CN110804077A - Preparation method of glucosamine hydrochloride - Google Patents
Preparation method of glucosamine hydrochloride Download PDFInfo
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- CN110804077A CN110804077A CN201911152014.4A CN201911152014A CN110804077A CN 110804077 A CN110804077 A CN 110804077A CN 201911152014 A CN201911152014 A CN 201911152014A CN 110804077 A CN110804077 A CN 110804077A
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- glucosamine hydrochloride
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- hydrochloric acid
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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
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen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
Abstract
The invention discloses a preparation method of glucosamine hydrochloride, which comprises the steps of taking crayfish shells as raw materials, preparing chitin after acid treatment and alkali treatment, and then hydrolyzing under the action of concentrated hydrochloric acid to prepare the glucosamine hydrochloride; the invention provides the reaction conditions which are most suitable for industrial production, and has the advantages of simple operation, low cost and high yield of glucosamine hydrochloride.
Description
Technical Field
The invention belongs to the technical field of biochemical synthesis, and particularly relates to a preparation method of glucosamine hydrochloride.
Background
Glucosamine (GleN) is an important hexosamine formed by substituting one hydroxyl group of glucose with an amino group, and there are two main types of glucosamine on the market today, one is glucosamine hydrochloride and the other is glucosamine sulfate. D-Glucosamine Hydrochloride (D-Glucosamine Hydrochloride), molecular formula C6H13NO5HCl, a white crystal, odorless, slightly sweet, readily soluble in water, slightly soluble in methanol, notThe compound is dissolved in organic solvents such as ethanol, has important physiological functions for human bodies, participates in liver and kidney detoxification, plays a role in resisting inflammation and protecting liver, has good curative effect on treating rheumatic arthritis and gastric ulcer, and is a main raw material for synthesizing antibiotics and anticancer drugs; can also be used in food, cosmetic and feed additive. Glucosamine hydrochloride is extracted from natural chitin, is a marine biological agent, and is the main component of chondroitin sulfate. It can promote the synthesis of mucopolysaccharide, raise the viscosity of joint synovial fluid, improve the metabolism of joint cartilage, promote the repair of joint cartilage and has obvious antiphlogistic and analgesic effects. It has the effect of promoting the injection efficiency of antibiotics, and can be used as nutritional supplement for diabetic patients.
The current methods for producing glucosamine mainly comprise an acid hydrolysis method, an enzymolysis method and a microbial fermentation method. Currently, glucosamine hydrochloride is industrially produced by hydrolyzing chitin raw material with hydrochloric acid, cooling, crystallizing, separating and other steps to obtain glucosamine hydrochloride product, but the method has the disadvantages of low production efficiency and the like. China is a large producing country and a large exporting country of glucosamine hydrochloride, and the annual export amount reaches 8000 million tons. Therefore, the production cost of the glucosamine hydrochloride is reduced, the production efficiency is improved, and the cost of enterprises is greatly reduced and the product yield is improved. In recent years, the crayfish cost aquatic products popular to the people in China, but the crayfish shells occupy a large space as garbage, so that the industrial production of the glucosamine hydrochloride by taking the crayfish shells as raw materials has important practical significance.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides an industrialized preparation method of glucosamine hydrochloride, which has the advantages of high production efficiency, low cost and simple operation.
The invention is realized by the following technical scheme:
the preparation method of the glucosamine hydrochloride is characterized by comprising the following steps:
the method comprises the following steps:
(1) cleaning and drying the shells of the crayfish which is taken as a raw material;
(2) soaking the dried crayfish shells in a hydrochloric acid solution with the concentration of 5-7%, then washing with water to be neutral, soaking in a hydrochloric acid solution with the concentration of 2-4% again to remove inorganic salts in the crayfish shells, washing with water to be neutral, and drying;
(3) adding NaOH solution with the concentration of 3-7% into a reaction kettle, heating to 105-120 ℃, slowly adding the crayfish shells subjected to acid treatment in the step (2) under the stirring condition, stirring for reaction, and washing reaction products to be neutral;
(4) soaking the product obtained in the step (3) in a potassium permanganate solution for decoloring, washing the product to be white, and drying the product to obtain chitin;
(5) adding concentrated hydrochloric acid into a reaction kettle, adding the chitin prepared in the step (4) in batches, slowly heating to 90-110 ℃ by adopting a gradient heating method, and maintaining the reaction temperature for reaction;
(6) and (5) decoloring and recrystallizing the reaction mixed solution obtained in the step (5) to obtain a glucosamine hydrochloride product which is white crystal, is easy to dissolve in water and is slightly soluble in ethanol.
