CN111848428A - Preparation method of gamma-type glycine and gamma-type glycine - Google Patents
Preparation method of gamma-type glycine and gamma-type glycine Download PDFInfo
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- CN111848428A CN111848428A CN202010518912.3A CN202010518912A CN111848428A CN 111848428 A CN111848428 A CN 111848428A CN 202010518912 A CN202010518912 A CN 202010518912A CN 111848428 A CN111848428 A CN 111848428A
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- glycine
- gamma
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- ball milling
- type glycine
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000004471 Glycine Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000000498 ball milling Methods 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of gamma-type glycine and the gamma-type glycine, and relates to the technical field of preparation processes of industrial raw materials. The preparation method comprises the following steps: mixing a glycine starting material with a catalyst to form a mixture; and ball-milling the mixture by adopting a ball milling method to obtain the gamma-type glycine. The preparation method can directly convert the glycine raw material alpha-type glycine into gamma-type glycine completely, does not need to adjust the production process in the preparation process, and is simple and mature in operation. In addition, the catalyst in the preparation method of the gamma-type glycine provided by the embodiment of the invention is nontoxic and inert, and the subsequent separation treatment of the product gamma-type glycine is not needed after the preparation, so that the preparation process is simpler.
Description
Technical Field
The invention relates to the technical field of preparation processes of industrial raw materials, and particularly relates to a preparation method of gamma-type glycine and the gamma-type glycine.
Background
Glycine is an amino acid with the simplest structure, and is an important raw material in the fields of food, medicine and the like. The common glycine crystal forms are 3 types: alpha, beta and gamma forms. Where gamma-type is the stable phase, alpha-type is the metastable phase and beta-type is the unstable phase. The α form exists stably under low-temperature drying conditions, but the α form is transformed into the stable phase γ form under a moist heat environment. Due to crystallization kinetics problems, metastable-phase alpha-forms are generally preferentially obtained during the preparation of glycine crystals in aqueous solution. If crystal form transformation occurs in the process of storing and transporting the alpha-type glycine, the product is agglomerated, and the use is inconvenient. The gamma-type glycine is an advanced and excellent piezoelectric material and nonlinear optical material due to a special asymmetric polar structure. Therefore, the gamma-type glycine can effectively solve the problem of poor stability of glycine products and improve the using effect of the glycine products.
At present, the glycine products abroad are mainly gamma-type. The nucleation and growth of gamma-type glycine are very sensitive, the method for preparing gamma-type glycine is mainly a solution phase method, such as crystallization preparation in glycine solution which is treated by acidification and alkalization or added with alkali metal salt, and preparation by heating and converting alpha-type glycine in glycine aqueous solution with a specified pH value, but the preparation process and conditions are not easy to control, and the gamma-type glycine prepared by the solution phase needs to be obtained by separating a final product.
Disclosure of Invention
The invention aims to provide a preparation method of gamma-type glycine, which is cheap, simple and convenient to operate and does not need to be separated.
The invention also aims to provide gamma-type glycine.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of gamma-type glycine, which is characterized by comprising the following steps:
mixing a glycine starting material with a catalyst to form a mixture; and
and performing ball milling treatment on the mixture by adopting a ball milling method to obtain the gamma-type glycine.
According to a preferred embodiment, the mass ratio of the glycine starting material to the catalyst in the mixture is: 500: (1-500).
According to a preferred embodiment, the mass percentage of catalyst in the mixture is 0.2 wt%.
According to a preferred embodiment, the catalyst is one or more of stabilized inorganic salts.
According to a preferred embodiment, the catalyst is selected from one or more of potassium chloride, potassium bromide, potassium sulfate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium chloride, sodium bromide or sodium sulfate.
According to a preferred embodiment, the glycine starting material is an alpha-glycine.
According to a preferred embodiment, the step of ball milling the mixture by ball milling further comprises: grinding aid ingredients are added, and the grinding aid ingredients are water or ethanol.
According to a preferred embodiment, the ball milling treatment time is between 10min and 2 h.
According to a preferred embodiment, the ball milling treatment temperature is from ambient temperature to 60 ℃.
The invention also provides gamma-type glycine prepared by the preparation method.
