CN106008297A - Novel methionine crystal form II and preparation method thereof - Google Patents
Novel methionine crystal form II and preparation method thereof Download PDFInfo
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- CN106008297A CN106008297A CN201610387326.3A CN201610387326A CN106008297A CN 106008297 A CN106008297 A CN 106008297A CN 201610387326 A CN201610387326 A CN 201610387326A CN 106008297 A CN106008297 A CN 106008297A
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- methionine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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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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Abstract
A methionine crystal form II has diffraction peaks at the diffraction angle 2 theta at 22.304 +/- 0.2 DEG, 33.757 +/- 0.2 DEG, 45.674 +/- 0.2 DEG, 28.104 +/- 0.2 DEG, 18.615 +/- 0.2 DEG, and 42.739 +/- 0.2 DEG. The methionine crystal form II is white crystal particles, has good reflection, large and uniform particles in flat blocks with length and width ratio of about 2:1, particles length in the range of 450-550 micron; and a single particle appearance is a compact crystal, and has excellent quality. At the same time, the inventors find that liquidity and bulk density of the crystal form II are related to the key peaks and relative peak intensity of X-ray powder diffraction patterns. The methionine crystal form II has high bulk density of up to 1-2g / cm<3>, and good processability; an injection method (fixed funnel method) is employed for the determination of the angle of repose of particles, and theta is no higher than 40 DEG. The novel methionine crystal form II is conducive to the subsequent large-scale industrial production and application.
Description
Technical field
The present invention relates to a kind of methionine novel crystal forms and preparation method thereof.
Background technology
Methionine (DL-Methionine) chemical formula is C5H11O2NS, white flakes crystallization or crystalline powder, there is spy
Different abnormal smells from the patient, taste is micro-sweet.For nutritional supplement, add in Herba bromi japonici, rye (Secale cereale L.), rice, Semen Maydis, Semen Tritici aestivi, peanut powder, Semen sojae atricolor, Rhizoma Solani tuber osi, Herba Spinaciae
Deng in food to improve amino acid balance, requirement is different with cystine intake, adult man's requirement be 1.1g/d.
Being also used for amino acid transfusion, comprehensive amino acid preparation, can be used as spice by China GB2760-86 regulation, it is still
A kind of requisite animal feed additive, the animal feed added with methionine can help animal the most rapid-result at short notice
Long so that it is to save the feedstuff of about 40%.Poultry lack methionine, can cause dysplasia, lose weight, Liver and kidney miopragia,
Amyotrophy, fur is rotten.
Chinese patent CN104926701 A discloses the purifying process of a kind of methionine, uses macroporous adsorbent resin to separate
Methionine and by-product salts substances, methionine is attracted on macroporous adsorbent resin then reclaim egg ammonia with strippant desorbing resin
Acid, by-product salts substances is not entered in absorption effluent by absorption with macroporous adsorbent resin in adsorption process, mainly includes following
Step: 1) resin absorption: methionine solution passes through macroporous adsorbent resin layer, when the ammonia on egg in resin column effluent
When acid content is more than or equal to 10% (w/w) of import content, stop resin absorption；Resin absorption effluent is as by-product salt
Class material；2) resin desorption: step 1) in complete the resin of absorption, pass through with strippant, desorbing tree
Fat, and collect stripping liquid；3) subsequent technique process: stripping liquid is according to existing technological process subsequent treatment.Through absorption, solve
Inhaling technique, the methionine product of available purity >=99%, methionine content≤0.03% in by-product salts substances, resin carries
Take methionine yield >=98%.
Chinese patent CN104177280 A discloses a kind of methionine production technology, step 1: by methionine crystalline mother solution
Separated by the continuous chromatography piece-rate system being filled with sodium form or potassium type chromatography resin, obtain methionine solution and inorganic salt is molten
Liquid；Step 2: methionine solution uses counter-infiltration system be concentrated to give methionine reverse osmosis concentrated liquid, by anti-for the methionine obtained
Osmosis concentration liquid returns Crystallization Procedure；This technique is simple, good separating effect, the advantages such as methionine purity is high, concentrated cost is low.
