CN106432020A - Separation and purification method of D,L-methionine - Google Patents
Separation and purification method of D,L-methionine Download PDFInfo
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- CN106432020A CN106432020A CN201610823258.0A CN201610823258A CN106432020A CN 106432020 A CN106432020 A CN 106432020A CN 201610823258 A CN201610823258 A CN 201610823258A CN 106432020 A CN106432020 A CN 106432020A
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- C07—ORGANIC CHEMISTRY
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- 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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Abstract
The invention provides a separation and purification method of D,L-methionine. The separation and purification method is realized through the following steps: hydrolyzing 5-(2-methylthio-ethyl)-hydantoin through an alkaline potassium compound to obtain a potassium methionine saponified solution containing potassium carbonate, introducing carbon dioxide into the saponified solution, crystalizing and separating to obtain methionine and a potassium bicarbonate water solution containing less methionine respectively, carrying out homogeneous membrane electroosmosis, heterogeneous membrane electroosmosis and the like on the potassium bicarbonate water solution respectively. By adopting the method provided by the invention, energy consumption needed by subsequent purification and concentration can be reduced and the operation is simple; the purity of the obtained methionine reaches up to 99.4 percent, the retention rate of the methionine reaches 98.8 percent, and the salt removing rate reaches 99.5 percent; the method can avoid a condition that the methionine is decomposed after being heated for a long time to generate malodorous gas; the method is low in cost, a condition that a lot of acidic and odorous wastewater is discharged is avoided, the method is green and environment-friendly, and the separated potassium bicarbonate can be completely circulated to the step of hydrolyzing the 5-(2-methylthioethyl)-hydantoin; fresh potassium carbonate, potassium bicarbonate or potassium hydroxide does not need to be supplemented.
Description
Technical field
The invention belongs to chemical field is and in particular to a kind of D, the isolation and purification method of L-Methionine.
Background technology
D, L-Methionine also known as methionine, are to constitute one of ultimate unit of protein, are unique in necessary aminoacid
Aminoacid containing sulfur, except participating in the synthesis of the transfer of methyl, the metabolism of phosphorus and epinephrine, choline, creatine in animal body
Outward, or the raw material of synthetic protein and cystine.
D, L-Methionine is widely used in the fields such as medicine, food, feedstuff and cosmetics, wherein as feed additive volume,
Consumption very big, the demand of global Methionine has reached 1,800,000 tons/year, China Methionine 2015 annual requirement exceed
160000 tons, and current China is in addition to 100,000 tons of Methionine of Ningxia purple light Tian Hua Methionine Co., Ltd are gone into operation, I
The Methionine of state also need to substantial amounts of from external import.
There are win wound, An Disu, Sumitomo, An Disu, Ningxia purple light sky in the whole world using the company that glycolylurea method prepares Methionine
And Russia's volga.The maximum difference of these company's glycolylurea method synthetic methionine techniques is embodied in two aspects；（1）Cyanogen source
Difference, that is, win wound, Sumitomo, An Disu are the 2- 2-hydroxy-4-methylthio fourths being obtained using hydrocyanic acid and methylthiopropionaldehyde reaction
Nitrile（Abbreviation cyanalcohol）For raw material production 5-（2-methylmercaptoethyl）- hydantoin（Abbreviation glycolylurea）, thus obtaining glycolylurea aqueous solution；
And Ningxia purple light sky and volga then adopt rowland-Planck production technology, with Cyanogran., methylthiopropionaldehyde, ammonia, titanium dioxide
The aqueous solution of carbon is raw material production 5-（2-methylmercaptoethyl）- hydantoin（Abbreviation glycolylurea）, thus obtaining containing sodium carbonate
Glycolylurea aqueous solution；（2）The alkali of hydrolysis glycolylurea is different.In win wound, the Methionine production technology of Sumitomo, the hydrolysis of glycolylurea uses and is
Potassium carbonate or potassium hydroxide aqueous solution, carbon dioxide is acidified, and potassium carbonate recycles, and production technology is cleaner；And pacify enlightening
Soviet Union, Ningxia purple light sky, the Methionine production technology of volga are all derived from the production technology of French rowland-Planck, because
The hydrolysis of this glycolylurea is all to use sodium hydrate aqueous solution, and sulphuric acid is acidified, by-product sodium sulfate.
