CN106589008A - Preparation method of glucosamine monomer - Google Patents
Preparation method of glucosamine monomer Download PDFInfo
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- CN106589008A CN106589008A CN201611187501.0A CN201611187501A CN106589008A CN 106589008 A CN106589008 A CN 106589008A CN 201611187501 A CN201611187501 A CN 201611187501A CN 106589008 A CN106589008 A CN 106589008A
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- glucosamine
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- monomer
- glucosamine hydrochloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
- C07H5/06—Aminosugars
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the technical field of chemical engineering, and particularly relates to a preparation method of a glucosamine monomer. The preparation method of the glucosamine monomer comprises the following steps of preparation of an aqueous solution of glucosamine hydrochloride, neutralization reaction, nanofiltration, concentration-crystallization and centrifugal filtration to obtain the glucosamine monomer. In the preparation method of the glucosamine monomer, the glucosamine hydrochloride is taken as a raw material, purified water is taken as a solvent, sodium hydroxide is taken as a deacidification agent to undergo the neutralization reaction with the glucosamine hydrochloride, a nanofiltration technology is adopted for desalination, and solid-liquid separation is performed through centrifugal filtration after concentration and crystallization in vacuum to obtain a glucosamine monomer crystal. Mother liquid produced in a crystalizing process after centrifugal filtration is reused in blending of raw material liquid, so that the recovery rate of glucosamine is increased.
Description
Technical field
The invention belongs to chemical technology field, particularly relates to a kind of preparation method of glucosamine monomer.
Background technology
Glucosamine (Glucosamine) is the compound that the 2- positions hydroxyl of glucose is replaced by an amino.Its point
Minor is C6H13O5N, is commonly called as amino sugar, glucamine, abbreviation D-glucosamine.Glucosamine is widely present in nature, generally with
N- acetyl derivatives (such as chitin) are present in micro- life with N- sulfuric esters and N- acetyl -3-O- lactic acid ether (3-O-.alpha.-carboxyethyl-D-glucosamine .) forms
Thing, the polysaccharide of animal origin and combine polysaccharide in.Glucosamine is the important nutrient that chondrocyte is formed in human body, is strong
The natural tissues composition of health articular cartilage.A large amount of medical researches show：Glucosamine can help repair and safeguard cartilage, and
The growth of chondrocyte can be stimulated.It has important physiological function to human body, participates in Liver and kidney removing toxic substances, plays antiinflammatory hepatoprotective and makees
With, there is good curative effect to treating rheumatism joint inflammation stomach function regulating ulcer, be the primary raw material of synthetic antibiotic and cancer therapy drug,
Food is applied also for, in cosmetics and feed additive.
Industrially the overwhelming majority is to hydrolyze to prepare using chitin Jing hydrochloric acid to glucosamine at present, it is also possible to uses and sends out
The 2-Acetamido-2-deoxy-D-glucose that ferment method is first produced hydrolyzes to prepare with hydrochloric acid again, but the product of gained is all the salt of glucosamine
Hydrochlorate.
Glucosamine monomer is the intermediate for synthesizing its various functions derivant, is to use amino Portugal in practical application mostly
Grape sugar hydrochlorate desalination acid is preparing.Li Jingyu, Liu Pu " synthesis of Novel D-glucosamine Schiff Bases " (《Synthesisization
Learn》, the 5th phase in 2006) in be exactly by glucosamine hydrochloride Jing naoh treatment filtration from sodium chloride in methyl alcohol,
Then directly carry out the chemical reaction of next step.Chinese patent application CN101899071A is the mixing in methanol or methanol and water
Entered using triethylamine, Feldalat NM, sodium carbonate, sodium bicarbonate, sodium hydroxide as acid binding agent and glucosamine hydrochloride in solvent
Row neutralization reaction, is filtered to remove the salt of generation, obtains the solution containing glucosamine, then adds in DAS
Chloralkane separates out glucosamine.CN103804434A is by acid binding agent and ammonia in the mixed solvent of methanol or methanol and water
Base glucosamine salt hydrochlorate is neutralized reaction, carries out solid-liquid separation by being centrifuged, solution of the acquisition containing glucosamine, then to
Ethanol or propanol is added to separate out glucosamine in DAS.Chinese patent CN103709208B is to use absolute methanol
Or dehydrated alcohol is used as reaction dissolvent, with diethylamine as deacidification agent, solid-liquid exchange reaction is carried out, glucosamine monomer keeps
Solid forms, filter off reaction dissolvent and obtain final product high-purity aminoglucose monomer.
