CN109384696A - A method of obtaining high-purity high-bulk-density methionine - Google Patents
A method of obtaining high-purity high-bulk-density methionine Download PDFInfo
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Abstract
The invention discloses one kind for D in the presence of methionine salt reagent is as methionine crystallization additive, the method that L-Methionine is crystallized, this method is under the conditions of existing for a certain amount of Sodium L-methioninate or methionine potassium, the method that methionine is recrystallized, the obtained D, the mass percentage of methionine is 4%~28% in L-Methionine aqueous solution and/or suspension, the mass percentage of Sodium L-methioninate or methionine potassium is 0.75%~7.3%, wherein the temperature of the aqueous solution and/or suspension directly or is gradually down to 10 DEG C~30 DEG C by 50 DEG C~110 DEG C, in temperature-fall period, 0.01%~1.0% crystal seed of methionine amount is added under the appropriate temperature conditions, so that D, L-Methionine precipitates as solid.The D obtained by crystallization, the main content of L-Methionine are at least 99.2%, and bulk density at least 0.65g/cm or more, 300~700 microns of partial size, particle diameter distribution is uniform.Method of the invention is equally relatively more suitable for the crystallization of the little substance or product of other similar solubility in water.
Description
Technical field
The invention belongs to chemical production technical fields.Specifically, the present invention relates to one kind for making in methionine salt reagent
Method to obtain high-purity high-bulk-density methionine in the presence of methionine crystallization additive.
Background technique
D, L-Methionine also known as methionine are one of the basic units for constituting protein, are unique in essential amino acid
Amino acid containing sulphur, the synthesis in addition to participating in the transfer of methyl, the metabolism of phosphorus and adrenaline, choline, creatine in animal body
Outside or the raw material of synthetic proteins matter and cystine.Methionine is widely used in the fields such as medicine, food, feed and cosmetics,
The middle dosage as feed addictive is very big.The demand of global methionine has reached 1,600,000 tons/year, Chinese methionine
The demand of methionine in 2014 has been more than 130,000 tons, but the methionine in China also needs in large quantities from external import at present,
Domestic yield is unable to meet demand.
It is used to prepare D, the method for L-Methionine is known, wherein D, and L-Methionine is first with 5-(2- methylmercaptan ethyl
Base)-hydantoins is raw material by sodium hydroxide, potassium carbonate, potassium hydroxide hydrolysis, first acquisition Sodium L-methioninate or methionine
Aqueous solutions of potassium is acidified to obtain D, L-Methionine product using sulfuric acid or carbon dioxide.
Chinese patent CN104926701 A discloses a kind of purifying process of methionine, is separated using macroporous absorbent resin
Then methionine and by-product salts substances, methionine are attracted on macroporous absorbent resin with strippant desorption resin recycling egg ammonia
Acid, by-product salts substances are not absorbed into absorption efflux in adsorption process by macroporous absorbent resin, mainly include following
Step: 1) resin adsorption: methionine solution passes through macroporous absorbent resin layer, when ammonia containing egg in resin column efflux
When acid content is more than or equal to 10% (w/w) of import content, stop resin adsorption；Resin adsorption efflux is as by-product salt
Substance；2) resin desorption: completing the resin of absorption, passed through with strippant in step 1), desorbs resin, and receive
Collect stripping liquid；3) subsequent technique process: stripping liquid is according to prior art process subsequent processing.It, can by Adsorption and desorption technique
The methionine product of purity >=99%, methionine content≤0.03% in by-product salts substances are obtained, resin extracts methionine and receives
Rate >=98%.
Chinese patent CN104177280 A discloses a kind of methionine production technology, step 1: by methionine crystalline mother solution
By the continuous chromatography separation system separation filled with sodium form or potassium type chromatography resin, obtains methionine solution and inorganic salts are molten
Liquid；Step 2: methionine solution is concentrated to give methionine reverse osmosis concentrated liquid using counter-infiltration system, obtained methionine is anti-
Osmosis concentration liquid returns to Crystallization Procedure；The simple process, good separating effect, methionine purity is high, concentrated cost is low.
