermore the ammonium sulfate isolated from organic layer contains a certain amount of methionine hydroxy
Analog after this part of sulfuric acid ammonium is mixed with water layer, when organic solvent such as alcohol miscible with water is added, necessarily leads to alcohol and egg
Esterification occurs for propylhomoserin hydroxy analogs, at this time if recycling methionine hydroxy analog, it is similar that there are methionine hydroxies
The quality problems of object, and if outlet, lead to the loss and environmental issue of methionine hydroxy analog.
A kind of method is the addition inorganic base sodium hydroxide into 2- 2-hydroxy-4-methylthio butyronitrile hydrolyzate, and layering obtains
Organic layer and water layer, organic layer are concentrated under reduced pressure, and filtering respectively obtains methionine hydroxy analog and solid sulfate salt.The party
Method can generate a large amount of reluctant solid waste (predominantly ammonium sulfate and sodium sulphate) and brine waste (main sulfur acid sodium,
Ammonium sulfate and methionine hydroxy analog), and this method does not refer to the processing of water layer and contains methionine hydroxy analog
Sulfate processing.This method fails the separation problem for being fully solved methionine hydroxy analog and ammonium sulfate, sodium sulphate.
By the studies above status it is found that how effectively to solve the problems, such as that methionine hydroxy analog is separated with ammonium sulfate, solved
Certainly the high problem of ammonium content in product methionine hydroxy analog, solve the problems, such as to avoid sulphur using organic dissolution and discharge
COD high, reluctant problem are issues that need special attentions in sour ammonium waste water.
Therefore it is extremely important for how finding the method that simple, the direct methionine hydroxy analog of one kind isolates and purifies
, directly affect production cost of methionine hydroxy analog and products thereof quality.In view of the above-mentioned deficiencies, more by inventor
The production practices in year, develop the methionine analog production method and its device of a kind of clean and environmental protection.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of methionine analog isolation and purification method,
This method can save equipment investment, avoid in traditional processing technology methionine hydroxy analog separated with ammonium salt difficult problem,
The problem of dimer and polymer increase solves the problems, such as that conventional production methods generate a large amount of waste water and by-product inorganic salts,
And solve the problems, such as that conventional production methods organic solvent extracts brought a series of and unfavorable factor.
The purpose of the present invention is in this way by realization:
A kind of isolation and purification method of methionine hydroxy analog, comprising the following steps:
Step (1): passing through accurate filter for the mixed liquor III containing methionine hydroxy analog and inorganic ammonium salt, subsequently into
Homogeneous membrane electric dialyzator carries out desalting processing, until the ammonium salt in light room is reduced to 2.0%-7.5wt%；Again by the ammonium salt in light room
0.01wt% is decreased below, the methionine hydroxy analog aqueous solution in light room and the ammonium salt aqueous solution of dense room are obtained；
Step (2): the methionine hydroxy analog aqueous solution that the light room of out-phase membrane electrodialysis obtains further is concentrated into 88wt% and is obtained
To methionine hydroxy analog product, homogeneous membrane electrodialysis and the electrodialytic dense room saline solution of heterogeneous membrane by concentration, crystallization,
It is dry, obtain byproduct inorganic ammonium salt.
It may further be preferable that the inorganic ammonium salt in the step (1) is ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, phosphoric acid hydrogen
One or more of ammonium, ammonium dihydrogen phosphate or ammonium phosphate.
It may further be preferable that the inorganic ammonium salt is ammonium sulfate, it is described to contain methionine hydroxy analog and Inorganic Ammonium
The mixed liquor I II of salt is made by following methods:
Step (A): using 2- 2-hydroxy-4-methylthio butyronitrile as raw material, by hydration reaction, 2- 2-hydroxy-4-methylthio butyryl is obtained
Amine salt aqueous solution；
Step (B): water appropriate is added into the 2- 2-hydroxy-4-methylthio butyramide saline solution that step (A) obtains, by water
Solution, obtains methionine hydroxy analog and inorganic ammonium salt mixed aqueous solution；
Step (C): being added ammonia into step (B) resulting mixed liquor and neutralized, and keeps the ammonium hydrogen sulfate in its mixed liquor whole
Ammonium sulfate, static layering are converted, upper layer is methionine hydroxy analog organic layer, and lower layer is ammonium sulfate solution I；By organic layer
It is concentrated into almost anhydrous, point isolated decorating film, the decorating film is ammonium sulfate solids, and filtrate adds water or methionine hydroxyl
Base analog dilute aqueous solution is diluted to 88wt%, and isolated solid content is dissolved in water, obtains containing methionine hydroxy analog
Ammonium sulfate solution II, ammonium sulfate solution I and II merge, and then obtain by accurate filter similar containing methionine hydroxy
The ammonium sulfate solution III of object.