In existing said method, there is an obvious shortcoming just to use volatile, inflammable and explosive organic molten
Agent, production safety have high demands, and consumption is also big, high cost.What is had is also toxic, and such as chloroform, dichloroethanes are poisonous, has potential carcinogenic
Property；Methanol and diethylamine are high toxicity.
The information for being disclosed in the background section is merely intended to increase the understanding of the general background to the present invention, and should not
When the prior art for being considered to recognize or imply the information structure in any form well known to persons skilled in the art.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide one kind is with glucosamine hydrochloride as raw material, with
Pure water is solvent, and with sodium hydroxide as deacidification agent, the technical matters combined with crystalline phase using nanofiltration are preparing aminoglucose
The method of sugar monomer.
The present invention provide concrete technical scheme be：
A kind of preparation method of glucosamine monomer, comprises the steps：
(1) preparation of glucosamine hydrochloride aqueous solution：The glucosamine hydrochloride of 200-1000g is added into 10L
Pure water in, stirring and dissolving obtains glucosamine hydrochloride solution；
(2) neutralization reaction：The hydrogen of 37.1-185.6g is added in the glucosamine hydrochloride solution that step (1) is obtained
Sodium oxide, stirring, until reaction is complete, obtain mixed solution；
(3) nanofiltration：The mixed solution that step (2) is obtained is filtered with NF membrane, is stopped when filtered solution reaches 6-9L
Only；
(4) condensing crystallizing：By remaining enrichment liquid, the vacuum evaporation crystallization at 60 DEG C, to be concentrated to 200-1000mL
When stop, being slow cooling to room temperature；
(5) centrifugal filtration：Crystallization and concentrated mother liquor are carried out into solid-liquid separation, the crystallization for being crystallized and being centrifugally separating to obtain
Mother solution；
(6) glucosamine hydrochloride of 80-400g is added in the crystalline mother solution obtained in step (5), and supplement is pure
To 10L, stirring is lower to add sodium hydroxide 14.8-59.4g to water purification, continues stirring until sodium hydroxide reaction is complete；Repeat step
(3) in nanofiltration in, step (4) in condensing crystallizing and step (5) centrifugal filtration operation, obtain glucosamine monomer.
Preferably, the concentration of the glucosamine hydrochloride solution described in step (1) is 2-10g/100mL.
Preferably, the glucosamine hydrochloride and the mol ratio of sodium hydroxide described in step (2) is 1：1.
Preferably, the retention component of the NF membrane described in step (3) is 200Dalton.
Preferably, the Sodium Chloride removal efficiency ＞ 80% in desalination of the nanofiltration described in step (3).
Compared with prior art, the present invention has the advantages that：
(1) method of the present invention uses pure water as solvent, it is to avoid using volatile, inflammable and explosive organic solvent,
Production environmental protection, safety preferably, reduce production cost.
(2) preparation method of glucosamine monomer of the invention is, with glucosamine hydrochloride as raw material, to adopt and receive
The technical matters combined with crystalline phase by filter, can improve the response rate of glucosamine.
Description of the drawings
Process chart of the accompanying drawing 1 for the preparation method of the glucosamine monomer of the present invention.
Specific embodiment
With reference to concrete example, the present invention is further detailed explanation.
Embodiment 1：
A kind of preparation method of glucosamine monomer, comprises the steps：
The glucosamine hydrochloride of 200g is added in the pure water of 10L, then stirring and dissolving adds sodium hydroxide
37.1g, continues stirring until sodium hydroxide reaction is complete；The mixed solution for obtaining is filtered with NF membrane, is worked as filtered solution
Stop when reaching 9L；The vacuum evaporation crystallization at 60 DEG C by remaining enrichment liquid, stops when being concentrated to 200ml, slow to drop
Temperature arrives room temperature；Solid-liquid separation is carried out through centrifugal filtration and obtains glucosamine monomer crystalline solid 58.1g, yield is 35.0%；
The crystalline mother solution that again centrifugal filtration is obtained carries out reuse, adds the glucosamine hydrochloride of 80g wherein and supplement is pure
To 10L, stirring is lower to add sodium hydroxide 14.8g to water purification, continues stirring until sodium hydroxide reaction is complete；Repetition is aforesaid to be received
Filter, condensing crystallizing, the process of centrifugal filtration, obtain glucosamine monomer crystalline solid 58.6g, and yield is 88.1%.