Chinese patent CN105764886A discloses one kind in the presence of ammonia, the method for methionine crystallization, process flow
Figure is as shown in Figure 1.
It is well known that the solubility of methionine in water is as shown in table 1.
1 methionine solubility of table
But no matter which kind of above-mentioned mode, in obtained methionine aqueous solution the mass percentage of methionine all only less than
7%, this necessarily causes the internal circulating load of methionine mother liquor bigger, and the single extraction efficiency of methionine is relatively low, and single extraction efficiency only has
Less than 70%, therefore, causes a large amount of methionine mother liquor to recycle, in order to enable its methionine to dissolve more Yu Shuizhong, need
It is carried out at higher temperature, the energy consumption for causing methionine to produce is higher；Furthermore in methionine methionine production process, always or
It mostly or is less faced with the recrystallization of methionine, i.e., methionine is dissolved in hot water, forms the methionine aqueous solution of saturation, then
By way of cooling, make to need to be precipitated out using acid in its egg ammonia, to reach the egg for obtaining high-purity, high-bulk-density
Propylhomoserin product.Therefore, in order to increase the solubility of its methionine in water, common operating method is to increase temperature, still,
Methionine is for a long time under conditions of high temperature, it may appear that a small amount of decomposition generates the dimethyl disulfide of stench, it is made to operate workshop
There is a large amount of stink, operating environment is poor.Methionine is due to using pure water to be recrystallized as solvent, the dissolution of methionine itself
Degree limits its concentration in aqueous solution, therefore, methionine setting using a large amount of water and its large volume in recrystallization process
Standby, this necessarily affects production efficiency.Although ammonia is added in methionine crystallization can increase the solubility of methionine (referring to next
From the solubility curve of JP2004-254690), still, in the presence of ammonia, to crystallization, that there are environmental requirements is relatively high, ammonia
Leakage cause crystallize workshop have a large amount of ammonia taste, influence the health of employee, and when dissolving by heating methionine in order to
Guarantee that methionine solubility is big, needs to prevent ammonia volatilization in solution, it is therefore desirable to it is carried out in pressure vessel, it is subsequent and need handle
The modes such as ammonia stripping or reduction vaporization reduce the ammonia in solution, this necessarily causes its complicated for operation, and energy consumption is higher, the loss of ammonia
Lead to the increased costs of methionine.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind in methionine salt reagent
In the presence of methionine crystallization additive, the method that methionine is crystallized is particularly suitable for methionine recrystallization method
Optimization.
In order to achieve the above objectives, the invention provides the following technical scheme:
One kind is for D in the presence of methionine salt reagent is as methionine crystallization additive, the method that L-Methionine is crystallized,
D is added into the aqueous solution of methionine salt, L-Methionine is configured to D, L-Methionine aqueous solution and/or suspension, the egg
Propylhomoserin salt is Sodium L-methioninate or methionine potassium, the obtained D, D in L-Methionine aqueous solution and/or suspension, L-Methionine
Mass percentage be 4%~28%, the mass percentage of Sodium L-methioninate or methionine potassium is 0.75%~7.3%, wherein institute
The temperature of the aqueous solution and/or suspension stated directly or is gradually down to 10 DEG C~30 DEG C by 50 DEG C~110 DEG C, in temperature-fall period
Middle addition D, the crystal seed that L-Methionine mass percentage content is 0.01%~1.0%, so that D, L-Methionine is precipitated as solid
Get off.
Further, the obtained D, D in L-Methionine aqueous solution and/or suspension, the quality percentage of L-Methionine contain
Measuring as the mass percentage of 10%~20%, Sodium L-methioninate or methionine potassium is 0.75%~5.0%, the D, L-Methionine water
The temperature of solution and/or suspension is 70 DEG C~100 DEG C.