Based on the technical scheme, the preparation method of the gamma-type glycine at least has the following technical effects:
the preparation method of the gamma-type glycine provided by the invention comprises the steps of mixing glycine raw materials and a catalyst to form a mixture, and then carrying out ball milling treatment on the mixture by adopting a ball milling method to obtain the gamma-type glycine. Under the combined action of physical ball milling and a catalyst, the preparation method can directly and completely convert the glycine raw material alpha-type glycine into gamma-type glycine, does not need to adjust the production process in the preparation process, and is simple and mature in operation.
In addition, the catalyst in the preparation method of the gamma-type glycine provided by the embodiment of the invention is nontoxic and inert, and the subsequent separation treatment of the product gamma-type glycine is not needed after the preparation, so that the preparation process is simpler.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD pattern of a product prepared according to example 1 of the present invention;
FIG. 2 is an XRD pattern of a product prepared according to example 2 of the present invention;
figure 3 is an XRD pattern of the product prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method for producing gamma-type glycine according to the embodiment of the present invention will be specifically described below.
The invention provides a preparation method of gamma-type glycine, which comprises the following steps:
mixing a glycine starting material with a catalyst to form a mixture; and
and performing ball milling treatment on the mixture by adopting a ball milling method to obtain the gamma-type glycine.
Preferably, the mass ratio of the glycine raw material to the catalyst in the mixture is as follows: 500: (1-500). Preferably, the mass percentage of catalyst in the mixture is 0.2 wt%. Preferably, the catalyst is one or more of stable inorganic salts. Preferably, the catalyst is selected from one or more of potassium chloride, potassium bromide, potassium sulfate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium chloride, sodium bromide or sodium sulfate. Therefore, the catalyst content in the mixture can be very low, and the mixture is non-toxic and inert, so that the subsequent separation treatment of the prepared gamma-type glycine is not needed, and the treatment process is simplified.
Preferably, the glycine starting material is alpha-glycine.
Preferably, the step of ball milling the mixture by ball milling further comprises: grinding aid components are added, and grinding aid components are added into water or ethanol. Preferably, the ball milling treatment time is 10min-2 h. Preferably, the ball milling treatment temperature is from room temperature to 60 ℃. The preparation method is simple and mature, can directly and completely convert the alpha-type glycine raw material into the gamma-type glycine, and does not need to adjust the process in the preparation process.
The invention also provides gamma-type glycine prepared by the preparation method. The gamma-type glycine prepared by the preparation method has higher purity.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a comparative example, which was prepared by a method comprising the steps of:
carrying out ball milling treatment on 1g of alpha-type glycine by a ball milling method, wherein the ball milling treatment time is 1 hour, and the ball milling treatment temperature is normal temperature, so as to obtain a ball milling product.
As shown in fig. 1, fig. 1 shows the XRD pattern of the ball-milled product of this example, and as can be seen from fig. 1, the ball-milled product prepared in this example is still the α -type glycine.
Example 2
The preparation method of this example includes the following steps:
mixing 1g of alpha glycine and 1g of potassium chloride to form a mixture;
and performing ball milling treatment on the mixture by adopting a ball milling method, wherein the ball milling treatment time is 1 hour, and the ball milling treatment temperature is normal temperature to obtain a ball milling product.
As shown in fig. 2, fig. 2 shows the XRD pattern of the ball-milled product of this example, and as can be seen from fig. 2, the ball-milled product prepared in this example is gamma-type glycine.
Example 3
The preparation method of this example includes the following steps:
mixing 1g of alpha glycine and 2mg of sodium chloride to form a mixture;
and performing ball milling treatment on the mixture by adopting a ball milling method, wherein the ball milling treatment time is 1 hour, and the ball milling treatment temperature is normal temperature to obtain a ball milling product.
As shown in fig. 3, fig. 3 shows the XRD pattern of the ball-milled product of this example, and as can be seen from fig. 3, the ball-milled product prepared in this example is gamma-type glycine.