It may further be preferable that the mass percentage of the 2- 2-hydroxy-4-methylthio butyronitrile in the step (A) is 60%
~99%, remaining is water；The 2- 2-hydroxy-4-methylthio butyronitrile is made using methylthiopropionaldehyde and hydrogen cyanide as raw material, the hydrogen
Cyanic acid is gaseous state, aqueous solution or high-purity liquid；The step (A) hydration reaction is carried out in the presence of acidic materials
, the acid is one or more of sulfuric acid, hydrochloric acid, phosphoric acid.
It may further be preferable that the acid of the hydration reaction is sulfuric acid, 2- 2-hydroxy-4-methylthio fourth in the step (A)
The molar ratio of nitrile and sulfuric acid is 1.0:0.70~1.0, and the hydration reaction temperature is 38 DEG C~65 DEG C, when hydration reaction
Between be 30~120min；
The hydrolysis of 2- 2-hydroxy-4-methylthio butyryl amine salt and water, 2- 2-hydroxy-4-methylthio butyramide in the step (B)
The molar ratio of salt and water is 1:3.6~12.0, and the hydrolysis temperature is 90 DEG C~110 DEG C, hydrolysis time 120
~240min；
Mixed system is heterogeneous system after step (C) the hydrolysis ammonification, and upper layer is organic layer, and main group becomes methionine hydroxyl
Base analog content is 8%~15wt% of content of 65%~80wt%, ammonium sulfate, and the content of water is 12%~20wt%；Lower layer is water
Layer, the content that main group becomes ammonium sulfate is 25%~40wt%, and the content of methionine hydroxy analog is 4%~12wt%, and point
Temperature is maintained at 40 DEG C~80 DEG C when layer.
It may further be preferable that group in the ammonium sulfate solution III containing methionine hydroxy analog in the step (C)
Content as ammonium sulfate is 15%~30wt%, and the content of methionine hydroxy analog is 4%~8wt%, and temperature is 25 DEG C~40
℃。
It may further be preferable that the methionine hydroxy analog organic layer enrichment facility is knifing steaming in step (c)
Send out device；
A kind of methionine hydroxy analog and solid ammonium sulfate mixture separate mode are centrifugation, mistake in step (c)
One of filter, filters pressing.
It may further be preferable that keeping feed liquid temperature in the homogeneous membrane and heterogeneous membrane electrodialytic process is 30 DEG C~35
℃；The light room enrichment facility is that MVR evaporator and luwa evaporator combine, and the dense room enrichment facility is MVR steaming
Send out device.
The beneficial effects of the present invention are: compared with prior art, point of methionine hydroxy analog provided by the invention
It is reasonably to organically combine using homogeneous membrane electrodialysis and out-phase membrane electrodialysis and solve biography from purification process and its process units
Methionine hydroxy analog separates the problem of difficulty with inorganic salts in system production technology, compared with the homogeneous membrane electrodialysis of single use or
Out-phase membrane electrodialysis is used for methionine hydroxy analog desalination field, and the two, which organically combines, has selectivity height, separating degree high, with
Chromatography desalination is compared, and the ammonium sulfate solution of homogeneous membrane electrodialysis and heterogeneous membrane electrodialysis process containing methionine hydroxy analog is not
It needs to be diluted, before and after the processing, the concentration of methionine hydroxy analog reduces needed for subsequent purification concentration there is no reducing
Energy consumption, easy to operate, salt rejection rate is high, it is at low cost, decomposed without methionine hydroxy analog, and solve traditional processing technology
The methionine hydroxy analog exposed separates COD in the inorganic ammonium salt waste water of difficult problem and discharge with inorganic ammonium salt
High, reluctant problem, this method have ammonium content in obtained methionine hydroxy analog product low, producing ammonium sulfate byproduct
It purity is high and is destitute of smell, it is no a large amount of acid waste water discharge, environmentally protective, the advantages that methionine hydroxy analog high income.
Detailed description of the invention
Fig. 1 is the basic arrangement mode schematic diagram of electrodialysis.
Specific embodiment
The present invention is described in further detail below by specific embodiment, it is not to limit that following embodiment, which is descriptive,
Property, this does not limit the scope of protection of the present invention.