But the potassium salt technique for Methionine, the mother solution after being separated due to Methionine still contains corresponding with its dissolubility
Amount Methionine, also contain potassium bicarbonate, it can be used as alkaline potassium compound recirculation.Therefore, mother solution can be above-mentioned
5-（2-methylmercaptoethyl）Recirculation in-hydantoin hydrolysis.High temperature divides potassium bicarbonate filtrate containing Methionine repeatedly
Solution, circulation concentrate, and in order to avoid the loss of Methionine, not outer as far as possible row's potassium bicarbonate mother solution, lead to Methionine when long
Between be under high temperature steaming, some methionine there occurs thermal decomposition, creates the Methyl disulfide with foul smell or first sulfur
Alcohol, these materials can remain in potassium carbonate mother solution and the cooling water of outer row in, lead to the potassium carbonate mother solution circulating for a long time to have
Foul smelling taste, plant operations bad environments, affect surrounding enviroment, and also result in Methionine decomposed, mother solution C OD of outer row
Higher it is difficult to carry out biochemical treatment, and potassium bicarbonate mother solution constantly circulates, and the Methionine in mother solution decomposes the impurity generating
Can constantly accumulate, these materials lead to the decline of follow-up Methionine crystallization and its Methionine product quality.Patent
CN104693082A discloses a kind of method isolating and purifying Methionine using continuous chromatography, and the method is exactly to use continuous chromatography
Process the sulphuric acid mother liquid of sodium containing Methionine, reach the purpose of desalination, but the problem of maximum has at 2 points：First is, chromatograph is invested
Greatly；Second is, the Methionine obtaining after chromatographic isolation and the concentration of sodium sulfate all dilute twice, remove in follow-up concentration
Water consumption is higher.
Furthermore, due to recirculation whole amount mother solution when, lead to the impurities accumulation in mother solution, therefore, mother solution must be with
Predetermined ratio exclusion, the mother solution of exclusion is not preferred as waste water dis posal, because containing valuable egg ammonia in mother solution
In acid and potassium bicarbonate, and mother solution, Methionine can consume partial alkaline potassium compound, leads to hydrolyze 5-（2-methylmercaptoethyl）-
During hydantoin, need to add fresh alkaline potassium compound；Or in order that its Methionine is separated thoroughly with potassium bicarbonate, plus
Enter organic solvent miscible with water such as methanol, ethanol, isopropanol etc..
Although out-phase EDBM can carry out desalting processing, it is low that this desalination is often merely able to removing salinity
Feed liquid, has strict requirements to processing the salinity in feed liquid, if salinity is too high, can lead to the electrodialytic desalination of heterogeneous membrane
The problem that power consumption is high, salt rejection rate is low, Methionine rejection is low.
Therefore, develop another produce D, L-Methionine new technology is to be highly desirable to, especially Methionine with inorganic
The the isolating and purifying of salt.
Content of the invention
It is an object of the invention to provide a kind of D, the isolation and purification method of L-Methionine, the method can overcome traditional D,
The potassium bicarbonate Recycling Mother Solution problem containing Methionine of L-Methionine production method, a difficult problem for energy waste, Methionine is decomposed
Problem.
The purpose of the present invention is realized by following technical measures：
A kind of D, the isolation and purification method of L-Methionine is it is characterised in that it comprises the steps：
1. use alkaline potassium compound to hydrolyze 5-（2-methylmercaptoethyl）- hydantoin, obtains the Methionine potassium containing potassium carbonate
Saponification liquor；
2. it is passed through carbon dioxide neutralization, crystallization in step 1 gained saponification liquor, separates, respectively obtain Methionine and contain egg ammonia
The potassium bicarbonate aqueous solution of acid；
3. the potassium bicarbonate aqueous solution containing a small amount of Methionine that step 2 obtains is carried out homogeneous membrane electricity after accurate filter
Electrodialysis desalination is processed, until the potassium bicarbonate content in the light room of homogeneous EDBM is reduced to 3 ~ 7wt%；
4. the solution in the homogeneous light room of EDBM after processing through step 3 carries out out-phase EDBM deep desalting again, until
Potassium bicarbonate in the light room of out-phase EDBM decreases below 0.1wt%, obtains Methionine aqueous solution, by Methionine aqueous solution
Condensing crystallizing obtains Methionine product further, and potassium bicarbonate aqueous solution is recycled to hydrolysis 5-（2-methylmercaptoethyl）- hydantoin
Step.