China granted patent CN101480385 B discloses the purposes of a kind of methionine, and methionine is in preparation treatment or pre-
Purposes in the compositions of anti-vestibulum auris internae hair cell disease, contains in its pharmaceutical composition: (a) 50-200 weight portion egg ammonia
Acid and/or its polypeptide；The pharmaceutically acceptable carrier of (b) 400-2000 weight portion；And the weight of (a)+(b) is drug regimen
The 50-99% of thing gross weight, described pharmaceutical composition is solid preparation or liquid preparation, and described liquid preparation includes breast
Turbid dose, solution, suspending agent, syrup, drop etc..But the granules of methionine product produced at present, also exists processing fluidity
Can be poor, bulk density is little, increase packed and transported cost.
Summary of the invention
It is an object of the invention to provide the methionine crystal formation II that a kind of processing fluidity is good.
Another object of the present invention is to provide the preparation method of above-mentioned methionine crystal formation II.
The object of the invention is achieved through the following technical solutions:
A kind of methionine crystal formation II, it is characterised in that: described crystal formation is in angle of diffraction 2θ22.304 ± 0.2 °, 33.757 ±
0.2 °, 45.674 ± 0.2 °, 28.104 ± 0.2 °, 18.615 ± 0.2 °, have diffraction maximum at 42.739 ± 0.2 °.
Specifically, methionine crystal formation II of the present invention is in angle of diffraction 2θ11.145 ± 0.2 °, 16.716 ± 0.2 °,
18.615±0.2°、22.304±0.2°、25.203±0.2°、28.104±0.2°、33.757±0.2°、42.739±
0.2 °, 45.674 ± 0.2 °, have diffraction maximum at 51.812 ± 0.2 °.
Say further, above-mentioned methionine crystal formation II, it is characterised in that: it has following d() value and relative intensity percentage
Than I(%) value expression-X-ray powder diffraction data,
D value I value
4.7627 1.6
3.9807 100
3.1724 2.2
2.6530 21.3
2.1139 1.2
1.9847 3.8。
Furthermore, above-mentioned methionine crystal formation II, it is characterised in that: it has following d() value and relative intensity hundred
Proportion by subtraction I(%) value expression-X-ray powder diffraction data,
D value I value
7.9321 0.8
5.2993 1.1
4.7627 1.6
3.9807 100
3.5307 1.0
3.1724 2.2
2.6530 21.3
2.1139 1.2
1.9847 3.8
1.7631 0.9 。
More specifically, above-mentioned methionine crystal formation II, it is characterised in that: the X-ray powder that it has as shown in Figure 1 spreads out
Penetrate figure.
The melting point peak temperature of above-mentioned methionine crystal formation II is 287 DEG C, and this crystal formation has DSC/TG collection of illustrative plates as shown in Figure 2.
Methionine crystal formation II of the present invention is identical with methionine chemical constitution, and quality better, processing flowability are excellent.
The preparation method of methionine crystal formation II of the present invention, employing following steps:
1, at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing in methionine sodium hydrolyzed solution
Adding concentration expressed in percentage by volume is the hydrochloric acid of 15%-37%, obtains the methionine neutralizer that pH value is 5.0-6.0；
2, add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.3-1.0mg/ of isopropanol
ML, is stirred continuously, mixing time 0.5-1.5 hour at 55 DEG C ~ 65 DEG C；This solution is put into-1 DEG C of-5 DEG C of environment is carried out pre-
Cold 1-2 hour；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C, crystallization temperature 0 DEG C
To-5 DEG C, stir speed (S.S.) 30-60r/min, vacuum 19-30kPa, crystallization time 3-6 hour.
The present invention has a following beneficial effect:
Methionine crystal formation II of the present invention is that white crystals granule, reflective are good, and its granule is big, more uniform, in length and width ratio about 2:
The flat bulk of 1, particle length concentrates in 450-550 micrometer range, and individual particle outward appearance is complete fine and close crystal, quality
Excellent.Inventor finds simultaneously, its mobility, bulk density and the crucial peak position of its X-ray powder diffraction spectrum, relative peak
Strong the most relevant, methionine crystal formation II bulk density of the present invention is big, reach 1-2g/cm3, processing fluidity is good, uses injection method (fixing
Funnel method) measure the angle of repose of crystalline particle, θ≤40 degree, follow-up large-scale industrial production application.
