CN112679565A - Preparation process of glucosamine sulfate - Google Patents
Preparation process of glucosamine sulfate Download PDFInfo
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- CN112679565A CN112679565A CN202011554512.4A CN202011554512A CN112679565A CN 112679565 A CN112679565 A CN 112679565A CN 202011554512 A CN202011554512 A CN 202011554512A CN 112679565 A CN112679565 A CN 112679565A
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Abstract
The invention relates to a preparation process of glucosamine sulfate, which comprises the following steps: (1) uniformly stirring glucosamine hydrochloride and monohydric alcohol to obtain an alcoholic solution of the glucosamine hydrochloride for later use; (2) adding an alkaline neutralizing agent into the alcoholic solution, adding a silver sulfate solution after the reaction is finished, stirring, standing, and then carrying out solid-liquid separation on a reaction system; (3) adjusting the liquid separated in the step (2) to be acidic, then distilling to obtain glucosamine sulfate, and recovering the distilled solvent. Compared with the traditional methods such as adsorption, extraction and the like, the method disclosed by the invention is efficient and rapid, more importantly, can thoroughly remove the chloride ions in the glucosamine hydrochloride, and the obtained silver precipitate is easy to separate and recycle and can be used as an industrial byproduct without generating additional solid waste.
Description
Technical Field
The invention relates to the technical field of glucosamine preparation, in particular to a glucosamine sulfate preparation process.
Background
The following in the background art merely refers to information that is understood by the inventor to be relevant to the present invention and is intended to augment understanding of the present invention through a description of some basic technical knowledge related to the present invention, which information does not necessarily have to constitute knowledge that is well known by those of ordinary skill in the art.
Because of glucosamine (molecular formula C)6H13NO5) The glucosamine is easy to oxidize and can not be stably stored at room temperature, and currently, commercialized glucosamine exists mainly in the forms of glucosamine hydrochloride and glucosamine sulfate, so that the amino in the glucosamine is prevented from being oxidized. Glucosamine sulfate (formula C)6H13NO8S) is an important component necessary for synthesizing proteoglycan in human articular cartilage matrix, glucosamine sulfate can stimulate cartilage cells to produce glycoprotein with normal polymer structure, inhibit certain enzymes capable of damaging articular cartilage, inhibit the generation of superoxide free radical of damaged cells, prevent the damage of corticoids and certain non-steroidal anti-inflammatory drugs to cartilage cells, and reduce the release of endotoxin factor of damaged cells, so glucosamine sulfate is frequently used for treating joint diseases.
Studies have shown that chloride ions stimulate the activity of a source of vasopressin, resulting in elevated blood pressure. However, because of the preparation process, the existing glucosamine sulfate often contains more chloride ions. The common arthritis patients are middle-aged and elderly people, and the proportion of people suffering from hypertension and cardiovascular diseases is large. Therefore, the chloride ion content of glucosamine sulfate should ideally be as low as possible to minimize the impact on the patient.
Disclosure of Invention
The main object of the present invention is to provide a method for reducing the impact of glucosamine sulphate on patients suffering from arthritis with hypertension or cardiovascular diseases, which does not contain chloride ions or keeps the chloride ion content at a low level. Therefore, the invention provides a preparation process of glucosamine sulfate, which effectively reduces the content of chloride ions in the glucosamine sulfate by separating the chloride ions in a precipitation form.
In order to realize the purpose, the invention discloses the following technical scheme:
a preparation process of glucosamine sulfate comprises the following steps:
(1) and uniformly stirring the glucosamine hydrochloride and the monohydric alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) And adding an alkaline neutralizing agent into the suspension, adding a silver sulfate solution after the reaction is finished, stirring, standing, and then carrying out solid-liquid separation on the reaction system.
(3) Adjusting the liquid separated in the step (2) to be acidic, then distilling to obtain glucosamine sulfate, and recovering the distilled solvent.
Further, in the step (1), the salt includes at least one of a sodium salt and a potassium salt.
Further, in the step (1), the monohydric alcohol comprises at least one of absolute methanol, absolute ethanol, propanol and the like. The glucosamine hydrochloride is slightly soluble or insoluble in monohydric alcohols such as anhydrous methanol, ethanol and the like, so that the glucosamine hydrochloride can be independently dispersed in the monohydric alcohols, and reaction conditions are created for subsequent neutralization reaction.
Further, in the step (1), ultrasonic stirring is adopted for stirring, so that the glucosamine hydrochloride is uniformly dispersed in the alcohol system to form a suspension, and agglomeration among the glucosamine hydrochloride is reduced.
Further, in the step (2), the alkaline neutralizing agent includes any one of sodium hydroxide and potassium hydroxide. One of the products of such neutralization of the lye with the glucosamine hydrochloride is water, which can be easily removed in subsequent processes avoiding the introduction of additional impurities.