The pressure being passed through carbon dioxide in described step 2 is 0.1 ~ 1.0Mpa.
Further, it is passed through neutral temperature during carbon dioxide in described step 2 and is 0 DEG C ~ 60 DEG C, preferable temperature is 0 DEG C ~ 30
℃.
Further, it is passed through the pH neutralizing during carbon dioxide in described step 2 and is controlled to 5.0 ~ 9.0, preferably pH is controlled to
6.0-8.0；In the described potassium bicarbonate aqueous solution containing Methionine, the mass percent content of Methionine is 1% ~ 10%, carbon
The mass percent content of potassium hydrogen phthalate is 5%-35%.
Further, in described step 3 and step 4, electrodialysis separation condition is：Separation temperature is 0 DEG C ~ 40 DEG C, separates feed liquid
PH value be 6 ~ 9.
Further, in described step 3 and step 4, electrodialysis separation temperature is preferably 10 DEG C ~ 30 DEG C, separates the pH value of feed liquid
It is preferably 6 ~ 7.5.
Further, described step 3 and the detached pH of step 4 electrodialysis need to be maintained at 6 ~ 7.5, be passed through titanium dioxide in feed liquid
Carbon.
Further, the 5- in described step 1（2-methylmercaptoethyl）- hydantoin is solid or aqueous solution, described 5-
（2-methylmercaptoethyl）- hydantoin is with 2- 2-hydroxy-4-methylthio butyronitrile or methylthiopropionaldehyde-hydrocyanic acid solution and carbon ammonium
Ammonia spirit reaction prepare, described alkaline potassium compound be one of potassium hydroxide, potassium bicarbonate, potassium carbonate or
Person is multiple, described alkaline potassium compound and 5-（2-methylmercaptoethyl）The molar ratio of-hydantoin is 1.0 ~ 3.0：1, institute
Stating hydrolysis temperature required is 140 DEG C ~ 200 DEG C, and described saponification liquor is Methionine potassium, potassium carbonate, potassium formate and its a small amount of Methionine
Dimer mixed liquor, its pH be 9-13, in described saponification liquor the mass percent content of Methionine potassium be 5%-30%, carbonic acid
The mass percent content of potassium is 1%-20%.
Further, described 5-（2-methylmercaptoethyl）- hydantoin is preferably aqueous solution, 5- in aqueous solution（2- methyl mercapto
Ethyl）The weight/mass percentage composition of-hydantoin is 1%-40%, and described alkaline potassium compound is preferably potassium carbonate, described alkalescence potassium
Compound and 5-（2-methylmercaptoethyl）The molar ratio of-hydantoin is preferably 1.0 ~ 2.0：1, described hydrolysis temperature is preferred
For 160 DEG C ~ 190 DEG C.
Optimum, 5- in aqueous solution（2-methylmercaptoethyl）The weight/mass percentage composition of-hydantoin is 10%-25%.
Further, the Methionine aqueous solution that described step 4 obtains after separating through out-phase EDBM is through concentrating, crystallizing
To Methionine product, described potassium bicarbonate aqueous solution is to being recycled to hydrolysis 5-（2-methylmercaptoethyl）- hydantoin step, or
Person's potassium bicarbonate aqueous solution, after concentration, pyrolytic, is recycled to hydrolysis 5-（2-methylmercaptoethyl）- hydantoin step.
Further, the Methionine product that described step 2 obtains can pass through washing, or recrystallization, obtains after drying
Highly purified Methionine product.
Further, during the Methionine recrystallization product burning that described step 2 obtains, flame is blue or purple, described egg
Propylhomoserin product is that white crystals granule, reflective are good, and its granule is big, more uniform, and in length, flat bulk, particle length concentrates on
In 250-650 micrometer range, individual particle outward appearance is completely fine and close crystal（As shown in Figure 1）.
