CN108794364A - A kind of isolation and purification method of methionine - Google Patents
A kind of isolation and purification method of methionine Download PDFInfo
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- CN108794364A CN108794364A CN201710302144.6A CN201710302144A CN108794364A CN 108794364 A CN108794364 A CN 108794364A CN 201710302144 A CN201710302144 A CN 201710302144A CN 108794364 A CN108794364 A CN 108794364A
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- methionine
- isolation
- purification method
- aqueous solution
- crude product
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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
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of isolation and purification method of methionine, includes at least following steps：1）Add water to carry out the desalinization of soil by flooding or leaching processing methionine of saliferous, is separated by solid-liquid separation, obtained solid is methionine crude product；2）By step 1）Obtained methionine crude product adds water that aqueous solution is made, and recrystallizes, and is separated by solid-liquid separation, obtained solid is finished product methionine.The methionine isolation and purification method of the present invention saves energy consumption, easy to operate, and the purity for the methionine product that this method obtains reaches 99.0% or more, is truly realized the maximization of the utilization of resources.
Description
Technical field
The present invention relates to methionine production technical fields, more particularly to a kind of isolation and purification method of methionine.
Background technology
Currently, the solid residue containing methionine, sodium sulphate and other impurities generated by methionine manufacturing enterprise is not only
Environment, cost of idleness are polluted, and it is big to be recycled difficulty, and no small loss is brought to enterprise, and this contains sodium sulphate, first
The methionine of the impurity such as hydrochlorate, ammonium sulfate, abbreviation secondary methionine.Because it has the characteristics that：1. composition is complicated and unstable
It is fixed：By weight, the content of methionine is in 20%-60%；The content of sodium sulphate is in 20%-60%；Quality hundred shared by moisture
Score is 10%-20%, and the mass percent shared by formate is 1%-6%, and the mass percent shared by ammonium sulfate is
0.5%-2%, the mass percent shared by polymer is 1% or so, or even sometimes contains resin and silt；2. color compared with
Deep, decoloration is difficult, consumes the decoloring substances such as big carbon content active, quality is not still up to standard.It is reported that the current country is found no rationally
Economic secondary methionine processing method, it is main or by the way of burning disposal.
A kind of existing processing mode is to use some exclusion devices, reduces the impurities accumulation in secondary methionine mother liquor,
The less mother liquor of impurity is obtained, mother liquor is then returned into system circulation, to reduce mother liquor as the amount of discharging of waste liquid, to subtract
Secondary methionine is not processed into qualified methionine product by the quantum of output of few secondary methionine, this method, is had larger
Limitation does not tackle the problem at its root.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of sides of isolating and purifying of methionine
The problems such as method, the processing method for solving methionine sub-quality products in the prior art is not good enough, and the methionine purity handled is low.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of side of isolating and purifying of methionine
Method includes at least following steps：
1) add water to carry out the desalinization of soil by flooding or leaching processing methionine of saliferous, be separated by solid-liquid separation, obtained solid is methionine crude product；
2) add water that aqueous solution is made the methionine crude product that step 1) obtains, recrystallize, be separated by solid-liquid separation, obtained solid is i.e.
For finished product methionine.
In some embodiments of the invention, in step 1), when the desalinization of soil by flooding or leaching is handled, it is the total matter of saliferous methionine to add the quality of water
0.5-1.2 times of amount.
In some embodiments of the invention, in step 1), when the desalinization of soil by flooding or leaching is handled, control solution temperature is at 20-40 DEG C.
In some embodiments of the invention, in step 1), when the desalinization of soil by flooding or leaching is handled, control solution temperature is at 30-40 DEG C.
In some embodiments of the invention, in step 1), the desalinization of soil by flooding or leaching time is 0.5h or more.Sodium sulphate in desalinization of soil by flooding or leaching aqueous solution
Close to saturation state, in order to which the later stage carries out continuous chromatography separation or electrodialysis.
In some embodiments of the invention, in step 1), the desalinization of soil by flooding or leaching time is 0.5-1.5h.