Further, the obtained D, D in L-Methionine aqueous solution and/or suspension, the quality percentage of L-Methionine contain
Measuring as the mass percentage of 10%~18%, Sodium L-methioninate or methionine potassium is 0.75%~3.0%, the D, L-Methionine water
The temperature of solution and/or suspension is 70 DEG C~95 DEG C.
Further, D, L-Methionine are used in the form of pure methionine and/or thick methionine, the pure methionine and/
Or the arbitrary process that thick methionine is produced from methionine, and be 0.1%~25% containing biodiversity percentage composition, methionine
Mass percentage is at least 75%.
Further, the crystal seed is one or more kinds of in methionine crystal, cellulose and citric acid, the crystal seed partial size
At 250~650 microns, preferably crystal seed is methionine crystal or cellulose.
Further, the D, L-Methionine crystallization are divided into two stages progress, wherein, will in the first crystallization stage
Sodium L-methioninate or methionine aqueous solutions of potassium are heated to 85 DEG C~100 DEG C, and D is then added, and L-Methionine solid heat molten
Solution maintains 85 DEG C~100 DEG C for the temperature of gained saturated mixture is constant；
In the second crystallization stage, the saturated mixture that the first crystallization stage obtains is cooled to 70 DEG C~95 DEG C and obtains D, L- egg ammonia
Sour saturated solution, is added D in above-mentioned saturated solution, the crystal seed that L-Methionine mass percentage content is 0.01%~1.0%, so
It is cooled to directly or gradually 10 DEG C~30 DEG C afterwards, so that D, L-Methionine precipitates as solid.
Further, the D, L-Methionine saturated solution after the addition of the seeds, 30~60min of insulated and stirred, then with
The cooling rate of 0.5 DEG C~1.5 DEG C/min is cooled to 10 DEG C~30 DEG C.
Further, the D of precipitating, L-Methionine are separated and are dried with mother liquor, and the crystalline mother solution is back to D,
L-Methionine crystallization stage.
On the other hand, the present invention provides a kind of D, L-Methionine is made by method described above, and described passes through knot
The D that crystalline substance obtains, the main content of L-Methionine are at least 99.2%, bulk density at least 0.65g/cm or more, and partial size 300~700 is micro-
Rice.
The beneficial effects of the present invention are: the methionine method for crystallising of high-purity high-bulk-density provided by the invention, no
The low problem of the single extraction efficiency of methionine crystallization is only addressed only, and the solubility for solving methionine is low, methionine knot
The big problem of brilliant Recycling Mother Solution amount；The method of the present invention is easy to operate, methionine crystalline mother solution can with recycled, have cleaning,
The features such as energy saving, the methionine product obtained by this method have many advantages, such as purity is high, large bulk density, uniform particle diameter.This
The method of invention is equally relatively more suitable for the crystallization of the little substance or product of other similar solubility in water.
Detailed description of the invention
Fig. 1 is the process flow chart of methionine method for crystallising disclosed in Chinese patent CN105764886A.
Fig. 2 is D of the present invention, L-Methionine crystallization processes flow chart.
Specific embodiment
The present invention is further explained in the light of specific embodiments, so that those skilled in the art can be better
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Test method without specific conditions in embodiment, usually according to normal condition or according to proposed by manufacturer
Condition.
Embodiment 1
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to 2000 grams and contain quality percentage
Content is to be heated to 90 DEG C to being completely dissolved, the methionine water formed by analysis in the crystallization bottle of 2% Sodium L-methioninate aqueous solution
Methionine mass percentage is 17.8% in solution, altogether the D of addition 95%, 248.1 grams of L-Methionine.Then 75 DEG C are cooled to,
Methionine crystal of 0.1% partial size of methionine quality at 250~650 microns is added, in 73 DEG C of insulated and stirred 60min, then
With the cooling rate of 0.5 DEG C/min, 10 DEG C are cooled to, a large amount of methionine crystal is precipitated, stops stirring, methionine crystal is basic
On be all deposited in crystallization bottle bottom.It filters, drying, obtains D, 189.5 grams of L-Methionine product, purity 99.5% is accumulated close
0.75g/cm is spent, 350~700 microns of partial size, it is 80% that the single of methionine, which takes brilliant rate,.Obtain methionine crystalline mother solution 2058.6
Gram, the content for analyzing wherein methionine is 4.3%, is recycled to next D, L-Methionine re-crystallization step.