Embodiment 1
327.50kg(2000 moles of 2- 2-hydroxy-4-methylthio butyronitrile aqueous solution for being 80wt% by mass percentage) and quality
Percentage composition is 150.00kg(1500 moles of the sulfuric acid of 98wt%) it is added in static mixer by flowmeter and is sufficiently mixed simultaneously
It closes, temperature rapid increase at this time to 45 DEG C, and subsequently into tubular reactor, material inlet temperature in tubular reactor is 48
DEG C, outlet temperature is 55 DEG C, and material residence time in tubular reactor is 40min.Material stream in tubular reactor adds to
In enamel reaction still with stirring, while water is added, the additional amount of water is 220.00kg, after adding, is warming up to 100 DEG C immediately
It is hydrolyzed, stirring heat preservation 3 hours obtains filemot mixed liquor；It is anti-that yellowish-brown mixed liquor is transferred to the neutralization with stirring
It answers in kettle, is subsequently cooled to 60 DEG C, be slowly added into the ammonium hydroxide 68kg of 25wt%, static split-phase in phase-splitter is transferred to after neutralization,
Temperature is maintained at 60 DEG C~70 DEG C, and upper layer is organic layer, and sampling analysis, wherein the content of methionine hydroxy analog is 70wt%,
The content of water is 18wt%, and the content of ammonium sulfate is 12wt%；Lower layer is ammonium sulfate solution, and through analyzing, wherein ammonium sulfate contains
Amount is 38wt%, and the content of methionine hydroxy analog is 6.4wt%, and ammonium sulfate solution is transferred in ammonium sulfate storage tank.
The organic layer that above-mentioned phase-splitter obtains is entered into luwa evaporator and remove water to moisture lower than 4wt%, is precipitated a large amount of
Solid, obtain liquid-solid mixture, which is handled by filter-pressing device, and obtained filtrate is transferred in dilution kettle and is added
Deionized water is diluted to 88wt%, is obtained the methionine hydroxy analog of commerical grade, is transferred to product storage tank；Filter cake adds water-soluble
Ammonium sulfate storage tank is transferred to after solution, observing mixed liquor in its storage tank is homogeneous system, and the content for analyzing wherein ammonium sulfate is 29wt%,
The content of methionine hydroxy analog is 5.8wt%.
By the ammonium sulfate solution obtained above containing methionine hydroxy analog after accurate filter is handled, directly
Into homogeneous membrane electrodialysis, desalting processing is carried out, salt of the desalination temperature control in 35 DEG C, light room is reduced to 2.5%-4wt%,
The ammonium sulfate solution of dense room is transferred to ammonium sulfate transfer kettle, and light room feed liquid is transferred to progress depth in heterogeneous membrane electrodialysis plant and removes
Salt obtains methionine hydroxy analog aqueous solution, wherein methionine hydroxy is similar until the salt in light room is reduced to 0 .001%
The content of object be 6.7wt%, this it is water-soluble first carry out MVR evaporator be concentrated into concentration be 58wt%, be then transferred to luwa evaporator into
Row is concentrated into 88wt%, as the methionine hydroxy analog product of commerical grade, is transferred to product storage tank, methionine in product storage tank
Hydroxy analogs amount to 339.89kg, yield 99.7%；Or the methionine hydroxy analog that out-phase membrane electrodialysis obtains is dilute water-soluble
Liquid is recycled to the methionine hydroxy analog of lower batch dilution kettle diluting high-concentration.Ammonium sulfate passes through drying, obtains byproduct sulphur
Sour ammonium, main content is 99%, almost without stink.
Embodiment 2
403.08kg(2000 moles of 2- 2-hydroxy-4-methylthio butyronitrile aqueous solution for being 65% by mass percentage) and quality hundred
160.00kg(1600 moles of the sulfuric acid that point content is 98%) it is added in static mixer and is sufficiently mixed simultaneously by flowmeter,
Temperature rapid increase at this time to 48 DEG C, and subsequently into tubular reactor, material inlet temperature in tubular reactor is 48 DEG C,
Outlet temperature is 60 DEG C, and material residence time in tubular reactor is 50min.Material stream in tubular reactor, which adds to, to be had
In the enamel reaction still of stirring, while water is added, the additional amount of water is 150.00kg, after adding, is warming up to 100 DEG C of progress immediately
Hydrolysis, stirring heat preservation 3 hours, obtains filemot mixed liquor；Yellowish-brown mixed liquor is transferred to the neutralization reaction kettle with stirring
In, 60 DEG C are subsequently cooled to, the ammonium hydroxide 65kg of 25wt% is slowly added into, static split-phase, temperature in phase-splitter are transferred to after neutralization
60 DEG C~70 DEG C are maintained at, upper layer is organic layer, and sampling analysis, wherein the content of methionine hydroxy analog is 74wt%, water
Content is 15wt%, and the content of ammonium sulfate is 11wt%；Lower layer is ammonium sulfate solution, and through analyzing, wherein the content of ammonium sulfate is
The content of 40wt%, methionine hydroxy analog are 5.7wt%, and ammonium sulfate solution is transferred in ammonium sulfate storage tank.