In some embodiments of the invention, in step 1), after filtering, filtrate is subjected to desalting processing, respectively obtains and contains
The aqueous solution of methionine and the aqueous solution of saliferous.
In some embodiments of the invention, in step 1), by the aqueous solution of saliferous by concentration, crystallization, finished product is obtained
Salt.
In some embodiments of the invention, in step 1), the method for desalting processing is continuous chromatography or electroosmose process.
In some embodiments of the invention, in step 1), the method for desalting processing is continuous chromatography or homogeneous membrane electricity
Dialysis.
In some embodiments of the invention, in step 2), methionine crude product aqueous solution and step 1) desalination are obtained
Aqueous solution containing methionine merges, then carries out subsequent processing.
In some embodiments of the invention, in step 2), when adding water that aqueous solution is made methionine crude product, methionine is thick
The mass ratio of product and water is 1：(5-8).
In some embodiments of the invention, in step 2), when preparing methionine crude product aqueous solution, aqueous temperature is controlled
It is 65-80 DEG C.
In some embodiments of the invention, in step 2), when recrystallization, it is cooled to 20-32 DEG C.
In some embodiments of the invention, in step 2), activated carbon is first added into solution and carries out decolorization, filtering
Isolating active charcoal and then filtrate is recrystallized.
In some embodiments of the invention, in step 2), the quality that activated carbon is added is methionine crude product quality
0.5-4%.
In some embodiments of the invention, in step 2), when recrystallization, the 1%~10% of total methionine quality is added
Methionine crystal seed.
In some embodiments of the invention, in step 2), when recrystallization, falling temperature gradient is：70 DEG C of heat preservation 10-20min,
69 DEG C of heat preservation 3min, are down to 58 DEG C from 68 DEG C, then be down to 20- from 58 DEG C with the rate of 2 DEG C/min with the rate of temperature fall of 1 DEG C/min
32℃。
In some embodiments of the invention, in step 2), the solid obtained after recrystallization and filtering is dried, is obtained into
Product methionine.
In some embodiments of the invention, in step 2), it is dried to methionine crystal water content≤0.1wt%.
In some embodiments of the invention, in step 2), drying temperature is 100-110 DEG C, time 2.0-2.5h.
In some embodiments of the invention, in step 2), drying temperature is 105 DEG C.
In some embodiments of the invention, in step 2), by the Recycling Mother Solution obtained after recrystallization and filtering to step
1) the recrystallization link of desalinization of soil by flooding or leaching link or step 2).
In some embodiments of the invention, in step 1), the methionine of the saliferous is secondary methionine, i.e. methionine
The solid residue containing methionine, sodium sulphate and other impurities generated when production, by weight, the content of methionine is
The content of 20%-60%, sodium sulphate are 20%-60%, and the content of moisture is 10%-20%, and the content of formate is 1%-
6%, the content of ammonium sulfate is 0.5%-2%, and the content of polymer is 1% or so, sometimes also contains resin and silt etc..
Second aspect of the present invention provides methionine made from the above method, and the purity of the methionine is higher, usually 99%
More than.
As described above, a kind of isolation and purification method of methionine of the present invention, has the advantages that：Present invention success
A kind of production method saved and recycle methionine product in energy consumption, the methionine easy to operate from saliferous is developed, this method obtains
To the purity of methionine product reach 99.0% or more, the single rate of recovery of methionine is high, is truly realized the utilization of resources most
Bigization.
Description of the drawings
Fig. 1 is shown as the secondary methionine separation purifying technique flow chart of the embodiment of the present invention.
Fig. 2 is shown as the methionine product crystal figure of the embodiment of the present invention 3.
Fig. 3 is shown as the single methionine crystal figure of the embodiment of the present invention 3.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Based on not good enough to the processing method of saliferous methionine (such as secondary methionine) in the prior art, the methionine of gained is pure
Relatively low, not qualified products are spent, low energy consumption, conjunction that is efficient, being capable of isolated high-purity this invention address that exploitation is a kind of
The method of lattice methionine product.