Embodiment 2
The D for being 95% by mass percentage, 199.5 grams of L-Methionine (wherein containing 4% moisture) and 1 gained methionine of embodiment
2058.6 grams of crystalline mother solution are added in 3000 milliliters of crystallization bottle, are heated to 95 DEG C to being completely dissolved, the egg formed by analysis
Methionine mass percentage is 17.8% in propylhomoserin aqueous solution.Then 75 DEG C are cooled to, 0.1% grain of methionine quality is added
Methionine crystal of the diameter at 250~650 microns, in 74 DEG C of insulated and stirred 60min, then with the cooling rate of 0.5 DEG C/min, drop
A large amount of methionine crystal is precipitated to 30 DEG C in temperature, stops stirring, and methionine crystal is substantially all the bottom for being deposited in crystallization bottle.
It filtering, drying obtains D, and 190 grams of L-Methionine product, purity 99.6%, 0.75 g/cm of bulk density, partial size 350~700
Micron, it is 81% that the single of methionine, which takes brilliant rate,.2058.1 grams of mother liquor are obtained, the content for analyzing wherein methionine is 4.2%, circulation
To next D, L-Methionine re-crystallization step.
Embodiment 3
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to 2000 grams and contain quality percentage
Content is to be heated to 86 DEG C to being completely dissolved, the methionine formed by analysis in the crystallization bottle of 2.2% methionine aqueous solutions of potassium
Methionine mass percentage is 17.8% in aqueous solution, altogether the D of addition 95%, 248.1 grams of L-Methionine.Then 75 are cooled to
DEG C, methionine crystal of 0.01% partial size at 250~650 microns of methionine quality is added, in 75 DEG C of insulated and stirred 60min,
Then with the cooling rate of 1.5 DEG C/min, 10 DEG C are cooled to, a large amount of methionine crystal is precipitated, stops stirring, methionine crystal
It is substantially all the bottom for being deposited in crystallization bottle.It filtering, drying obtains D, and 189.5 grams of L-Methionine product, purity 99.2%, heap
Product 0.65 g/cm of density, 350~700 microns of partial size, it is 80% that the single of methionine, which takes brilliant rate,.Obtain methionine crystalline mother solution
2059.6 grams, the content for analyzing wherein methionine is 4.1%, is recycled to next D, L-Methionine re-crystallization step.
Embodiment 4
The D for being 95% by mass percentage, 199.5 grams of L-Methionine (wherein containing 4% moisture) and 1 gained methionine of embodiment
2058.6 grams of crystalline mother solution are added in 3000 milliliters of crystallization bottle, are heated to 86 DEG C to being completely dissolved, the egg formed by analysis
Methionine mass percentage is 17.8% in propylhomoserin aqueous solution.Then 70 DEG C are cooled to, 0.1% grain of methionine quality is added
Methionine crystal of the diameter at 250~650 microns, in 70 DEG C of insulated and stirred 30min, then with the cooling rate of 0.5 DEG C/min, drop
A large amount of methionine crystal is precipitated to 10 DEG C in temperature, stops stirring, and methionine crystal is substantially all the bottom for being deposited in crystallization bottle.
It filtering, drying obtains D, and 190 grams of L-Methionine product, purity 99.6%, 0.74 g/cm of bulk density, partial size 350~700
Micron, it is 81% that the single of methionine, which takes brilliant rate,.2058.1 grams of mother liquor are obtained, the content for analyzing wherein methionine is 4.2%, circulation
To next D, L-Methionine re-crystallization step.