The organic layer that above-mentioned phase-splitter obtains is entered into luwa evaporator and remove water to moisture lower than 2wt%, is precipitated a large amount of
Solid, obtain liquid-solid mixture, which is handled by filter-pressing device, and obtained filtrate is transferred in dilution kettle and is added
Deionized water is diluted to 88wt%, is obtained the methionine hydroxy analog of commerical grade, is transferred to product storage tank；Filter cake adds water-soluble
Ammonium sulfate storage tank is transferred to after solution, observing mixed liquor in its storage tank is homogeneous system, and the content for analyzing wherein ammonium sulfate is 30wt%,
The content of methionine hydroxy analog is 6.0wt%.
By the ammonium sulfate solution obtained above containing methionine hydroxy analog after accurate filter is handled, directly
Into homogeneous membrane electrodialysis, desalting processing is carried out, salt of the desalination temperature control in 35 DEG C, light room is reduced to 2.5%-3wt%,
The ammonium sulfate solution of dense room is transferred to ammonium sulfate transfer kettle, and light room feed liquid is transferred to progress depth in heterogeneous membrane electrodialysis plant and removes
Salt obtains methionine hydroxy analog aqueous solution, wherein methionine hydroxy is similar until the salt in light room is reduced to 0.001%
The content of object be 6.5wt%, this it is water-soluble first carry out MVR evaporator be concentrated into concentration be 60wt%, be then transferred to luwa evaporator into
Row is concentrated into 88wt%, as the methionine hydroxy analog product of commerical grade, is transferred to product storage tank, methionine in product storage tank
Hydroxy analogs amount to 340.89kg, yield 99.8%；Or the methionine hydroxy analog that out-phase membrane electrodialysis obtains is dilute water-soluble
Liquid is recycled to the methionine hydroxy analog of lower batch dilution kettle diluting high-concentration.Ammonium sulfate passes through drying, obtains byproduct sulphur
Sour ammonium, main content is 99%, almost without stink.
Embodiment 3
264.65kg(2000 moles of 2- 2-hydroxy-4-methylthio butyronitrile aqueous solution for being 99% by mass percentage) and quality hundred
210.00kg(1500 moles of the sulfuric acid that point content is 70%) it is added in static mixer and is sufficiently mixed simultaneously by flowmeter,
Temperature rapid increase at this time to 50 DEG C, and subsequently into tubular reactor, material inlet temperature in tubular reactor is 50 DEG C,
Outlet temperature is 60 DEG C, and material residence time in tubular reactor is 30min.Material stream in tubular reactor, which adds to, to be had
In the enamel reaction still of stirring, while water is added, the additional amount of water is 300.00kg, after adding, is warming up to 100 DEG C of progress immediately
Hydrolysis, stirring heat preservation 2.5 hours, obtains filemot mixed liquor；Yellowish-brown mixed liquor is transferred to the neutralization reaction with stirring
In kettle, 60 DEG C are subsequently cooled to, is slowly added into the ammonium hydroxide 65kg of 25wt%, static split-phase in phase-splitter is transferred to after neutralization, temperature
Degree is maintained at 60 DEG C~70 DEG C, and upper layer is organic layer, and sampling analysis, wherein the content of methionine hydroxy analog is 78wt%, water
Content be 12wt%, the content of ammonium sulfate is 10wt%；Lower layer is ammonium sulfate solution, through analyzing, the wherein content of ammonium sulfate
Content for 40wt%, methionine hydroxy analog is 5.7wt%, and ammonium sulfate solution is transferred in ammonium sulfate storage tank.
The organic layer that above-mentioned phase-splitter obtains is entered into luwa evaporator and remove water to moisture lower than 2wt%, is precipitated a large amount of
Solid, obtain liquid-solid mixture, which is handled by filter-pressing device, and obtained filtrate is transferred in dilution kettle and is added
The methionine hydroxy analog dilute aqueous solution that 2 out-phase membrane electrodialysis of embodiment obtains is diluted to 88wt%, obtains commerical grade
Methionine hydroxy analog is transferred to product storage tank；Filter cake is transferred to ammonium sulfate storage tank after being dissolved in water, observe mixed liquor in its storage tank
For homogeneous system, the content for analyzing wherein ammonium sulfate is 30wt%, and the content of methionine hydroxy analog is 6.0wt%.