Preferably, the crayfish shells cleaned in the step (1) are dried for 3-8h at 100 ℃.
Preferably, in the step (2), the dried crayfish shells are soaked in 5-6% hydrochloric acid for 18-24h, washed to be neutral by water, and then soaked in 3% hydrochloric acid solution for 8-10h again, and washed to be neutral by water; the inorganic salt in the shrimp shells can be sufficiently removed under the hydrochloric acid concentration and the soaking time.
Preferably, the crayfish shells subjected to the secondary acid treatment in the step (2) are dried for 3 to 8 hours at a temperature of between 80 and 120 ℃.
As a preferable scheme, the concentration of the NaOH solution used in the step (3) is 4-6%, the stirring reaction time is 20-35min, the concentration of the NaOH solution is lower than 4%, a large amount of glycoprotein in the shrimp shells cannot be completely removed, the chitin molecule main chain is easily broken when the concentration of the NaOH solution is higher than 6%, and the shrimp shells can form micropores after being treated by the NaOH solution, so that the full action of hydrochloric acid and calcium is facilitated, and the reaction time is reduced.
As a preferable scheme, the concentration of the potassium permanganate solution used in the step (4) is 0.3-0.6%, and the soaking time is 25-35 min.
Preferably, in the step (5), the temperature rise rate is 10-15 ℃/h, the temperature is raised to 90-110 ℃, and the reaction temperature is maintained for 10-20min under the condition, so that the phenomenon of coking caused by simultaneous breakage of the glycosidic bond and the amido bond of the chitin can be prevented.
Preferably, the decoloring process in the step (6) is as follows: adding the crude glucosamine product mixed solution into a stirring tank, adding activated carbon for decolorization and adsorption, stirring at 40-50 ℃ for 2-4h, and filtering.
Preferably, the mass fraction of the activated carbon in the stirring tank is 4-8%.
Further, in the step (6), recrystallization is carried out by using an 85-95% ethanol solution.
The invention has the beneficial effects that: the invention takes the cheap crayfish shells as the raw material, obtains the most suitable industrialized acidolysis reaction conditions through a large amount of grope, not only reduces the reaction cost, but also improves the yield of glucosamine, and is beneficial to industrialized production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof to assist those skilled in the art in providing a more complete, accurate and thorough understanding of the inventive concept and aspects thereof, and the scope of the present invention includes, but is not limited to, the following examples, and any modifications in the details and form of the technical aspects thereof that fall within the spirit and scope of the present application are intended to be included therein.
Example 1
Cleaning 50kg of crayfish shells, drying the crayfish shells at 100 ℃ for 3h, soaking the dried crayfish shells in a hydrochloric acid solution with the concentration of 5% for 24h, then washing the crayfish shells to be neutral with water, soaking the crayfish shells in a hydrochloric acid solution with the concentration of 2% for 10h, removing inorganic salt in the crayfish shells, washing the crayfish shells to be neutral with water, and drying the crayfish shells at 100 ℃ for 5 h; adding a NaOH solution with the concentration of 3% into a reaction kettle, heating to 120 ℃, slowly adding the acid-treated crayfish shells under the stirring condition, stirring for reacting for 35min, and washing the reaction product to be neutral; soaking the washed product in 0.6% potassium permanganate solution for decolorizing for 25min, washing with water to white, and oven drying at 100 deg.C for 3 hr to obtain chitin; adding 30% concentrated hydrochloric acid into a reaction kettle, adding chitin into the reaction kettle in 3 batches, wherein the chitin is prepared from the following components in percentage by mass: 1:3, slowly heating to 110 ℃ by adopting a gradient heating method, keeping the reaction temperature for 20min, and cooling to finish the reaction to obtain a glucosamine crude product, wherein the heating rate is 10 ℃/h; feeding the crude product into a stirring tank, adding activated carbon for decolorization and adsorption, wherein the mass fraction of the activated carbon in the stirring tank is 7%, stirring for 2h at 40-50 ℃, and filtering; recrystallizing the decolored feed liquid by using an 8% ethanol solution to obtain a glucosamine hydrochloride product, wherein the product yield is 82.3%.