Embodiment 5
The D for being 90% by mass percentage, L-Methionine (wherein contain 9.5% moisture) are added to 2000 grams and contain quality hundred
Divide in the crystallization bottle that content is 3% Sodium L-methioninate aqueous solution, is heated to 90 DEG C to being completely dissolved, the methionine formed by analysis
Methionine mass percentage is 17.7% in aqueous solution, altogether the D of addition 90%, 444.8 grams of L-Methionine.Then 74 are cooled to
DEG C, cellulose crystal seed of 1.0% partial size at 250~650 microns of methionine quality is added, in 73 DEG C of insulated and stirred 40min,
Then with the cooling rate of 1.0 DEG C/min, 10 DEG C are cooled to, a large amount of methionine crystal is precipitated, stops stirring, methionine crystal
It is substantially all the bottom for being deposited in crystallization bottle.It filtering, drying obtains D, and 321.2 grams of L-Methionine product, purity 99.7%, heap
Product density is 0.72 g/cm, and it is 80% that the single of methionine, which takes brilliant rate,.2122.8 grams of methionine crystalline mother solution are obtained, analysis is wherein
The content of methionine is 3.5%, is recycled to next D, L-Methionine re-crystallization step.
Embodiment 6
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to 2000 grams and contain quality percentage
Content is to be heated to 110 DEG C to being completely dissolved, the methionine formed by analysis in the crystallization bottle of 2.2% methionine aqueous solutions of potassium
Methionine mass percentage is 17.8% in aqueous solution, altogether the D of addition 95%, 248.1 grams of L-Methionine.Then 90 are cooled to
DEG C, cellulose crystal seed of 0.02% partial size at 250~650 microns of methionine quality is added, in 70 DEG C of insulated and stirred 60min,
Then with the cooling rate of 0.5 DEG C/min, 10 DEG C are cooled to, a large amount of methionine crystal is precipitated, stops stirring, methionine crystal
It is substantially all the bottom for being deposited in crystallization bottle.It filtering, drying obtains D, and 189.5 grams of L-Methionine product, purity 99.5%, heap
Product density is 0.76 g/cm, and it is 80% that the single of methionine, which takes brilliant rate,.2059.6 grams of methionine crystalline mother solution are obtained, analysis is wherein
The content of methionine is 4.1%, is recycled to next D, L-Methionine re-crystallization step.
Embodiment 7
The D for being 75% by mass percentage, L-Methionine (wherein contain 25% moisture) are added to 2000 grams and contain quality hundred
Divide in the crystallization bottle that content is 7.3% methionine aqueous solutions of potassium, is heated to 100 DEG C to being completely dissolved, the egg ammonia formed by analysis
Methionine mass percentage is 16.7% in aqueous acid, altogether the D of addition 75%, 368.1 grams of L-Methionine.Then it is cooled to
95 DEG C, cellulose crystal seed of 0.02% partial size of methionine quality at 250~650 microns is added, in 80 DEG C of insulated and stirreds
45min is cooled to 10 DEG C then with the cooling rate of 0.5 DEG C/min, and a large amount of methionine crystal is precipitated, and stops stirring, egg ammonia
Acid crystal is substantially all the bottom for being deposited in crystallization bottle.It filters, drying obtains D, and 221.97 grams of L-Methionine product, purity is
99.5%, bulk density is 0.76 g/cm, and it is 80% that the single of methionine, which takes brilliant rate,.2143 grams of methionine crystalline mother solution are obtained, point
The content for analysing wherein methionine is 4.1%, is recycled to next D, L-Methionine re-crystallization step.