Accompanying drawing explanation
Fig. 1 is crystal type methionine X-ray powder diffraction figure of the present invention；
Fig. 2 is differential scanning calorimeter (DSC)/thermogravimetric analysis (TG) figure of crystal type methionine of the present invention；
Fig. 3 is the crystal type methionine of the present invention scanning electron microscope (SEM) photograph under 100 times.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be that following example are only used
In being further described the present invention, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
The present invention made some nonessential improvement and adjustment according to the invention described above content.
Embodiment 1
The preparation method of methionine crystal formation II, is carried out as follows:
(1), at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing methionine sodium hydrolyzed solution
Middle addition concentration expressed in percentage by volume is the hydrochloric acid of 20%-25%, obtains the methionine neutralizer that pH value is 5.5；
(2), add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.5-of isopropanol
0.6mg/mL, is stirred continuously, mixing time 1 hour at 60 DEG C；This solution is put in 0 DEG C of-1 DEG C of environment and carry out pre-cooling 1.5
Hour；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C, and crystallization temperature-2 DEG C is stirred
Mix speed 40-45r/min, vacuum 22-25kPa, crystallization time 4.5 hours.
Embodiment 2
By the methionine crystal obtained by embodiment 1, it is XRD and tests:
Radiation source is Cu target, and wavelength is 1.54060 nm, and scanning angle is 10 ° ~ 70 °, and voltage is 30 kV, and electric current is 20 mA,
Scanning speed is 2.4 °/min.Its X-ray powder diffraction figure is as shown in Figure 1.
Described crystal type methionine is in angle of diffraction 2θ11.145 ± 0.2 °, 16.716 ± 0.2 °, 18.615 ±
0.2°、22.304±0.2°、25.203±0.2°、28.104±0.2°、33.757±0.2°、42.739±0.2°、45.674
± 0.2 °, have diffraction maximum at 51.812 ± 0.2 °.
The crystal type methionine of the present invention, its powder X-ray diffraction pattern is with interplanar distance D, Bragg angle (2θ), relative intensity
Percentage ratio I(%) and the expression of intensity (I value) crystal formation, as follows:
| Diffraction maximum is numbered | Peak position (2 θ values/°) | Intensity (I value) | Relative intensity (%) | Interplanar distance (D value/angstrom) |
| 1 | 22.304 | 57848 | 100 | 3.9807 |
| 2 | 33.757 | 12167 | 21.3 | 2.6530 |
| 3 | 45.674 | 2336 | 3.8 | 1.9847 |
| 4 | 28.104 | 1357 | 2.2 | 3.1724 |
| 5 | 18.615 | 1058 | 1.6 | 4.7627 |
| 6 | 42.739 | 764 | 1.2 | 2.1139 |
| 7 | 16.716 | 604 | 1.1 | 5.2993 |
| 8 | 25.203 | 580 | 1.0 | 3.5307 |
| 9 | 51.812 | 520 | 0.9 | 1.7631 |
| 10 | 11.145 | 500 | 0.8 | 7.9321 |
The differential scanning calorimeter (DSC) of crystal type methionine of the present invention is as in figure 2 it is shown, its endothermic transition temperature is at 287 C；
Its thermogravimetric analysis figure (TG) is as in figure 2 it is shown, proceed by first reaction in about 246 DEG C, and 287 DEG C carry out second reaction,
Terminate to reaction when 381 DEG C.
Methionine crystal type granule scanning electron microscope (SEM) photograph under 100 times as it is shown on figure 3, its granule is big, more uniform, in length,
The wide flat bulk than about 2:1, particle length concentrates in 450-550 micrometer range, and individual particle outward appearance is complete fine and close
Crystal.