By the ammonium sulfate solution obtained above containing methionine hydroxy analog after accurate filter is handled, directly
Into homogeneous membrane electrodialysis, desalting processing is carried out, salt of the desalination temperature control in 35 DEG C, light room is reduced to 2.5%-3wt%,
The ammonium sulfate solution of dense room is transferred to ammonium sulfate transfer kettle, and light room feed liquid is transferred to progress depth in heterogeneous membrane electrodialysis plant and removes
Salt obtains methionine hydroxy analog aqueous solution, wherein methionine hydroxy is similar until the salt in light room is reduced to 0.001%
The content of object be 6.5wt%, this it is water-soluble first carry out MVR evaporator be concentrated into concentration be 60wt%, be then transferred to luwa evaporator into
Row is concentrated into 88wt%, as the methionine hydroxy analog product of commerical grade, is transferred to product storage tank, methionine in product storage tank
Hydroxy analogs amount to 340.89kg, yield 99.8%；Or the methionine hydroxy analog that out-phase membrane electrodialysis obtains is dilute water-soluble
Liquid is recycled to the methionine hydroxy analog of lower batch dilution kettle diluting high-concentration.Ammonium sulfate passes through drying, obtains byproduct sulphur
Sour ammonium, main content is 99%, almost without stink.
Embodiment 4
A kind of isolation and purification method of methionine hydroxy analog, comprising the following steps:
Step (1): passing through accurate filter for the mixed liquor III containing methionine hydroxy analog and inorganic ammonium salt, subsequently into
Homogeneous membrane electric dialyzator carries out desalting processing, until the ammonium salt in light room is reduced to 2.0wt%；The ammonium salt in light room is reduced again
To 0.01wt% is lower than, the methionine hydroxy analog aqueous solution in light room and the ammonium salt aqueous solution of dense room are obtained；
Step (2): the methionine hydroxy analog aqueous solution that the light room of out-phase membrane electrodialysis obtains further is concentrated into 88wt% and is obtained
To methionine hydroxy analog product, homogeneous membrane electrodialysis and the electrodialytic dense room saline solution of heterogeneous membrane by concentration, crystallization,
It is dry, obtain byproduct inorganic ammonium salt.
It may further be preferable that the inorganic ammonium salt in the step (1) is ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, phosphoric acid hydrogen
One or more of ammonium, ammonium dihydrogen phosphate or ammonium phosphate.
It may further be preferable that the inorganic ammonium salt is ammonium sulfate, it is described to contain methionine hydroxy analog and Inorganic Ammonium
The mixed liquor I II of salt is made by following methods:
Step (A): using 2- 2-hydroxy-4-methylthio butyronitrile as raw material, by hydration reaction, 2- 2-hydroxy-4-methylthio butyryl is obtained
Amine salt aqueous solution；
Step (B): water appropriate is added into the 2- 2-hydroxy-4-methylthio butyramide saline solution that step (A) obtains, by water
Solution, obtains methionine hydroxy analog and inorganic ammonium salt mixed aqueous solution；
Step (C): being added ammonia into step (B) resulting mixed liquor and neutralized, and keeps the ammonium hydrogen sulfate in its mixed liquor whole
Ammonium sulfate, static layering are converted, upper layer is methionine hydroxy analog organic layer, and lower layer is ammonium sulfate solution I；By organic layer
It is concentrated into almost anhydrous, point isolated decorating film, the decorating film is ammonium sulfate solids, and filtrate adds water or methionine hydroxyl
Base analog dilute aqueous solution is diluted to 88wt%, and isolated solid content is dissolved in water, obtains containing methionine hydroxy analog
Ammonium sulfate solution II, ammonium sulfate solution I and II merge, and then obtain by accurate filter similar containing methionine hydroxy
The ammonium sulfate solution III of object.
It may further be preferable that the mass percentage of the 2- 2-hydroxy-4-methylthio butyronitrile in the step (A) is 60%,
Remaining is water；The 2- 2-hydroxy-4-methylthio butyronitrile is made using methylthiopropionaldehyde and hydrogen cyanide as raw material, and the hydrogen cyanide is
Gaseous state, aqueous solution or high-purity liquid；The step (A) hydration reaction is carried out in the presence of acidic materials, institute
The acid stated is one or more of sulfuric acid, hydrochloric acid, phosphoric acid.