Further, when the Methionine product after the washing of described step 2 burns, flame is blue or purple, described egg ammonia
Acid product is that white crystals granule, reflective are good, and its granule is big, in near-spherical and granularity concentrates on 110-130 micron, more equal
Even（As shown in Figure 2）.
Electrodialysis principle in described step 3 and step 4 is as shown in Figure 3.
The present invention has following beneficial effect：
D of the present invention, the environment-protecting clean isolation and purification method of L-Methionine can reduce subsequent purification and concentrate required energy consumption, operation letter
Single, gained Methionine purity may be up to more than 99.4%, and the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%, we
Method is not required to for the inorganic salt filtrate containing Methionine concentration be repeated, and the long-time decomposes of Methionine can be avoided to generate evil
Odour, and this method acid and stink discharge of wastewater, environmental protection, detached potassium bicarbonate with low cost, no substantial amounts of
It is recycled to completely hydrolyze 5-（2-methylmercaptoethyl）- hydantoin step, need not add fresh potassium carbonate, potassium bicarbonate or
Potassium hydroxide, worth marketing application.
Brief description
Fig. 1：Crystal electron-microscope scanning figure after isolation and purification method Methionine recrystallization of the present invention；
Fig. 2：Crystal electron-microscope scanning figure after isolation and purification method Methionine washing of the present invention；
Fig. 3：Electrodialysis schematic diagram of the present invention.
Specific embodiment
Below by embodiment, the present invention is specifically described it is necessary to it is pointed out here that be that following examples are only used
In being further described to the present invention it is impossible to be interpreted as limiting the scope of the invention, without departing substantially from present invention spirit
In the case of essence, the modification that the inventive method, step or condition are made or replacement, belong to the scope of the present invention.
Embodiment 1
Take 5-（2-methylmercaptoethyl）3484.4 grams of the aqueous solution of-hydantoin is added in autoclave, wherein 5-（2- first
Sulfenyl ethyl）696.88 grams of-hydantoin（4mol）, it is subsequently adding 1658.4 grams of the wet chemical that mass fraction is 50%,
Enclosed high pressure reactor, is warming up to 180 DEG C immediately, insulation reaction 20 minutes, and then to normal pressure, the saponification liquor obtaining passes through for pressure release
After air stripping, the ammonia residual in saponification liquor is less than 50ppm；It is passed through carbon dioxide in the saponification liquor after deamination, be passed through carbon dioxide
Pressure be 0.5MPa, neutral temperature is 20 DEG C, and the pH of neutralization terminal is 6.8, sucking filtration crystal, a small amount of wash, obtain Methionine
Wet product, through drying, obtains 415.9 grams of content 99.3% Methionine product；Wash water is merged with sucking filtration mother solution, obtains containing egg ammonia
3659.44 grams of the potassium bicarbonate aqueous solution of acid（Methionine mass percent content is 5%, and potassium bicarbonate mass percent content is
32.7%, potassium carbonate, potassium formate, potassium acetate etc. about account for the 1% about of mother solution gross mass）, this mother solution is homogeneous faint yellow
Prescribed liquid.
By the potassium bicarbonate aqueous solution containing Methionine obtained above through accurate filter, maintain the temperature at 25 DEG C of bars
Enter homogeneous EDBM under part and carry out desalting processing, homogeneous EDBM has three Room, be pole liquid room, feed liquid room respectively（Light
Room）And receiving chamber（Dense room）, in desalination processes, because potassium bicarbonate migrates to dense room, feed liquid is passed through carbon dioxide and keeps pH
7.0 about.When the potassium bicarbonate in feed liquid room is reduced to 5%, the material in feed liquid room proceeds to heterogeneous membrane electrodialysis process system
System carries out deep desalting, and through electrodialysis desalination twice, the potassium bicarbonate content in feed liquid is less than 0.05%, and methionine content is
4.5%；After electrodialysis desalination twice, the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%.
By D, L-Methionine clear liquid carries out being concentrated into concentration, then crystallisation by cooling, and sucking filtration, drying obtain D, L-Methionine
178.26 grams of product, purity is 99.4%；Potassium bicarbonate clear liquid obtained above, through being heated to 120 DEG C, obtains potash water
Molten, 5- can be recycled to（2-methylmercaptoethyl）- hydantoin hydrolysis alkali.