Embodiment 2：
A kind of preparation method of glucosamine monomer, comprises the steps：
The glucosamine hydrochloride of 400g is added in the pure water of 10L, then stirring and dissolving adds sodium hydroxide
74.2g, continues stirring until sodium hydroxide reaction is complete；The mixed solution for obtaining is filtered with NF membrane, is worked as filtered solution
Stop when reaching 9L；The vacuum evaporation crystallization at 60 DEG C by remaining enrichment liquid, stops when being concentrated to 300ml, slow to drop
Temperature arrives room temperature；Solid-liquid separation is carried out through centrifugal filtration and obtains glucosamine monomer crystalline solid 167.1g, yield is 50.3%；
The crystalline mother solution that again centrifugal filtration is obtained carries out reuse, adds the glucosamine hydrochloride of 220g wherein and supplement is pure
To 10L, stirring is lower to add sodium hydroxide 40.8g to water purification, continues stirring until sodium hydroxide reaction is complete；Repetition is aforesaid to be received
Filter, condensing crystallizing, the process of centrifugal filtration, obtain glucosamine monomer crystalline solid 167.5g, and yield is 91.7%.
Embodiment 3：
A kind of preparation method of glucosamine monomer, comprises the steps：
The glucosamine hydrochloride of 600g is added in the pure water of 10L, then stirring and dissolving adds sodium hydroxide
111.4g, continues stirring until sodium hydroxide reaction is complete；The mixed solution for obtaining is filtered with NF membrane, is worked as filtered solution
Stop when reaching 7L, pure water is supplemented in enrichment liquid to 10L, followed by being filtered with NF membrane, when filtered solution reaches 8L
When stop；The vacuum evaporation crystallization at 60 DEG C by remaining enrichment liquid, stops when being concentrated to 600ml, is slow cooling to room
Temperature；Solid-liquid separation is carried out through centrifugal filtration and obtains glucosamine monomer crystalline solid 177.5g, yield is 35.6%；Again will be from
The crystalline mother solution that the heart is filtrated to get carries out reuse, adds the glucosamine hydrochloride of 240g wherein and supplements pure water and arrives
10L, stirring is lower to add sodium hydroxide 44.5g, continues stirring until sodium hydroxide reaction is complete；The aforesaid nanofiltration of repetition, concentration
Crystallization, the process of centrifugal filtration, obtain glucosamine monomer crystalline solid 178.6g, and yield is 89.6%.
Embodiment 4：
A kind of preparation method of glucosamine monomer, comprises the steps：
The glucosamine hydrochloride of 800g is added in the pure water of 10L, then stirring and dissolving adds sodium hydroxide
148.5g, continues stirring until sodium hydroxide reaction is complete；The mixed solution for obtaining is filtered with NF membrane, is worked as filtered solution
Stop when reaching 7L, pure water is supplemented in enrichment liquid to 10L, followed by being filtered with NF membrane, when filtered solution reaches 8L
When stop；The vacuum evaporation crystallization at 60 DEG C by remaining enrichment liquid, stops when being concentrated to 800ml, is slow cooling to room
Temperature；Solid-liquid separation is carried out through centrifugal filtration and obtains glucosamine monomer crystalline solid 226.3g, yield is 34.1%；Again will be from
The crystalline mother solution that the heart is filtrated to get carries out reuse, adds the glucosamine hydrochloride of 320g wherein and supplements pure water and arrives
10L, stirring is lower to add sodium hydroxide 59.4g, continues stirring until sodium hydroxide reaction is complete；The aforesaid nanofiltration of repetition, concentration
Crystallization, the process of centrifugal filtration, obtain glucosamine monomer crystalline solid 227.7g, and yield is 85.7%.