After measured, above-mentioned methionine crystal formation II bulk density is 2g/cm3；Methionine crystal obtained above is carried out not
Only angle measures: this test uses injection method (fixed funnel method) to measure the angle of repose of the methionine crystal of above-mentioned preparation.By to be measured
Funnel poured into by sample so that it is fall into disc centre lightly, equably, forms a cone, when material is from powder body hypotenuse edge
Stop charging when disk border freely falls, measure angle of repose with protractor, be repeated three times and be respectively as follows: angle of repose
36.4,34.7,33.5 degree, this crystal grain mobility is excellent.
Embodiment 3
The preparation method of methionine crystal formation II, employing following steps:
(1), at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing methionine sodium hydrolyzed solution
Middle addition concentration expressed in percentage by volume is the hydrochloric acid of 15%-18%, obtains the methionine neutralizer that pH value is 6.0；
(2), add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.9-of isopropanol
1.0mg/mL, is stirred continuously, mixing time 0.5 hour at 65 DEG C；This solution is put in-1 DEG C of environment to carry out pre-cooling 1 little
Time；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C, crystallization temperature-5 DEG C, stirring
Speed 30-35r/min, vacuum 19-21kPa, crystallization time 6 hours.
Identifying by the method for embodiment 2, for methionine crystal formation II of the present invention, bulk density is 1.5g/cm3, angle of repose, θ was
37.1 degree.
Embodiment 4
The preparation method of methionine crystal formation II, employing following steps:
(1), at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing methionine sodium hydrolyzed solution
Middle addition concentration expressed in percentage by volume is the hydrochloric acid of 35%-37%, obtains the methionine neutralizer that pH value is 5.0；
(2), add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.3-of isopropanol
0.4mg/mL, is stirred continuously, mixing time 1.5 hours at 55 DEG C；This solution is put in 4 DEG C of-5 DEG C of environment and carry out pre-cooling 2
Hour；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C, crystallization temperature 0 DEG C, stirring
Speed 55-60r/min, vacuum 28-30kPa, crystallization time 3 hours.
Identifying by the method for embodiment 2, for methionine crystal formation II of the present invention, bulk density is 1.0g/cm3, angle of repose, θ was
35.9 degree.
Embodiment 5
The preparation method of methionine crystal formation II, employing following steps:
(1), at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing methionine sodium hydrolyzed solution
Middle addition concentration expressed in percentage by volume is the hydrochloric acid of 28%-32%, obtains the methionine neutralizer that pH value is 5..5；
(2), add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.7-of isopropanol
0.8mg/mL, is stirred continuously, mixing time 0.8 hour at 62 DEG C；This solution is put in 2 DEG C of-3 DEG C of environment and carry out pre-cooling 1-
2 hours；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C, and crystallization temperature-1 DEG C is stirred
Mix speed 50r/min, vacuum 20-22kPa, crystallization time 5 hours.
Identifying by the method for embodiment 2, for methionine crystal formation II of the present invention, bulk density is 1.3g/cm3, angle of repose, θ was
34.3 degree.
Claims (7)
1. a methionine crystal formation II, it is characterised in that: described crystal formation II is in angle of diffraction 2θ22.304 ± 0.2 °, 33.757
± 0.2 °, 45.674 ± 0.2 °, 28.104 ± 0.2 °, 18.615 ± 0.2 °, have diffraction maximum at 42.739 ± 0.2 °.
2. methionine crystal formation II as claimed in claim 1, it is characterised in that: described crystal formation is in angle of diffraction 2θ11.145 ±
0.2°、16.716±0.2°、18.615±0.2°、22.304±0.2°、25.203±0.2°、28.104±0.2°、33.757
± 0.2 °, 42.739 ± 0.2 °, 45.674 ± 0.2 °, have diffraction maximum at 51.812 ± 0.2 °.
3. methionine crystal formation II as claimed in claim 1 or 2, it is characterised in that: the X-ray powder that it has as shown in Figure 1 spreads out
Penetrate figure.