Comparative example 1
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to equipped with 2000 grams of deionized waters
It crystallizes in bottle, is heated to 95 DEG C to being completely dissolved, methionine mass percentage in the methionine aqueous solution formed by analysis
Be 6.9%, altogether be added 95% D, 156.6 grams of L-Methionine.Then 10 DEG C are directly cooled to, a large amount of methionine crystal is precipitated,
Stop stirring.It filtering, drying obtains D, and 101.7 grams of L-Methionine product, purity 99.5%, 0.35 g/cm of bulk density, egg
It is 68% that the single of propylhomoserin, which takes brilliant rate,.2069.8 grams of methionine crystalline mother solution are obtained, the content for analyzing wherein methionine is 2.3%,
It is recycled to next D, L-Methionine re-crystallization step.
Comparative example 2
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to equipped with 2000 grams of deionized waters
It crystallizes in bottle, is heated to 95 DEG C to being completely dissolved, methionine mass percentage in the methionine aqueous solution formed by analysis
Be 6.9%, altogether be added 95% D, 156.6 grams of L-Methionine.Then 90 DEG C are cooled to, 0.02% grain of methionine quality is added
Cellulose crystal seed of the diameter at 250~650 microns, in 70 DEG C of insulated and stirred 60min, then with the cooling rate of 0.5 DEG C/min, drop
A large amount of methionine crystal is precipitated to 10 DEG C in temperature, stops stirring, and methionine crystal is substantially all the bottom for being deposited in crystallization bottle.
It filtering, drying obtains D, and 101.7 grams of L-Methionine product, purity 99.5%, 0.58 g/cm of bulk density, the list of methionine
It is secondary take brilliant rate be 68%.2069.8 grams of methionine crystalline mother solution are obtained, the content for analyzing wherein methionine is 2.3%, is recycled to down
Secondary D, L-Methionine re-crystallization step.
Comparative example 3
The D for being 95% by mass percentage, L-Methionine (wherein contain 4% moisture) are added to equipped with 2000 grams of deionized waters
It crystallizes in bottle, is heated to 95 DEG C to being completely dissolved, methionine mass percentage in the methionine aqueous solution formed by analysis
Be 6.9%, altogether be added 95% D, 156.6 grams of L-Methionine.Then 75 DEG C are cooled to, turbid phenomenon, egg ammonia occurs in aqueous solution
Acid has been precipitated, and cellulose crystal seed of 0.02% partial size of methionine quality at 250~650 microns is added, stirs in 75 DEG C of heat preservations
60min is mixed, then with the cooling rate of 0.5 DEG C/min, is cooled to 10 DEG C, a large amount of methionine crystal is precipitated, stops stirring, egg
Propylhomoserin crystal has in liquid surface and bottom.It filtering, drying obtains D, and 101.7 grams of L-Methionine product, purity 99.5%,
0.55 g/cm of bulk density, it is 68% that the single of methionine, which takes brilliant rate,.2069.8 grams of methionine crystalline mother solution are obtained, analysis is wherein
The content of methionine is 2.3%, is recycled to next D, L-Methionine re-crystallization step.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. one kind is for D, the side that L-Methionine is crystallized in the presence of methionine salt reagent is as methionine crystallization additive
Method, which is characterized in that be added D into the aqueous solution of methionine salt, L-Methionine is configured to D, L-Methionine aqueous solution and/or
Suspension, the methionine salt are Sodium L-methioninate or methionine potassium, the obtained D, L-Methionine aqueous solution and/or suspension
D in liquid, the mass percentage of L-Methionine is 4%~28%, the mass percentage of Sodium L-methioninate or methionine potassium is 0.75%
~7.3%, wherein the temperature of the aqueous solution and/or suspension directly or is gradually down to 10 DEG C~30 by 50 DEG C~110 DEG C
DEG C, D, the crystal seed that L-Methionine mass percentage content is 0.01%~1.0%, so that D, L- egg ammonia are added in temperature-fall period
Acid precipitates as solid.
2. the method according to claim 1, wherein the obtained D, L-Methionine aqueous solution and/or suspension
D in liquid, the mass percentage of L-Methionine is 10%~20%, the mass percentage of Sodium L-methioninate or methionine potassium is
The temperature of 0.75%~5.0%, the D, L-Methionine aqueous solution and/or suspension is 70 DEG C~100 DEG C.