Embodiment 5：
A kind of preparation method of glucosamine monomer, comprises the steps：
The glucosamine hydrochloride of 1000g is added in the pure water of 10L, then stirring and dissolving adds hydroxide
Sodium 185.6g, continues stirring until sodium hydroxide reaction is complete；The mixed solution for obtaining is filtered with NF membrane, is worked as filtration
Liquid stops when reaching 6L, supplements pure water to 10L, followed by being filtered with NF membrane, when filtered solution reaches in enrichment liquid
Stop during 6L, then pure water is supplemented in enrichment liquid to 10L, followed by being filtered with NF membrane, when filtered solution reaches 6L
Stop；The vacuum evaporation crystallization at 60 DEG C by remaining enrichment liquid, stops when being concentrated to 1000ml, is slow cooling to room
Temperature.Solid-liquid separation is carried out through centrifugal filtration and obtains glucosamine monomer crystalline solid 284.2g, yield is 34.2%；Again will be from
The crystalline mother solution that the heart is filtrated to get carries out reuse, adds the glucosamine hydrochloride of 400g wherein and supplements pure water and arrives
10L, stirring is lower to add sodium hydroxide 59.4g, continues stirring until sodium hydroxide reaction is complete；The aforesaid nanofiltration of repetition, concentration
Crystallization, the process of centrifugal filtration, obtain glucosamine monomer crystalline solid 285.1g, and yield is 85.8%.
The present invention is studied with the removal efficiency relation of Sodium Chloride to the volume of filtered solution in nanofiltration process in step (3),
Obtain a result as shown in table 1.
The volume of 1 filtered solution of table and the removal efficiency relation of Sodium Chloride
| Filtered solution volume (%) | Sodium Chloride removal efficiency (%) |
| 50 | 38.4 |
| 60 | 47.1 |
| 70 | 56.9 |
| 80 | 67.6 |
| 90 | 80.2 |
Therefore, the mixed solution containing glucosamine monomer and Sodium Chloride for obtaining filtered with NF membrane
In operation, due to the difference of initial concentration, the cycles of concentration of nanofiltration also can be different, carry out a nanofiltration and do not reach in the case of having
The requirement of dechlorination sodium, at this moment will supplement to add water in enrichment liquid carries out twice or repeatedly nanofiltration removing Sodium Chloride.
The yield of the glucosamine monomer of preparation method in embodiment 1-5 in the present invention is counted, as a result such as table 2
It is shown.
The yield of the preparation method of the glucosamine monomer of 2 present invention of table
| Process | The yield (%) of glucosamine monomer |
| Embodiment 1 | 88.1 |
| Embodiment 2 | 91.7 |
| Embodiment 3 | 89.6 |
| Embodiment 4 | 85.7 |
| Embodiment 5 | 85.8 |
As shown in Table 2, in embodiments of the invention 1-5 the yield of glucosamine monomer more than 85%, amino Portugal
The yield of grape sugar monomer is high, has broad application prospects.
It is aforementioned to the present invention specific illustrative embodiment description be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, much can be changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should
With so that those skilled in the art can realize and using the present invention a variety of exemplaries and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (5)
1. a kind of preparation method of glucosamine monomer, it is characterised in that comprise the steps：
(1) preparation of glucosamine hydrochloride aqueous solution：By the pure of the glucosamine hydrochloride addition 10L of 200-1000g
In water purification, stirring and dissolving obtains glucosamine hydrochloride solution；
(2) neutralization reaction：The hydroxide of 37.1-185.6g is added in the glucosamine hydrochloride solution that step (1) is obtained
Sodium, stirring, until reaction is complete, obtain mixed solution；
(3) nanofiltration：The mixed solution that step (2) is obtained is filtered with NF membrane, is stopped when filtered solution reaches 6-9L；
(4) condensing crystallizing：By remaining enrichment liquid at 60 DEG C vacuum evaporation crystallization, it is to be concentrated to 200-1000mL when stop
Only, it is slow cooling to room temperature；
(5) centrifugal filtration：Crystallization and concentrated mother liquor are carried out into solid-liquid separation, the crystallization for being crystallized and being centrifugally separating to obtain is female
Liquid；
(6) glucosamine hydrochloride of 80-400g is added in the crystalline mother solution obtained in step (5), and supplements pure water
To 10L, stirring is lower to add sodium hydroxide 14.8-59.4g, continues stirring until sodium hydroxide reaction is complete；In repeat step (3)
In nanofiltration, step (4) in condensing crystallizing and step (5) centrifugal filtration operation, obtain glucosamine monomer.