4. methionine crystal formation II as claimed in claim 1, it is characterised in that: it has following d() value and relative intensity percentage
Than I(%) value expression-X-ray powder diffraction data,
D value I value
4.7627 1.6
3.9807 100
3.1724 2.2
2.6530 21.3
2.1139 1.2
1.9847 3.8。
5. the methionine crystal formation II as described in claim 1,2,3 or 4, it is characterised in that: it has following d() value is with relative
Intensity percent I(%) value expression-X-ray powder diffraction data:
D value I value
7.9321 0.8
5.2993 1.1
4.7627 1.6
3.9807 100
3.5307 1.0
3.1724 2.2
2.6530 21.3
2.1139 1.2
1.9847 3.8
1.7631 0.9 。
6. methionine crystal formation II as claimed in claim 1 or 2, it is characterised in that: it has DSC/TG collection of illustrative plates as shown in Figure 2,
Its melting point peak temperature is 287 DEG C.
7. the preparation method of methionine crystal formation II as described in any one of claim 1-6, it is characterised in that employing following steps:
(1), at 5-(β-first mercaptoethyl) hydantoin react with sodium hydroxide solution obtain containing methionine sodium hydrolyzed solution
Middle addition concentration expressed in percentage by volume is about the hydrochloric acid of 15%-37%, obtains the methionine neutralizer that pH value is 5.0-6.0；
(2), add in isopropanol solvent by above-mentioned methionine neutralizer, methionine neutralizer is in concentration 0.3-of isopropanol
1.0mg/mL, is stirred continuously, about mixing time 0.5-1.5 hour at 55 DEG C ~ 65 DEG C；This solution is put into-1 DEG C of-5 DEG C of ring
Border carries out pre-cooling 1-2 hour；Carrying out vacuum crystallization again, the cooling medium of crystallization is ethylene glycol, coolant temperature-10 DEG C,
Crystallization temperature 0 DEG C to-5 DEG C, stir speed (S.S.) 30-60r/min, vacuum 19-30kPa, crystallization time 3-6 hour.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610387326.3A CN106008297B (en) | 2016-06-03 | 2016-06-03 | A kind of methionine novel crystal forms II and preparation method thereof |
| PCT/CN2017/084385 WO2017206704A1 (en) | 2016-06-03 | 2017-05-15 | Methionine new crystal form ii and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610387326.3A CN106008297B (en) | 2016-06-03 | 2016-06-03 | A kind of methionine novel crystal forms II and preparation method thereof |
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| CN106008297A true CN106008297A (en) | 2016-10-12 |
| CN106008297B CN106008297B (en) | 2018-11-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206704A1 (en) * | 2016-06-03 | 2017-12-07 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine new crystal form ii and preparation method therefor |
| CN108157908A (en) * | 2018-02-09 | 2018-06-15 | 武晓丹 | It is a kind of to utilize the method for vacuumizing and preparing high heap density I+G mixed crystal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4324890B1 (en) * | 1966-08-25 | 1968-10-28 | ||
| CN1274717A (en) * | 1999-05-21 | 2000-11-29 | 住友化学工业株式会社 | Prepn. of methionine |
| CN104203912A (en) * | 2012-03-20 | 2014-12-10 | 赢创工业集团股份有限公司 | Preparation method of 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009292796A (en) * | 2008-06-09 | 2009-12-17 | Sumitomo Chemical Co Ltd | Method for producing methionine |
| CN106008297B (en) * | 2016-06-03 | 2018-11-30 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of methionine novel crystal forms II and preparation method thereof |
-
2016
- 2016-06-03 CN CN201610387326.3A patent/CN106008297B/en active Active
-
2017
- 2017-05-15 WO PCT/CN2017/084385 patent/WO2017206704A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4324890B1 (en) * | 1966-08-25 | 1968-10-28 | ||
| CN1274717A (en) * | 1999-05-21 | 2000-11-29 | 住友化学工业株式会社 | Prepn. of methionine |
| CN104203912A (en) * | 2012-03-20 | 2014-12-10 | 赢创工业集团股份有限公司 | Preparation method of 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206704A1 (en) * | 2016-06-03 | 2017-12-07 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine new crystal form ii and preparation method therefor |
| CN108157908A (en) * | 2018-02-09 | 2018-06-15 | 武晓丹 | It is a kind of to utilize the method for vacuumizing and preparing high heap density I+G mixed crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017206704A1 (en) | 2017-12-07 |
| CN106008297B (en) | 2018-11-30 |
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