Therefore, as can be seen from the comparison between example 1 and example 2 and example 3, the complete conversion of the α -type glycine to the γ -type glycine can be achieved by the ball milling treatment under the action of the catalyst, and the γ -type glycine can be prepared by the combined action of the physical ball milling and the catalyst. In addition, the applicant has found through experiments that the amount of glycine raw material and catalyst is enlarged by 20 times on the basis of examples 2 and 3, and the result shows that the ball-milled product is gamma-type glycine, so that the preparation method of the invention can be used for industrial production and has great economic value for the production of gamma-type glycine.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of gamma-type glycine is characterized by comprising the following steps:
mixing a glycine starting material with a catalyst to form a mixture; and
and performing ball milling treatment on the mixture by adopting a ball milling method to obtain the gamma-type glycine.
2. The preparation method according to claim 1, wherein the mass ratio of the glycine raw material to the catalyst in the mixture is as follows: 500: (1-500).
3. The method according to claim 2, wherein the mass percentage of the catalyst in the mixture is 0.2 wt%.
4. The method according to claim 1, wherein the catalyst is one or more stable inorganic salts.
5. The preparation method according to claim 4, wherein the catalyst is selected from one or more of potassium chloride, potassium bromide, potassium sulfate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium chloride, sodium bromide or sodium sulfate.
6. The method according to claim 1, wherein the glycine starting material is an α -type glycine.
7. The method of claim 1, wherein the step of ball milling the mixture by ball milling further comprises: grinding aid ingredients are added, and the grinding aid ingredients are water or ethanol.
8. The preparation method according to claim 7, wherein the ball milling treatment time is 10min to 2 h.
9. The method according to claim 8, wherein the ball-milling treatment temperature is from room temperature to 60 ℃.
10. Gamma-glycine prepared by the process according to any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010518912.3A CN111848428A (en) | 2020-06-09 | 2020-06-09 | Preparation method of gamma-type glycine and gamma-type glycine |
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| CN202010518912.3A CN111848428A (en) | 2020-06-09 | 2020-06-09 | Preparation method of gamma-type glycine and gamma-type glycine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102491010B1 (en) * | 2021-09-07 | 2023-01-20 | 경희대학교 산학협력단 | Method for producing stable-phase crystals using physical grinding |
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| US20050256300A1 (en) * | 2004-04-13 | 2005-11-17 | Garetz Bruce A | Method for using a static electric field to induce crystallization and to control crystal form |
| CN1950327A (en) * | 2004-04-07 | 2007-04-18 | 旭化成化学株式会社 | Method of purifying amino acid |
| CN106442607A (en) * | 2016-08-31 | 2017-02-22 | 河北科技大学 | Method for controlling temperature of glycine cooling crystallization crystal point |
| CN107021908A (en) * | 2016-01-29 | 2017-08-08 | 重庆润泽医药有限公司 | The method for preparing levo-oxiracetam crystal formation II |
| CN108117554A (en) * | 2018-03-08 | 2018-06-05 | 董丹丹 | A kind of method that ball-milling method prepares istradefylline crystal form III |
-
2020
- 2020-06-09 CN CN202010518912.3A patent/CN111848428A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950327A (en) * | 2004-04-07 | 2007-04-18 | 旭化成化学株式会社 | Method of purifying amino acid |
| US20050256300A1 (en) * | 2004-04-13 | 2005-11-17 | Garetz Bruce A | Method for using a static electric field to induce crystallization and to control crystal form |
| CN107021908A (en) * | 2016-01-29 | 2017-08-08 | 重庆润泽医药有限公司 | The method for preparing levo-oxiracetam crystal formation II |
| CN106442607A (en) * | 2016-08-31 | 2017-02-22 | 河北科技大学 | Method for controlling temperature of glycine cooling crystallization crystal point |
| CN108117554A (en) * | 2018-03-08 | 2018-06-05 | 董丹丹 | A kind of method that ball-milling method prepares istradefylline crystal form III |
Non-Patent Citations (3)
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| 罗运军: "《新型含能材料》", 31 January 2015, 国防工业出版社 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102491010B1 (en) * | 2021-09-07 | 2023-01-20 | 경희대학교 산학협력단 | Method for producing stable-phase crystals using physical grinding |
| US20230084034A1 (en) * | 2021-09-07 | 2023-03-16 | University-Industry Cooperation Group Of Kyung Hee University | Method for producing stable-phase crystals using physical grinding |
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