Embodiment 2
Take 5-（2-methylmercaptoethyl）3484.4 grams of the aqueous solution of-hydantoin is added in autoclave, wherein 5-（2- first
Sulfenyl ethyl）696.88 grams of-hydantoin（4mol）, it is subsequently adding the wet chemical 1474.13 that mass fraction is 60%
Gram, enclosed high pressure reactor, it is warming up to 185 DEG C immediately, insulation reaction 15 minutes, then pressure release is to normal pressure, the saponification liquor obtaining
After air stripping, the ammonia residual in saponification liquor is less than 40ppm；It is passed through carbon dioxide in the saponification liquor after deamination, be passed through dioxy
The pressure changing carbon is 0.8MPa, and neutral temperature is 15 DEG C, and the pH of neutralization terminal is 6.0, sucking filtration crystal, and a small amount of washing obtains egg
Propylhomoserin wet product, through drying, obtains 445.65 grams of content 99.3% Methionine product；Wash water is merged with sucking filtration mother solution, is contained
3725 grams of the potassium bicarbonate aqueous solution of Methionine（Methionine mass percent content is 4%, potassium bicarbonate mass percent content
For 34.0%, potassium carbonate, potassium formate, potassium acetate etc. about account for the 1% about of mother solution gross mass）, this mother solution is homogeneous faint yellow
Transparency liquid.
By the potassium bicarbonate aqueous solution containing Methionine obtained above through accurate filter, maintain the temperature at 25 DEG C of bars
Enter homogeneous EDBM under part and carry out desalting processing, homogeneous EDBM has three Room, be pole liquid room, feed liquid room respectively（Light
Room）And receiving chamber（Dense room）, in desalination processes, because potassium bicarbonate migrates to dense room, feed liquid is passed through carbon dioxide and keeps pH
7.0 about.When the potassium bicarbonate in feed liquid room is reduced to 5%, the material in feed liquid room proceeds to heterogeneous membrane electrodialysis process system
System carries out deep desalting, and through electrodialysis desalination twice, the potassium bicarbonate content in feed liquid is less than 0.05%, and methionine content is
5.5%；After electrodialysis desalination twice, the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%.
By D, L-Methionine clear liquid carries out being concentrated into concentration, then crystallisation by cooling, and sucking filtration, drying obtain D, L-Methionine
148.4 grams of product, purity is 99.4%；Through being heated to 120 DEG C, it is water-soluble to obtain potassium carbonate for potassium bicarbonate clear liquid obtained above,
5- can be recycled to（2-methylmercaptoethyl）- hydantoin hydrolysis alkali.
Embodiment 3
Take 5-（2-methylmercaptoethyl）3484.4 grams of the aqueous solution of-hydantoin is added in autoclave, wherein 5-（2- first
Sulfenyl ethyl）696.88 grams of-hydantoin（4mol）, it is subsequently adding the wet chemical 1474.13 that mass fraction is 60%
Gram, enclosed high pressure reactor, it is warming up to 185 DEG C immediately, insulation reaction 15 minutes, then pressure release is to normal pressure, the saponification liquor obtaining
After air stripping, the ammonia residual in saponification liquor is less than 40ppm；It is passed through carbon dioxide in the saponification liquor after deamination, be passed through dioxy
The pressure changing carbon is 0.8MPa, and neutral temperature is 15 DEG C, and the pH of neutralization terminal is 6.0, and sucking filtration crystal obtains Methionine wet product,
The wet product obtaining is carried out recrystallization, sucking filtration crystal, through drying, obtains 312.0 grams of content 99.6% Methionine product, obtain
Methionine product be scanned through electronic microscope photos, as shown in figure 1, Methionine product is that white crystals granule, reflective are good, its
Grain is big, more uniform, and in length, flat bulk, particle length concentrates in 250-650 micrometer range, and individual particle outward appearance is complete
Fine and close crystal；Recrystallization mother liquor is merged with sucking filtration mother solution, obtains 3725 grams of the potassium bicarbonate aqueous solution containing Methionine（Egg ammonia
Sour mass percent content is 7.6%, and potassium bicarbonate mass percent content is 34.0%, and potassium carbonate, potassium formate, potassium acetate etc. are big
About account for the 2% about of mother solution gross mass）, this mother solution is homogeneous light yellow transparent liquid.