It may further be preferable that the acid of the hydration reaction is sulfuric acid, 2- 2-hydroxy-4-methylthio fourth in the step (A)
The molar ratio of nitrile and sulfuric acid is 1.0:0.70, and the hydration reaction temperature is 38 DEG C, and the hydration reaction time is 30min；
The hydrolysis of 2- 2-hydroxy-4-methylthio butyryl amine salt and water, 2- 2-hydroxy-4-methylthio butyramide in the step (B)
The molar ratio of salt and water is 1:3.6, and the hydrolysis temperature is 90 DEG C, hydrolysis time 120min；
Mixed system is heterogeneous system after step (C) the hydrolysis ammonification, and upper layer is organic layer, and main group becomes methionine hydroxyl
Base analog content is the content 8wt% of 65wt%, ammonium sulfate, and the content of water is 12wt%；Lower layer is water layer, and main group becomes sulphur
The content of sour ammonium is 25wt%, and the content of methionine hydroxy analog is 4wt%, and temperature is maintained at 40 DEG C DEG C when layering.
It may further be preferable that group in the ammonium sulfate solution III containing methionine hydroxy analog in the step (C)
Content as ammonium sulfate is 15%wt%, and the content of methionine hydroxy analog is 4%wt%, and temperature is 25 DEG C.
It may further be preferable that the methionine hydroxy analog organic layer enrichment facility is knifing steaming in step (c)
Send out device；
A kind of methionine hydroxy analog and solid ammonium sulfate mixture separate mode are centrifugation, mistake in step (c)
One of filter, filters pressing.
It may further be preferable that keeping feed liquid temperature in the homogeneous membrane and heterogeneous membrane electrodialytic process is 30 DEG C；It is described
The light room enrichment facility is that MVR evaporator and luwa evaporator combine, and the dense room enrichment facility is MVR evaporator.
The beneficial effects of the present invention are: compared with prior art, point of methionine hydroxy analog provided by the invention
It is reasonably to organically combine using homogeneous membrane electrodialysis and out-phase membrane electrodialysis and solve biography from purification process and its process units
Methionine hydroxy analog separates the problem of difficulty with inorganic salts in system production technology, compared with the homogeneous membrane electrodialysis of single use or
Out-phase membrane electrodialysis is used for methionine hydroxy analog desalination field, and the two, which organically combines, has selectivity height, separating degree high, with
Chromatography desalination is compared, and the ammonium sulfate solution of homogeneous membrane electrodialysis and heterogeneous membrane electrodialysis process containing methionine hydroxy analog is not
It needs to be diluted, before and after the processing, the concentration of methionine hydroxy analog reduces needed for subsequent purification concentration there is no reducing
Energy consumption, easy to operate, salt rejection rate is high, it is at low cost, decomposed without methionine hydroxy analog, and solve traditional processing technology
The methionine hydroxy analog exposed separates COD in the inorganic ammonium salt waste water of difficult problem and discharge with inorganic ammonium salt
High, reluctant problem, this method have ammonium content in obtained methionine hydroxy analog product low, producing ammonium sulfate byproduct
It purity is high and is destitute of smell, it is no a large amount of acid waste water discharge, environmentally protective, the advantages that methionine hydroxy analog high income.
Embodiment 5
A kind of isolation and purification method of methionine hydroxy analog, comprising the following steps:
Step (1): passing through accurate filter for the mixed liquor III containing methionine hydroxy analog and inorganic ammonium salt, subsequently into
Homogeneous membrane electric dialyzator carries out desalting processing, until the ammonium salt in light room is reduced to 7.5wt%；The ammonium salt in light room is reduced again
To 0.01wt% is lower than, the methionine hydroxy analog aqueous solution in light room and the ammonium salt aqueous solution of dense room are obtained；
Step (2): the methionine hydroxy analog aqueous solution that the light room of out-phase membrane electrodialysis obtains further is concentrated into 88wt% and is obtained
To methionine hydroxy analog product, homogeneous membrane electrodialysis and the electrodialytic dense room saline solution of heterogeneous membrane by concentration, crystallization,
It is dry, obtain byproduct inorganic ammonium salt.
It may further be preferable that the inorganic ammonium salt in the step (1) is ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, phosphoric acid hydrogen
One or more of ammonium, ammonium dihydrogen phosphate or ammonium phosphate.