Example 2
Cleaning 50kg of crayfish shells, drying the crayfish shells at 100 ℃ for 5h, soaking the dried crayfish shells in a hydrochloric acid solution with the concentration of 6% for 20h, then washing the crayfish shells to be neutral with water, soaking the crayfish shells in a hydrochloric acid solution with the concentration of 3% for 8h again, removing inorganic salt in the crayfish shells, washing the crayfish shells to be neutral with water, and drying the crayfish shells at 100 ℃ for 6 h; adding a 4% NaOH solution into a reaction kettle, heating to 110 ℃, slowly adding the acid-treated crayfish shells under the stirring condition, stirring for reacting for 20min, and washing the reaction product to be neutral; soaking the washed product in 0.5% potassium permanganate solution for decolorizing for 25min, washing with water to white, and oven drying at 100 deg.C for 3 hr to obtain chitin; adding 35% concentrated hydrochloric acid into a reaction kettle, and adding the prepared chitin into the reaction kettle in 5 batches according to the mass ratio of the chitin: 1:3.6 of concentrated hydrochloric acid, slowly heating to 95 ℃ by adopting a gradient heating method, wherein the heating rate is 14 ℃/h, maintaining the reaction temperature for 17min, and then cooling to finish the reaction to obtain a glucosamine crude product; feeding the crude product into a stirring tank, adding active carbon for decolorization and adsorption, wherein the mass fraction of the active carbon in the stirring tank is 6%, stirring for 3h at 40-50 ℃, and filtering; recrystallizing the decolored feed liquid by adopting 95 percent ethanol solution to obtain a glucosamine hydrochloride product, wherein the product yield is 89.4 percent.
Example 3
Cleaning 50kg of crayfish shells, drying at 100 ℃ for 4h, soaking the dried crayfish shells in a 7% hydrochloric acid solution for 21h, then washing with water to be neutral, soaking in a 2% hydrochloric acid solution again for 10h, removing inorganic salt in the crayfish shells, washing with water to be neutral, and drying at 100 ℃ for 8 h; adding a NaOH solution with the concentration of 7% into a reaction kettle, heating to 105 ℃, slowly adding the acid-treated crayfish shells under the stirring condition, stirring for reacting for 35min, and washing the reaction product to be neutral; soaking the washed product in 0.6% potassium permanganate solution for decolorizing for 35min, washing with water to white, and oven drying at 100 deg.C for 8 hr to obtain chitin; adding 35% concentrated hydrochloric acid into a reaction kettle, adding the chitin prepared in the step (4) in batches, wherein the mass ratio of the chitin to the concentrated hydrochloric acid is as follows: and (5) slowly heating to 95 ℃ by adopting a gradient heating method, wherein the heating rate is 15 ℃/h, maintaining the reaction temperature for 20min, then cooling to finish the reaction to obtain a glucosamine crude product, feeding the crude product into a stirring tank, adding activated carbon for decolorization and adsorption, stirring the activated carbon in the stirring tank for h at 40-50 ℃, filtering, recrystallizing the decolorized feed liquid by adopting a 90% ethanol solution to obtain a glucosamine hydrochloride product, wherein the product yield is 86.1%.