2. the preparation method of glucosamine monomer according to claim 1, it is characterised in that described in step (1)
The concentration of glucosamine hydrochloride solution is 2-10g/100mL.
3. the preparation method of glucosamine monomer according to claim 1, it is characterised in that：Described in step (2)
Glucosamine hydrochloride is 1 with the mol ratio of sodium hydroxide：1.
4. the preparation method of glucosamine monomer according to claim 1, it is characterised in that：Described in step (3)
The retention component of NF membrane is 200Dalton.
5. the preparation method of glucosamine monomer according to claim 1, it is characterised in that：Described in step (3)
Nanofiltration Sodium Chloride removal efficiency ＞ 80% in desalination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187501.0A CN106589008A (en) | 2016-12-20 | 2016-12-20 | Preparation method of glucosamine monomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187501.0A CN106589008A (en) | 2016-12-20 | 2016-12-20 | Preparation method of glucosamine monomer |
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| CN106589008A true CN106589008A (en) | 2017-04-26 |
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| CN201611187501.0A Pending CN106589008A (en) | 2016-12-20 | 2016-12-20 | Preparation method of glucosamine monomer |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475611A (en) * | 2008-11-20 | 2009-07-08 | 浙江海力生制药有限公司 | Method for preparing high-purity aminoglucose hydrochloride |
| CN101899071A (en) * | 2009-05-31 | 2010-12-01 | 欣凯医药化工中间体（上海）有限公司 | Method for preparing glucosamine monomer from glucosamine hydrochloride |
| WO2011060807A1 (en) * | 2009-11-23 | 2011-05-26 | Pharma Base S.A. | Method for producing n-acetyl-d-glucosamine |
| CN102464679A (en) * | 2010-11-04 | 2012-05-23 | 江苏江山制药有限公司 | Production process for preparing high-purity D-glucosamine hydrochloride from citric acid fermentation residues |
| CN102850411A (en) * | 2012-10-12 | 2013-01-02 | 江苏澳新生物工程有限公司 | Preparation method of D-glucosamine sulfate potassium chloride salt |
| CN103709208A (en) * | 2014-01-16 | 2014-04-09 | 江苏九寿堂生物制品有限公司 | Method for preparing glucosamine monomer |
| CN103804434A (en) * | 2012-11-09 | 2014-05-21 | 扬州鸿信生物制品有限公司 | Glucosamine preparation method |
-
2016
- 2016-12-20 CN CN201611187501.0A patent/CN106589008A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475611A (en) * | 2008-11-20 | 2009-07-08 | 浙江海力生制药有限公司 | Method for preparing high-purity aminoglucose hydrochloride |
| CN101899071A (en) * | 2009-05-31 | 2010-12-01 | 欣凯医药化工中间体（上海）有限公司 | Method for preparing glucosamine monomer from glucosamine hydrochloride |
| WO2011060807A1 (en) * | 2009-11-23 | 2011-05-26 | Pharma Base S.A. | Method for producing n-acetyl-d-glucosamine |
| CN102464679A (en) * | 2010-11-04 | 2012-05-23 | 江苏江山制药有限公司 | Production process for preparing high-purity D-glucosamine hydrochloride from citric acid fermentation residues |
| CN102850411A (en) * | 2012-10-12 | 2013-01-02 | 江苏澳新生物工程有限公司 | Preparation method of D-glucosamine sulfate potassium chloride salt |
| CN103804434A (en) * | 2012-11-09 | 2014-05-21 | 扬州鸿信生物制品有限公司 | Glucosamine preparation method |
| CN103709208A (en) * | 2014-01-16 | 2014-04-09 | 江苏九寿堂生物制品有限公司 | Method for preparing glucosamine monomer |
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