It may further be preferable that the inorganic ammonium salt is ammonium sulfate, it is described to contain methionine hydroxy analog and Inorganic Ammonium
The mixed liquor I II of salt is made by following methods:
Step (A): using 2- 2-hydroxy-4-methylthio butyronitrile as raw material, by hydration reaction, 2- 2-hydroxy-4-methylthio butyryl is obtained
Amine salt aqueous solution；
Step (B): water appropriate is added into the 2- 2-hydroxy-4-methylthio butyramide saline solution that step (A) obtains, by water
Solution, obtains methionine hydroxy analog and inorganic ammonium salt mixed aqueous solution；
Step (C): being added ammonia into step (B) resulting mixed liquor and neutralized, and keeps the ammonium hydrogen sulfate in its mixed liquor whole
Ammonium sulfate, static layering are converted, upper layer is methionine hydroxy analog organic layer, and lower layer is ammonium sulfate solution I；By organic layer
It is concentrated into almost anhydrous, point isolated decorating film, the decorating film is ammonium sulfate solids, and filtrate adds water or methionine hydroxyl
Base analog dilute aqueous solution is diluted to 88wt%, and isolated solid content is dissolved in water, obtains containing methionine hydroxy analog
Ammonium sulfate solution II, ammonium sulfate solution I and II merge, and then obtain by accurate filter similar containing methionine hydroxy
The ammonium sulfate solution III of object.
It may further be preferable that the mass percentage of the 2- 2-hydroxy-4-methylthio butyronitrile in the step (A) is 99%,
Remaining is water；The 2- 2-hydroxy-4-methylthio butyronitrile is made using methylthiopropionaldehyde and hydrogen cyanide as raw material, and the hydrogen cyanide is
Gaseous state, aqueous solution or high-purity liquid；The step (A) hydration reaction is carried out in the presence of acidic materials, institute
The acid stated is one or more of sulfuric acid, hydrochloric acid, phosphoric acid.
It may further be preferable that the acid of the hydration reaction is sulfuric acid, 2- 2-hydroxy-4-methylthio fourth in the step (A)
The molar ratio of nitrile and sulfuric acid is 1.0:1.0, and the hydration reaction temperature is 65 DEG C, and the hydration reaction time is 120min；
The hydrolysis of 2- 2-hydroxy-4-methylthio butyryl amine salt and water, 2- 2-hydroxy-4-methylthio butyramide in the step (B)
The molar ratio of salt and water is 1:12.0, and the hydrolysis temperature is 110 DEG C, hydrolysis time 240min；
Mixed system is heterogeneous system after step (C) the hydrolysis ammonification, and upper layer is organic layer, and main group becomes methionine hydroxyl
Base analog content is the content 15wt% of 80wt%, ammonium sulfate, and the content of water is 20wt%；Lower layer is water layer, and main group becomes sulphur
The content of sour ammonium is 40wt%, and the content of methionine hydroxy analog is 12wt%, and temperature is maintained at 80 DEG C when layering.
It may further be preferable that group in the ammonium sulfate solution III containing methionine hydroxy analog in the step (C)
Content as ammonium sulfate is 30wt%, and the content of methionine hydroxy analog is 8wt%, and temperature is 40 DEG C.
It may further be preferable that the methionine hydroxy analog organic layer enrichment facility is knifing steaming in step (c)
Send out device；
A kind of methionine hydroxy analog and solid ammonium sulfate mixture separate mode are centrifugation, mistake in step (c)
One of filter, filters pressing.
It may further be preferable that keeping feed liquid temperature in the homogeneous membrane and heterogeneous membrane electrodialytic process is 35 DEG C；It is described
The light room enrichment facility is that MVR evaporator and luwa evaporator combine, and the dense room enrichment facility is MVR evaporator.
Claims (8)
1. a kind of isolation and purification method of methionine hydroxy analog, which comprises the following steps:
Step (1): passing through accurate filter for the mixed liquor III containing methionine hydroxy analog and inorganic ammonium salt, subsequently into
Homogeneous membrane electric dialyzator carries out desalting processing, until the ammonium salt in light room is reduced to 2.0%-7.5wt%；Again by the ammonium salt in light room
0.01wt% is decreased below, the methionine hydroxy analog aqueous solution in light room and the ammonium salt aqueous solution of dense room are obtained；
Step (2): the methionine hydroxy analog aqueous solution that the light room of out-phase membrane electrodialysis obtains further is concentrated into 88wt% and is obtained
To methionine hydroxy analog product, homogeneous membrane electrodialysis and the electrodialytic dense room saline solution of heterogeneous membrane by concentration, crystallization,
It is dry, obtain byproduct inorganic ammonium salt.
2. a kind of isolation and purification method of methionine hydroxy analog as described in claim 1, which is characterized in that the step
(1) inorganic ammonium salt in is one of ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate
Or it is a variety of.