Further, in the step (2), the separation method includes any one of centrifugation, filtration and the like. The silver chloride precipitate formed can be conveniently separated from the reaction system by mechanical separation.
Further, in the step (2), the alkaline neutralizing agent provides the same molar ratio of hydroxide ions to glucosamine hydrochloride.
Further, in the step (3), the pH of the liquid is adjusted to 3.5-5.5 by using dilute sulfuric acid.
Further, in the step (3), the distillation is vacuum distillation, and the monohydric alcohol is preferentially separated under vacuum conditions due to the low boiling point, so that the glucosamine sulfate salt with high purity is obtained.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the prior art, glucosamine hydrochloride is dissolved in aqueous solution and then neutralized with alkali liquor, however, a large amount of heat is generated during neutralization under the condition, which causes the temperature of a reaction system to be difficult to control well.
(2) Compared with the traditional methods such as adsorption, extraction and the like, the method disclosed by the invention is efficient and rapid, more importantly, can thoroughly remove the chloride ions in the glucosamine hydrochloride, and the obtained silver precipitate is easy to separate and recycle and can be used as an industrial byproduct without generating additional solid waste. Meanwhile, silver sulfate is adopted for fixing chloride ions, and sulfate radicals are exactly the components required for preparing glucosamine sulfate, so that extra impurities cannot be introduced in the method, and the subsequent impurity removal process is avoided.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. The invention will now be further illustrated by specific examples.
Example 1
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with absolute ethanol according to a ratio of 1 g: mixing the materials in a ratio of 15mL, and then ultrasonically stirring the materials for 30min to fully disperse the glucosamine hydrochloride in the absolute ethyl alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 4.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Example 2
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with anhydrous methanol according to a ratio of 1 g: mixing at a ratio of 20mL, and then ultrasonically stirring for 30min to fully disperse the glucosamine hydrochloride in the anhydrous methanol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 5.0 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Example 3
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (potassium salt) was mixed with propanol at a ratio of 1 g: 20mL, and then ultrasonically stirred for 30min to fully disperse the glucosamine hydrochloride in the propanol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the potassium hydroxide of 1:1, gradually adding potassium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 3.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Example 4
A preparation process of glucosamine sulfate comprises the following steps:
(1) mixing glucosamine hydrochloride (potassium salt) and absolute ethyl alcohol according to the proportion of 1 g: mixing at a ratio of 20mL, and then ultrasonically stirring for 30min to fully disperse the glucosamine hydrochloride in the absolute ethyl alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the potassium hydroxide of 1:1, gradually adding potassium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 5.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Example 5
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with absolute ethanol according to a ratio of 1 g: mixing at a ratio of 20mL, and then ultrasonically stirring for 30min to fully disperse the glucosamine hydrochloride in the absolute ethyl alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the potassium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 4.0 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Test example 1
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with absolute ethanol according to a ratio of 1 g: mixing the materials in a ratio of 15mL, and then ultrasonically stirring the materials for 30min to fully disperse the glucosamine hydrochloride in the absolute ethyl alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) And (3) adding dilute sulfuric acid into the reaction system in the step (2), adjusting the pH of the liquid to 4.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Test example 2
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with anhydrous methanol according to a ratio of 1 g: mixing at a ratio of 20mL, and then ultrasonically stirring for 30min to fully disperse the glucosamine hydrochloride in the anhydrous methanol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) And (3) adding dilute sulfuric acid into the reaction system in the step (2), adjusting the pH of the liquid to 5.0 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Test example 3
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with absolute ethanol according to a ratio of 1 g: mixing the materials in a ratio of 15mL, and then ultrasonically stirring the materials for 30min to fully disperse the glucosamine hydrochloride in the absolute ethyl alcohol to obtain a glucosamine hydrochloride suspension for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding sodium hydroxide powder into the glucosamine hydrochloride suspension to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver nitrate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 4.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Test example 4
A preparation process of glucosamine sulfate comprises the following steps:
(1) glucosamine hydrochloride (sodium salt) was mixed with deionized water at a ratio of 1 g: mixing the materials according to the proportion of 15mL, and then carrying out ultrasonic stirring for 30min to fully dissolve the glucosamine hydrochloride to obtain an aqueous solution of the glucosamine hydrochloride for later use.
(2) According to the molar ratio of the glucosamine hydrochloride to the sodium hydroxide of 1:1, gradually adding the sodium hydroxide into the aqueous solution of the glucosamine hydrochloride to neutralize redundant acid, slowly and mechanically stirring, monitoring the pH value of the system at any time during the reaction, and finishing the reaction when the reaction system is neutral.
(3) After the neutralization reaction in the step (2) is finished, dropwise adding a silver sulfate solution into the reaction system according to the molar ratio of chloride ions to silver ions of 1:1, stirring and standing until no precipitate is generated, then filtering the reaction system, separating out the generated silver chloride precipitate, recovering the silver chloride precipitate, and reserving a liquid part for later use.