By the potassium bicarbonate aqueous solution containing Methionine obtained above through accurate filter, maintain the temperature at 25 DEG C of bars
Enter homogeneous EDBM under part and carry out desalting processing, homogeneous EDBM has three Room, be pole liquid room, feed liquid room respectively（Light
Room）And receiving chamber（Dense room）, in desalination processes, because potassium bicarbonate migrates to dense room, feed liquid is passed through carbon dioxide and keeps pH
7.0 about.When the potassium bicarbonate in feed liquid room is reduced to 5%, the material in feed liquid room proceeds to heterogeneous membrane electrodialysis process system
System carries out deep desalting, and through electrodialysis desalination twice, the potassium bicarbonate content in feed liquid is less than 0.05%, and methionine content is
5.5%；After electrodialysis desalination twice, the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%.
By D, L-Methionine clear liquid carries out being concentrated into concentration, then crystallisation by cooling, and sucking filtration, drying obtain D, L-Methionine
243.5 grams of product, purity is 99.5%；Through being heated to 120 DEG C, it is water-soluble to obtain potassium carbonate for potassium bicarbonate clear liquid obtained above,
5- can be recycled to（2-methylmercaptoethyl）- hydantoin hydrolysis alkali.
Embodiment 4
Take 5-（2-methylmercaptoethyl）3484.4 grams of the aqueous solution of-hydantoin is added in autoclave, wherein 5-（2- first
Sulfenyl ethyl）696.88 grams of-hydantoin（4mol）, it is subsequently adding the wet chemical 1474.13 that mass fraction is 60%
Gram, enclosed high pressure reactor, it is warming up to 185 DEG C immediately, insulation reaction 15 minutes, then pressure release is to normal pressure, the saponification liquor obtaining
After air stripping, the ammonia residual in saponification liquor is less than 40ppm；It is passed through carbon dioxide in the saponification liquor after deamination, be passed through dioxy
The pressure changing carbon is 0.8MPa, and neutral temperature is 25 DEG C, and the pH of neutralization terminal is 7.6, and sucking filtration crystal obtains Methionine wet product,
The wet product obtaining is carried out recrystallization, sucking filtration crystal, through drying, obtains 312.0 grams of content 99.6% Methionine product, obtain
Methionine product be scanned through electronic microscope photos, as shown in figure 1, Methionine product is that white crystals granule, reflective are good, its
Grain is big, more uniform, and in length, flat bulk, particle length concentrates in 250-650 micrometer range, and individual particle outward appearance is complete
Fine and close crystal；Recrystallization mother liquor is merged with sucking filtration mother solution, obtains 3725 grams of the potassium bicarbonate aqueous solution containing Methionine（Egg ammonia
Sour mass percent content is 8.0%, and potassium bicarbonate mass percent content is 32.0%, and potassium carbonate, potassium formate, potassium acetate etc. are big
About account for the 4% about of mother solution gross mass）, this mother solution is homogeneous light yellow transparent liquid.
By the potassium bicarbonate aqueous solution containing Methionine obtained above through accurate filter, maintain the temperature at 25 DEG C of bars
Enter homogeneous EDBM under part and carry out desalting processing, homogeneous EDBM has three Room, be pole liquid room, feed liquid room respectively（Light
Room）And receiving chamber（Dense room）, in desalination processes, because potassium bicarbonate migrates to dense room, feed liquid is passed through carbon dioxide and keeps pH
7.0 about.When the potassium bicarbonate in feed liquid room is reduced to 5%, the material in feed liquid room proceeds to heterogeneous membrane electrodialysis process system
System carries out deep desalting, and through electrodialysis desalination twice, the potassium bicarbonate content in feed liquid is less than 0.05%, and methionine content is
5.5%；After electrodialysis desalination twice, the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%.
By D, L-Methionine clear liquid carries out being concentrated into concentration, then crystallisation by cooling, and sucking filtration, drying obtain D, L-Methionine
224.4 grams of product, purity is 99.5%；Through being heated to 120 DEG C, it is water-soluble to obtain potassium carbonate for potassium bicarbonate clear liquid obtained above,
5- can be recycled to（2-methylmercaptoethyl）- hydantoin hydrolysis alkali.