3. the method according to claim 1, wherein the obtained D, L-Methionine aqueous solution and/or suspension
D in liquid, the mass percentage of L-Methionine is 10%~18%, the mass percentage of Sodium L-methioninate or methionine potassium is
The temperature of 0.75%~3.0%, the D, L-Methionine aqueous solution and/or suspension is 70 DEG C~95 DEG C.
4. the method according to claim 1, wherein D, L-Methionine is with pure methionine and/or thick methionine
Form uses, the arbitrary process that the pure methionine and/or thick methionine are produced from methionine, and contains biodiversity hundred
Dividing content is 0.1%~25%, and the mass percentage of methionine is at least 75%.
5. the method according to claim 1, wherein the crystal seed is methionine crystal, cellulose and citric acid
Middle one or more, the crystal seed partial size is at 250~650 microns.
6. according to the method described in claim 5, it is characterized in that, the crystal seed is methionine crystal or cellulose.
7. method described according to claim 1~one of 6, which is characterized in that the D, L-Methionine crystallization are divided into two
Stage carries out, wherein in the first crystallization stage, Sodium L-methioninate or methionine aqueous solutions of potassium are heated to 85 DEG C~100 DEG C,
Then D is added, L-Methionine solid is dissolved by heating, and maintains 85 DEG C~100 for the temperature of gained saturated mixture is constant
℃；
In the second crystallization stage, the saturated mixture that the first crystallization stage obtains is cooled to 70 DEG C~95 DEG C and obtains D, L- egg ammonia
Sour saturated solution, is added D in above-mentioned saturated solution, the crystal seed that L-Methionine mass percentage content is 0.01%~1.0%, so
It is cooled to directly or gradually 10 DEG C~30 DEG C afterwards, so that D, L-Methionine precipitates as solid.
8. the method according to the description of claim 7 is characterized in that the D, crystal seed is being added in L-Methionine saturated solution
Afterwards, then 30~60min of insulated and stirred is cooled to 10 DEG C~30 DEG C with the cooling rate of 0.5 DEG C~1.5 DEG C/min.
9. the method according to the description of claim 7 is characterized in that the D of precipitating, L-Methionine are separated and are done with mother liquor
It is dry, the crystalline mother solution is back to D, L-Methionine crystallization stage.
10. a kind of D, L-Methionine are made by claim 7 the method, which is characterized in that described to be obtained by crystallization
D, the main content of L-Methionine are at least 99.2%, bulk density at least 0.65g/cm or more, and 300~700 microns of partial size.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920675A (en) * | 2022-04-20 | 2022-08-19 | 天津大学 | Methionine crystal and preparation method and application thereof |
| CN115043763A (en) * | 2022-06-14 | 2022-09-13 | 天津大学 | Gas-liquid continuous crystallization method of DL-methionine |
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| JPH05320124A (en) * | 1992-05-22 | 1993-12-03 | Sumitomo Chem Co Ltd | Production of methionine |
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| CN105764886A (en) * | 2013-09-17 | 2016-07-13 | 赢创德固赛有限公司 | Process for obtaining methionine |
| CN104744326A (en) * | 2015-02-12 | 2015-07-01 | 山东新和成氨基酸有限公司 | Method for continuously preparing high-bulk density methionine crystals |
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| CN114920675A (en) * | 2022-04-20 | 2022-08-19 | 天津大学 | Methionine crystal and preparation method and application thereof |
| CN114920675B (en) * | 2022-04-20 | 2024-02-06 | 天津大学 | Methionine crystal and preparation method and application thereof |
| CN115043763A (en) * | 2022-06-14 | 2022-09-13 | 天津大学 | Gas-liquid continuous crystallization method of DL-methionine |
| CN115043763B (en) * | 2022-06-14 | 2024-04-05 | 天津大学 | Gas-liquid continuous crystallization method of DL-methionine |
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