Following embodiment is tested by taking secondary methionine as an example, it should be noted that this method is also applied for other classes
As saliferous methionine isolate and purify.
It is as shown in Figure 1 the process flow chart of following embodiment, in figure, MTN refers to methionine.
Embodiment 1
A kind of isolation and purification method of methionine, includes the following steps：
1) taking 500g secondary methionines, (by weight, methionine content 35%, sodium sulphate content 44%, moisture contains
Amount is 15%, and formic acid radical content is 5%, also contains a small amount of methionine dimer and unknown impuritie), it is added to 500ml's
In water, be heated and maintained at 35-40 DEG C, be then turned on stirring 1 hour, then filtered, respectively obtain methionine crude product and
Filtrate pH is adjusted to 5.5 or so by 650ml filtrates, and filtrate is 40 DEG C by continuous chromatography desalination, chromatographic isolation temperature, go from
Sub- water respectively obtains extracting solution (methionine aqueous solution) 950ml and raffinate (salt-containing solution) 1200ml as mobile phase, wherein
Extracting solution is recycled to step 2) and is used as methionine crude product recrystallization water, and raffinate passes through concentration, and crystallisation by cooling obtains sodium sulphate.
2) the methionine crude solid for obtaining step 1) is added in 1050ml water, and the 950ml obtained with step 1) is carried
Liquid is taken to merge, heating, stirring and dissolving, temperature are controlled at 75 DEG C, and until completely dissolved, 4.5g activated carbons are added, and (i.e. methionine is thick
The 3% of quality) decoloration 30min.After the completion of decoloration, continue that this temperature is kept to be filtered, obtained filtrate enters cooling knot
Brilliant process, when crystallization, rate of temperature fall controls the degree that room temperature (20 DEG C -25 DEG C) are down in 1.5h-2h, to ensure that crystal form is good,
Without package impurity.It after the completion of crystallization, filters again, and by upper layer crystal with room temperature desalted water (raffinate i.e. after step 1) desalination)
It rinses twice, then wet product methionine feeding drying box is dried into 2h at 105 DEG C, obtain methionine product 114.44
Gram, the single rate of recovery of purity 99.4%, methionine product is 65.39%, and the recrystallization filtrate of methionine crude product then returns
To secondary methionine desalinization of soil by flooding or leaching step.
By repeatedly recycling, the rate of recovery of methionine can reach 97% or more.
Embodiment 2
A kind of isolation and purification method of methionine, includes the following steps：
1) taking 500g secondary methionines, (by weight, methionine content 35%, sodium sulphate content 44%, moisture contains
Amount is 15%, and formic acid radical content is 5%, also contains a small amount of methionine dimer and unknown impuritie), it is added to 500ml's
In water, 35-40 DEG C is heated and kept, stirring 1 hour is then turned on, then filtered, respectively obtains methionine crude product and 650ml
Filtrate pH is adjusted to 5.5 or so by filtrate, and filtrate is handled by homogeneous membrane electrodialysis desalination, and desalination temperature is 35 DEG C, respectively
To methionine aqueous solution 610ml and salt-containing solution 650ml, wherein methionine water solution cycle to step 2) is used as methionine thick
Product recrystallization water, and salt-containing solution passes through concentration, crystallisation by cooling obtains sodium sulphate.
2) the methionine crude solid for obtaining step 1) is added in 1350ml water, and the 610ml obtained with step 1) is carried
Liquid is taken to merge, heating, stirring and dissolving, temperature are controlled at 75 DEG C, and until completely dissolved, 4.5g activated carbons are added, and (i.e. methionine is thick
The 3% of quality) decoloration 30min.After the completion of decoloration, continue that this temperature is kept to be filtered, obtained filtrate enters cooling knot
Brilliant process, when crystallization, rate of temperature fall controls the degree that room temperature is down in 1.5h-2h, to ensure that crystal form is good, no package impurity.