3. a kind of isolation and purification method of methionine hydroxy analog as claimed in claim 2, which is characterized in that described inorganic
Ammonium salt is ammonium sulfate, and the mixed liquor I II containing methionine hydroxy analog and inorganic ammonium salt is made by following methods:
Step (A): using 2- 2-hydroxy-4-methylthio butyronitrile as raw material, by hydration reaction, 2- 2-hydroxy-4-methylthio butyryl is obtained
Amine salt aqueous solution；
Step (B): water appropriate is added into the 2- 2-hydroxy-4-methylthio butyramide saline solution that step (A) obtains, by water
Solution, obtains methionine hydroxy analog and inorganic ammonium salt mixed aqueous solution；
Step (C): being added ammonia into step (B) resulting mixed liquor and neutralized, and keeps the ammonium hydrogen sulfate in its mixed liquor whole
Ammonium sulfate, static layering are converted, upper layer obtains methionine hydroxy analog organic layer, and lower layer obtains ammonium sulfate solution I；To have
Machine layer carries out concentration and separation and decorating film is precipitated, and the decorating film is ammonium sulfate solids；Filtrate adds water or methionine hydroxy analog
Dilute aqueous solution is diluted to 88wt%；Isolated ammonium sulfate solid content is dissolved in water, is obtained containing methionine hydroxy analog
Ammonium sulfate solution II, ammonium sulfate solution I and II merge, and then obtain by accurate filter similar containing methionine hydroxy
The ammonium sulfate solution III of object.
4. a kind of isolation and purification method of methionine analog as claimed in claim 3, which is characterized in that the step (A)
In 2- 2-hydroxy-4-methylthio butyronitrile mass percentage be 60%~99%, remaining is water；The 2- 2-hydroxy-4-methylthio
Butyronitrile is made using methylthiopropionaldehyde and hydrogen cyanide as raw material, and the hydrogen cyanide is gaseous state, aqueous solution or high-purity liquid；Institute
Stating step (A) described hydration reaction is carried out in the presence of acidic materials, and the acid is sulfuric acid, hydrochloric acid, one in phosphoric acid
Kind is a variety of.
5. a kind of isolation and purification method of methionine analog as claimed in claim 3, which is characterized in that the step (A)
In, the acid of the hydration reaction is sulfuric acid, the molar ratio of 2- 2-hydroxy-4-methylthio butyronitrile and sulfuric acid be 1.0:0.70~
1.0, the hydration reaction temperature is 38 DEG C~65 DEG C, and the hydration reaction time is 30~120min；
The hydrolysis of 2- 2-hydroxy-4-methylthio butyryl amine salt and water, 2- 2-hydroxy-4-methylthio butyramide in the step (B)
The molar ratio of salt and water is 1:3.6~12.0, and the hydrolysis temperature is 90 DEG C~110 DEG C, hydrolysis time 120
~240min；
Mixed system is heterogeneous system after step (C) the hydrolysis ammonification, and upper layer is organic layer, and main group becomes methionine hydroxyl
Base analog content is 8%~15wt% of content of 65%~80wt%, ammonium sulfate, and the content of water is 12%~20wt%；Lower layer is water
Layer, the content that main group becomes ammonium sulfate is 25%~40wt%, and the content of methionine hydroxy analog is 4%~12wt%, and point
Temperature is maintained at 40 DEG C~80 DEG C when layer.
6. a kind of isolation and purification method of methionine hydroxy analog as claimed in claim 5, which is characterized in that the step
(C) it is 15%~30wt%, egg that group, which becomes the content of ammonium sulfate, in the ammonium sulfate solution III in containing methionine hydroxy analog
The content of propylhomoserin hydroxy analogs is 4%~8wt%, and temperature is 25 DEG C~40 DEG C.
7. a kind of isolation and purification method of methionine hydroxy analog as claimed in claim 6, which is characterized in that in step
(C) enrichment facility of methionine hydroxy analog organic layer described in is luwa evaporator；
A kind of methionine hydroxy analog and solid ammonium sulfate mixture separate mode are centrifugation, mistake in step (c)
One of filter, filters pressing.
8. a kind of isolation and purification method of methionine hydroxy analog as described in claim 1, which is characterized in that described homogeneous
It is 30 DEG C~35 DEG C that feed liquid temperature is kept in film and heterogeneous membrane electrodialytic process；The light room enrichment facility be MVR evaporator and
Luwa evaporator combines, and the dense room enrichment facility is MVR evaporator.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110407388A (en) * | 2019-08-16 | 2019-11-05 | 江南大学 | A kind of electricity such as glutamic acid concentration extract the recycling processing method of waste liquid |
| WO2021043188A1 (en) * | 2019-09-03 | 2021-03-11 | 蓝星安迪苏南京有限公司 | Mixture containing methionine hydroxy analog and oligomer thereof, and preparation method therefor |
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