Embodiment 5
Take 5-（2-methylmercaptoethyl）3484.4 grams of the aqueous solution of-hydantoin is added in autoclave, wherein 5-（2- first
Sulfenyl ethyl）696.88 grams of-hydantoin（4mol）, it is subsequently adding the wet chemical 1474.13 that mass fraction is 60%
Gram, enclosed high pressure reactor, it is warming up to 185 DEG C immediately, insulation reaction 15 minutes, then pressure release is to normal pressure, the saponification liquor obtaining
After air stripping, the ammonia residual in saponification liquor is less than 40ppm；The activated carbon adding saponification liquor quality 0.1% carries out desolventing technology,
Filter activity charcoal, obtains essentially colorless transparent saponification liquor.
It is passed through carbon dioxide in the saponification liquor of decolouring, the pressure being passed through carbon dioxide is 0.8MPa, and neutral temperature is 15
DEG C, the pH of neutralization terminal is 6.0, and sucking filtration crystal obtains Methionine wet product, the wet product obtaining is carried out recrystallization, sucking filtration crystal,
Through drying, obtain 312.0 grams of content 99.6% Methionine product, the Methionine product obtaining is scanned through electronic microscope photos, such as scheme
Shown in 1, Methionine product is that white crystals granule, reflective are good, and its granule is big, more uniform, and in length, flat bulk, granule is long
Degree concentrates in 250-650 micrometer range, and individual particle outward appearance is completely fine and close crystal；Recrystallization mother liquor is closed with sucking filtration mother solution
And, obtain 3725 grams of the potassium bicarbonate aqueous solution containing Methionine（Methionine mass percent content is 7.6%, potassium bicarbonate matter
Amount relative content is 34.0%, and potassium carbonate, potassium formate, potassium acetate etc. about account for the 2% about of mother solution gross mass）, this mother solution
For homogeneous light yellow transparent liquid.
By the potassium bicarbonate aqueous solution containing Methionine obtained above through accurate filter, maintain the temperature at 25 DEG C of bars
Enter homogeneous EDBM under part and carry out desalting processing, homogeneous EDBM has three Room, be pole liquid room, feed liquid room respectively（Light
Room）And receiving chamber（Dense room）, in desalination processes, because potassium bicarbonate migrates to dense room, feed liquid is passed through carbon dioxide and keeps pH
7.0 about.When the potassium bicarbonate in feed liquid room is reduced to 5%, the material in feed liquid room proceeds to heterogeneous membrane electrodialysis process system
System carries out deep desalting, and through electrodialysis desalination twice, the potassium bicarbonate content in feed liquid is less than 0.05%, and methionine content is
5.5%；After electrodialysis desalination twice, the rejection of Methionine reaches 98.8%, and desalination rate reaches 99.5%.
By D, L-Methionine clear liquid carries out being concentrated into concentration, then crystallisation by cooling, and sucking filtration, drying obtain D, L-Methionine
243.5 grams of product, purity is 99.5%；Through being heated to 120 DEG C, it is water-soluble to obtain potassium carbonate for potassium bicarbonate clear liquid obtained above,
5- can be recycled to（2-methylmercaptoethyl）- hydantoin hydrolysis alkali.
Claims (10)
1. a kind of D, the isolation and purification method of L-Methionine is it is characterised in that it comprises the steps：
A. hydrolyze 5- using alkaline potassium compound（2-methylmercaptoethyl）- hydantoin, obtains the Methionine potassium containing potassium carbonate
Saponification liquor；
B. it is passed through carbon dioxide neutralization, crystallization in step A gained saponification liquor, separates, respectively obtain Methionine and contain egg ammonia
The potassium bicarbonate aqueous solution of acid；
C. the potassium bicarbonate aqueous solution containing Methionine that step B obtains is carried out homogeneous membrane electrodialysis after accurate filter
Desalting processing is until the potassium bicarbonate in the light room of homogeneous EDBM is reduced to 3 ~ 7wt%；
D. the solution in the homogeneous light room of EDBM after processing through step C carries out out-phase EDBM again and carries out deep desalting,
Until the potassium bicarbonate in the light room of out-phase EDBM decreases below 0.1wt%, obtain Methionine aqueous solution, by Methionine water
The further condensing crystallizing of solution obtains Methionine product, and potassium bicarbonate aqueous solution is recycled to hydrolysis 5-（2-methylmercaptoethyl）In-second
Uride step.