It is filtered again after the completion of crystallization, and crystal room temperature desalted water in upper layer is rinsed twice, wet product methionine is then sent into drying
Case dries 2h at 105 DEG C, obtains 115.71 grams of methionine product, and the single of purity 99.4%, methionine product returns
Yield is 66.12%, and the recrystallization filtrate of methionine crude product is then back to secondary methionine desalinization of soil by flooding or leaching step.
By repeatedly recycling, the rate of recovery of methionine can reach 97% or more.
Embodiment 3
A kind of isolation and purification method of methionine, includes the following steps：
1) taking 500g secondary methionines, (by weight, methionine content 35%, sodium sulphate content 44%, moisture contains
Amount is 15%, and formic acid radical content is 5%, also contains a small amount of methionine dimer and unknown impuritie), it is added to 500ml's
In water, 35-40 DEG C is heated and kept, stirring 1 hour is then turned on, then filtered, respectively obtains methionine crude product and 650mL
Filtrate pH is adjusted to 5.5 or so by filtrate, and filtrate is by continuous chromatography desalination, and chromatographic isolation temperature is 40 DEG C, and deionized water is made
For mobile phase, extracting solution (methionine aqueous solution) 950ml and raffinate (salt-containing solution) 1200ml, wherein extracting solution are respectively obtained
It is recycled to step 2) and is used as methionine crude product recrystallization water, and raffinate passes through concentration, crystallisation by cooling obtains sodium sulphate.
2) the methionine crude solid for obtaining step 1) is added in 1050ml water, and the 950ml obtained with step 1) is carried
Liquid is taken to merge, heating, stirring and dissolving, temperature are controlled at 75 DEG C, and 5.0 activated carbons (i.e. methionine crude product quality is added after to be dissolved
4%) decoloration 30min.After the completion of decoloration, to continue that this temperature is kept to be filtered, obtained filtrate enters decrease temperature crystalline process,
Rate of temperature fall is controlled when crystallization, methionine forms certain degree of subcooling under the conditions of 70 DEG C, and methionine crystal seed is then added
(quality of methionine crystal seed is 1% of methionine quality in aqueous solution), keeps the temperature 10-20min, then at 69 DEG C at 70 DEG C
3min is kept the temperature, 58 DEG C is down to from 68 DEG C with the rate of 1 DEG C/min, then cool down from 58 DEG C with the rate of 2 DEG C/min, is finally down to knot
30 DEG C of brilliant temperature, obtained methionine product crystal form is good (as shown in Figures 2 and 3), no package impurity.After the completion of crystallization again
Filtering, and bottom methionine crystal room temperature desalted water is rinsed twice, wet product methionine is then sent into drying box in 105 DEG C
Lower drying 2h, obtains 114.78 grams of methionine product, and the single rate of recovery of purity 99.4%, methionine product is
65.59%, the recrystallization filtrate of methionine crude product is then back to secondary methionine desalinization of soil by flooding or leaching step.
By repeatedly recycling, the rate of recovery of methionine can reach 97% or more.
Methionine product crystalline form made from the present embodiment 2 θ=21.521 ± 0.2 ° of the angle of diffraction, 34.763 ± 0.2 °,
There are diffraction maximum, melting point peak temperature at 44.623 ± 0.2 °, 27.142 ± 0.2 °, 18.573 ± 0.2 °, 43.694 ± 0.2 °
It is 287 DEG C.
In conclusion the methionine isolation and purification method of the present invention saves energy consumption, easy to operate, hence it is evident that simplify operation step
Suddenly, reduce water consumption, the purity for the methionine product that this method obtains reaches 99.0% or more, fundamentally solves methionine
The problem of recycling, is truly realized the maximization of the utilization of resources.