(4) And (4) adding dilute sulfuric acid into the liquid separated in the step (3), adjusting the pH of the liquid to 4.5 +/-0.1, then placing the liquid in a vacuum distillation device for distillation to obtain glucosamine sulfate, and recovering the distilled solvent.
Performance testing
The content (weight percentage) of chloride ions in glucosamine sulfate prepared in the above examples and test examples was measured by high performance liquid chromatography, and the results are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Test example 1 | Test example 2 | Test example 3 | Test example 4 | |
| Cl-Content/% | 0.011 | 0.021 | 0.014 | 0.017 | 0.013 | 0.12 | 0.14 | 0.013 | 0.018 |
As can be seen from Table 1, the content of chloride ions in glucosamine sulfate prepared in examples was significantly reduced compared to those of test examples 1 and 2, because silver sulfate was not added to test examples 1 and 2, and thus chloride ions in glucosamine sulfate could not be immobilized, resulting in that chloride ions in glucosamine hydrochloride were always retained in glucosamine sulfate. The method adopts silver sulfate to fix chloride ions in glucosamine hydrochloride in a silver precipitation mode, so that the method is efficient and rapid, and can more thoroughly remove the chloride ions in the glucosamine hydrochloride.
In addition, the temperature of the system in the neutralization reaction process of the embodiment 1 and the experiment 4 is tested, and the result shows that the temperature of the embodiment 1 is lower than that of the experiment 4 by more than 30 ℃, which shows that the neutralization reaction carried out in the reaction system of monohydric alcohol effectively reduces the intensity of the reaction and improves the controllability and the safety of the reaction.
In addition, in test example 3, a large amount of nitrate, which is an impurity ion, was also detected, resulting in a decrease in the purity of glucosamine sulfate obtained in test example 3.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation process of glucosamine sulfate is characterized by comprising the following steps:
(1) uniformly stirring glucosamine hydrochloride and monohydric alcohol to obtain a glucosamine hydrochloride suspension for later use;
(2) adding an alkaline neutralizing agent into the suspension, adding a silver sulfate solution after the reaction is finished, stirring, standing, and then carrying out solid-liquid separation on a reaction system;
(3) adjusting the liquid separated in the step (2) to be acidic, then distilling to obtain glucosamine sulfate, and recovering the distilled solvent.
2. The process for preparing glucosamine sulfate according to claim 1, wherein in step (1), the salt comprises at least one of sodium salt and potassium salt.
3. The process for preparing glucosamine sulfate according to claim 1, wherein in step (1), the monohydric alcohol comprises at least one of absolute methanol, absolute ethanol and propanol.
4. The process for preparing glucosamine sulfate according to claim 1, wherein in the step (1), the stirring is performed by ultrasonic stirring.
5. The process for preparing glucosamine sulfate according to claim 1, wherein in the step (2), the alkaline neutralizing agent comprises any one of sodium hydroxide and potassium hydroxide.
6. The process for preparing glucosamine sulfate according to claim 1, wherein in the step (2), the separation method comprises any one of centrifugation and filtration.
7. The process for preparing glucosamine sulfate according to claim 1, wherein in step (2), the molar ratio of hydroxide ions to glucosamine hydrochloride provided by the alkaline neutralizing agent is the same.
8. The process for preparing glucosamine sulfate according to claim 1, wherein the distillation in step (3) is vacuum distillation.
9. The process for preparing glucosamine sulfate according to any one of claims 1-8, wherein in step (3), the pH of the liquid is adjusted to 3.5-5.5 with dilute sulfuric acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710483A (en) * | 2014-09-11 | 2015-06-17 | 迪沙药业集团有限公司 | Preparation method for glucosamine sulfate |
| CN106967131A (en) * | 2017-05-17 | 2017-07-21 | 山西同达药业有限公司 | A kind of Glucosamine Sulphate product and preparation method thereof |
| CN110862426A (en) * | 2019-12-09 | 2020-03-06 | 山东润德生物科技有限公司 | Method for preparing high-purity glucosamine sulfate |
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- 2020-12-24 CN CN202011554512.4A patent/CN112679565A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710483A (en) * | 2014-09-11 | 2015-06-17 | 迪沙药业集团有限公司 | Preparation method for glucosamine sulfate |
| CN106967131A (en) * | 2017-05-17 | 2017-07-21 | 山西同达药业有限公司 | A kind of Glucosamine Sulphate product and preparation method thereof |
| CN110862426A (en) * | 2019-12-09 | 2020-03-06 | 山东润德生物科技有限公司 | Method for preparing high-purity glucosamine sulfate |
Non-Patent Citations (1)
| Title |
|---|
| 张仁志等，主编: "《环境工程实验》", 28 February 2019, 中国环境出版集团 * |
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Application publication date: 20210420 |