2. a kind of D as claimed in claim 1, the isolation and purification method of L-Methionine is it is characterised in that logical in described step B
The pressure entering carbon dioxide is 0.1 ~ 1.0Mpa.
3. a kind of D as claimed in claim 1 or 2, the isolation and purification method of L-Methionine is it is characterised in that in described step B
It is passed through neutral temperature during carbon dioxide and is 0 DEG C ~ 60 DEG C, preferable temperature is 0 DEG C ~ 30 DEG C.
4. a kind of D as described in any one of claim 1,2 or 3, the isolation and purification method of L-Methionine is it is characterised in that walk
It is passed through, in rapid B, the pH neutralizing during carbon dioxide and is controlled to 5.0 ~ 9.0, preferably pH is controlled to 6.0-8.0；Described contains Methionine
Potassium bicarbonate aqueous solution in, the mass percent content of Methionine is 1% ~ 10%, and the mass percent content of potassium bicarbonate is
5%-35%.
5. a kind of D as described in any one of claim 1 ~ 4, the isolation and purification method of L-Methionine is it is characterised in that described step
In rapid C and step D, electrodialysis separation condition is：Separation temperature is 0 DEG C ~ 40 DEG C, and the pH value separating feed liquid is 6 ~ 9.
6. a kind of D as described in any one of claim 1 ~ 5, the isolation and purification method of L-Methionine is it is characterised in that described step
In rapid C and step D, electrodialysis separation temperature is preferably 10 DEG C ~ 30 DEG C, and the pH value separating feed liquid is preferably 6 ~ 7.5.
7. a kind of D as described in any one of claim 1 ~ 6, the isolation and purification method of L-Methionine is it is characterised in that described step
The rapid C and detached pH of step D electrodialysis need to be maintained at 6 ~ 7.5, is passed through carbon dioxide in feed liquid.
8. a kind of D as described in any one of claim 1 ~ 7, the isolation and purification method of L-Methionine is it is characterised in that described step
5- in rapid A（2-methylmercaptoethyl）- hydantoin is solid or aqueous solution, described 5-（2-methylmercaptoethyl）Acyl in-second
Urea is to react with the ammonia spirit of 2- 2-hydroxy-4-methylthio butyronitrile or methylthiopropionaldehyde-hydrocyanic acid solution and carbon ammonium to be prepared into
Arrive, described alkaline potassium compound is one of potassium hydroxide, potassium bicarbonate, potassium carbonate or multiple, described alkalescence potassium
Compound and 5-（2-methylmercaptoethyl）The molar ratio of-hydantoin is 1.0 ~ 3.0：1, described hydrolysis is temperature required to be 140
DEG C ~ 200 DEG C, described saponification liquor is Methionine potassium, the dimer mixed liquor of potassium carbonate, potassium formate and its a small amount of Methionine, its pH
For 9-13, in described saponification liquor, the mass percent content of Methionine potassium is 5%-30%, the mass percent content of potassium carbonate
For 1%-20%.
9. a kind of D as described in any one of claim 1 ~ 8, the isolation and purification method of L-Methionine is it is characterised in that described 5-
（2-methylmercaptoethyl）- hydantoin is preferably aqueous solution, 5- in aqueous solution（2-methylmercaptoethyl）The quality hundred of-hydantoin
Point content is 1%-40%, and described alkaline potassium compound is preferably potassium carbonate, described alkaline potassium compound and 5-（2- methylmercaptan ethyl
Base）The molar ratio of-hydantoin is preferably 1.0 ~ 2.0：1, described hydrolysis temperature is preferably 160 DEG C ~ 190 DEG C.
10. a kind of D as claimed in claim 9, the isolation and purification method of L-Methionine is it is characterised in that in described aqueous solution
5-（2-methylmercaptoethyl）The weight/mass percentage composition of-hydantoin is 10%-25%.
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