Traditional electrodialysis desalination has to that homogeneous system is made in material liquid under the conditions of 30 DEG C -40 DEG C, it is necessary to by two
Grade methionine adds water to be completely dissolved (within 40 DEG C), and this method needs a large amount of water, and electrodialytic treating capacity will be apparent
It increases, the investment of electrodialytic membranes also will be increased obviously, and then raise production cost, and complicated for operation, and the present invention successfully overcomes
The above problem.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of isolation and purification method of methionine, which is characterized in that include at least following steps：
1) add water to carry out the desalinization of soil by flooding or leaching processing methionine of saliferous, be separated by solid-liquid separation, obtained solid is methionine crude product；
2) add water that aqueous solution is made the methionine crude product that step 1) obtains, recrystallize, be separated by solid-liquid separation, obtained solid be at
Product methionine.
2. isolation and purification method according to claim 1, it is characterised in that：In step 1), when the desalinization of soil by flooding or leaching is handled, solution is controlled
Temperature is at 20-40 DEG C.
3. isolation and purification method according to claim 1, it is characterised in that：In step 1), after separation of solid and liquid, it will detach
The liquid arrived carries out desalting processing, respectively obtains the aqueous solution of aqueous solution and saliferous containing methionine.
4. isolation and purification method according to claim 3, it is characterised in that：In step 1), the aqueous solution of saliferous is passed through
Concentration, crystallization, obtain finished product salt.
5. isolation and purification method according to claim 3, it is characterised in that：In step 1), the method for desalting processing is color
Spectrometry or electroosmose process.
6. isolation and purification method according to claim 3, it is characterised in that：In step 2), by methionine crude product aqueous solution
Merge with the aqueous solution containing methionine that step 1) desalination obtains, then carries out subsequent processing.
7. isolation and purification method according to claim 1, it is characterised in that：In step 2), methionine crude product is added into water system
When at aqueous solution, the mass ratio of methionine crude product and water is 1：(5-8).
8. isolation and purification method according to claim 1, it is characterised in that：In step 2), it is water-soluble to prepare methionine crude product
When liquid, control aqueous temperature is 65-80 DEG C；When recrystallization, it is cooled to 20-32 DEG C.
9. isolation and purification method according to claim 1, it is characterised in that：In step 2), activity is first added into solution
Charcoal carries out decolorization, is separated by filtration activated carbon and then is recrystallized to filtrate.
10. according to methionine made from claim 1-9 any one of them isolation and purification methods.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645357A (en) * | 2020-12-22 | 2021-04-13 | 宁夏紫光天化蛋氨酸有限责任公司 | Post-treatment method of sodium sulfate mother liquor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644514A (en) * | 1968-11-18 | 1972-02-22 | Montedison Spa | Process for separating pure methionine from the hydrolysis product of its nitrile |
| CN102827045A (en) * | 2012-08-31 | 2012-12-19 | 重庆紫光天化蛋氨酸有限责任公司 | Method and apparatus for removing impurity in secondary methionine mother liquor |
| CN104174181A (en) * | 2014-05-14 | 2014-12-03 | 重庆紫光化工股份有限公司 | Separation and purification system of organic synthesis feed liquid and separation and purification method thereof |
| CN106349131A (en) * | 2016-08-26 | 2017-01-25 | 宁夏紫光天化蛋氨酸有限责任公司 | Separation and purification method of methionine |
-
2017
- 2017-05-02 CN CN201710302144.6A patent/CN108794364A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644514A (en) * | 1968-11-18 | 1972-02-22 | Montedison Spa | Process for separating pure methionine from the hydrolysis product of its nitrile |
| CN102827045A (en) * | 2012-08-31 | 2012-12-19 | 重庆紫光天化蛋氨酸有限责任公司 | Method and apparatus for removing impurity in secondary methionine mother liquor |
| CN104174181A (en) * | 2014-05-14 | 2014-12-03 | 重庆紫光化工股份有限公司 | Separation and purification system of organic synthesis feed liquid and separation and purification method thereof |
| CN106349131A (en) * | 2016-08-26 | 2017-01-25 | 宁夏紫光天化蛋氨酸有限责任公司 | Separation and purification method of methionine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645357A (en) * | 2020-12-22 | 2021-04-13 | 宁夏紫光天化蛋氨酸有限责任公司 | Post-treatment method of sodium sulfate mother liquor |
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Application publication date: 20181113 |