Example 4
Cleaning 50kg of crayfish shells, drying the crayfish shells at 100 ℃ for 5h, soaking the dried crayfish shells in a hydrochloric acid solution with the concentration of 6% for 20h, then washing the crayfish shells to be neutral with water, soaking the crayfish shells in a hydrochloric acid solution with the concentration of 3% for 9h, removing inorganic salt in the crayfish shells, washing the crayfish shells to be neutral with water, and drying the crayfish shells at 100 ℃ for 5 h; adding a 4% NaOH solution into a reaction kettle, heating to 115 ℃, slowly adding the acid-treated crayfish shells under the stirring condition, stirring for reacting for 20min, and washing the reaction product to be neutral; soaking the washed product in 0.3% potassium permanganate solution for decolorizing for 25min, washing with water to white, and oven drying at 100 deg.C for 6 hr to obtain chitin; adding 40% concentrated hydrochloric acid into a reaction kettle, adding chitin into the reaction kettle in 3 batches, wherein the chitin is prepared from the following components in percentage by mass: 1:4.5 of concentrated hydrochloric acid, slowly heating to 100 ℃ by adopting a gradient heating method, wherein the heating rate is 13 ℃/h, maintaining the reaction temperature for 15min, and then cooling to finish the reaction to obtain a glucosamine crude product; feeding the crude product into a stirring tank, adding activated carbon for decolorization and adsorption, wherein the mass fraction of the activated carbon in the stirring tank is 7%, stirring for 4h at 40-50 ℃, and filtering; recrystallizing the decolored feed liquid by adopting a 90% ethanol solution to obtain a glucosamine hydrochloride product, wherein the product yield is 85.3%.
Example 5
Cleaning 50kg of crayfish shells, drying the crayfish shells at 100 ℃ for 6h, soaking the dried crayfish shells in a 7% hydrochloric acid solution for 19h, then washing the crayfish shells to be neutral, soaking the crayfish shells in a 4% hydrochloric acid solution for 8h, removing inorganic salt in the crayfish shells, washing the crayfish shells to be neutral, and drying the crayfish shells at 100 ℃ for 4 h; adding a 5% NaOH solution into a reaction kettle, heating to 105 ℃, slowly adding the acid-treated crayfish shells under the stirring condition, stirring for reacting for 35min, and washing the reaction product to be neutral; soaking the washed product in 0.4% potassium permanganate solution for decolorizing for 30min, washing with water to white, and oven drying at 100 deg.C for 5 hr to obtain chitin; adding 40% concentrated hydrochloric acid into a reaction kettle, adding chitin into the reaction kettle in 4 batches, wherein the chitin is prepared from the following components in percentage by mass: 1:4.5 of concentrated hydrochloric acid, slowly heating to 100 ℃ by adopting a gradient heating method, wherein the heating rate is 13 ℃/h, maintaining the reaction temperature for 20min, and then cooling to finish the reaction to obtain a glucosamine crude product; feeding the crude product into a stirring tank, adding activated carbon for decolorization and adsorption, wherein the mass fraction of the activated carbon in the stirring tank is 7%, stirring for 3h at 40-50 ℃, and filtering; recrystallizing the decolored feed liquid by adopting 95 percent ethanol solution to obtain a glucosamine hydrochloride product, wherein the product yield is 84.9 percent.
Claims (10)
1. A preparation method of glucosamine hydrochloride is characterized by comprising the following steps: the method comprises the following steps:
(1) cleaning and drying the shells of the crayfish which is taken as a raw material;
(2) soaking the dried crayfish shells in a hydrochloric acid solution with the concentration of 5-7%, then washing with water to be neutral, soaking in a hydrochloric acid solution with the concentration of 2-4% again to remove inorganic salts in the crayfish shells, washing with water to be neutral, and drying;
(3) adding NaOH solution with the concentration of 3-7% into a reaction kettle, heating to 105-120 ℃, slowly adding the crayfish shells subjected to acid treatment in the step (2) under the stirring condition, stirring for reaction, and washing reaction products to be neutral;
(4) soaking the product obtained in the step (3) in a potassium permanganate solution for decoloring, washing the product to be white, and drying the product to obtain chitin;
(5) adding concentrated hydrochloric acid into a reaction kettle, adding the chitin prepared in the step (4) in batches, slowly heating to 90-110 ℃ by adopting a gradient heating method, and maintaining the reaction temperature for reaction;
(6) and (5) decoloring and recrystallizing the reaction mixed solution obtained in the step (5) to obtain a glucosamine hydrochloride product.
2. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: and (2) drying the crayfish shells cleaned in the step (1) at 100 ℃ for 3-8 h.
3. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: in the step (2), the dried crayfish shells are soaked in 5-6% hydrochloric acid for 18-24h, washed to be neutral, and then soaked in 3% hydrochloric acid solution for 8-10h, and washed to be neutral.
4. The method for preparing glucosamine hydrochloride according to claim 1 or 3, wherein the method comprises the steps of: and (3) drying the crayfish shells subjected to the secondary acid treatment in the step (2) at 100 ℃ for 3-8 h.
5. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: the concentration of the NaOH solution used in the step (3) is 4-6%, and the stirring reaction time is 20-35 min.
6. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: the concentration of the potassium permanganate solution used in the step (4) is 0.3-0.6%, and the soaking time is 25-35 min.
7. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: in the step (5), the heating rate is 10-15 ℃/h, the temperature is increased to 90-110 ℃, and the reaction temperature is maintained for 10-20 min.
8. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: the decoloring process in the step (6) is as follows: and (3) adding the mixed solution obtained in the step (5) into a stirring tank, adding activated carbon for decoloring and adsorbing, stirring at 40-50 ℃ for 2-4h, and filtering.
9. The method for preparing glucosamine hydrochloride according to claim 8, wherein the method comprises the steps of: the mass fraction of the activated carbon in the stirring tank is 4-8%.
10. The method for preparing glucosamine hydrochloride according to claim 1, wherein the method comprises the following steps: and (4) recrystallizing in 85-95% ethanol solution in step (6).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471075A (en) * | 2020-05-09 | 2020-07-31 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine potassium sulfate particles |
| CN111533769A (en) * | 2020-05-09 | 2020-08-14 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine hydrochloride granules |
| CN112279878A (en) * | 2020-12-08 | 2021-01-29 | 山东润德生物科技有限公司 | Method for preparing high-purity glucosamine potassium sulfate and application thereof |
| CN112574259A (en) * | 2020-12-25 | 2021-03-30 | 山东润德生物科技有限公司 | Process for preparing D-glucosamine hydrochloride by using biomass |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020147318A1 (en) * | 2001-04-09 | 2002-10-10 | Cho Fu Chuan | Preparation method of water soluble carboxylmethyl chitosan having anti-lipid peroxidation ability |
| CN101275155A (en) * | 2008-03-17 | 2008-10-01 | 青岛贝尔特生物科技有限公司 | Clean production method for zitan and chitin |
| CN102106502A (en) * | 2011-02-01 | 2011-06-29 | 完美（中国）有限公司 | Health-care food with functions of improving skin moisture and reinforcing immunity |
| CN103342821A (en) * | 2013-07-10 | 2013-10-09 | 南京林业大学 | Method for preparing chitin nanofibre by using shrimp and crab shells |
| CN104788585A (en) * | 2015-03-16 | 2015-07-22 | 华东理工大学 | Method for synthesizing chitin and derivatives thereof from glucosamine |
| CN109438532A (en) * | 2018-12-25 | 2019-03-08 | 庄臣酿酒（福建）有限公司 | A method of extracting D- Glucosamine |
| CN110229250A (en) * | 2019-07-09 | 2019-09-13 | 张大庆 | A method of utilizing soda acid " three de- methods " chitin extraction |
-
2019
- 2019-11-22 CN CN201911152014.4A patent/CN110804077A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020147318A1 (en) * | 2001-04-09 | 2002-10-10 | Cho Fu Chuan | Preparation method of water soluble carboxylmethyl chitosan having anti-lipid peroxidation ability |
| CN101275155A (en) * | 2008-03-17 | 2008-10-01 | 青岛贝尔特生物科技有限公司 | Clean production method for zitan and chitin |
| CN102106502A (en) * | 2011-02-01 | 2011-06-29 | 完美（中国）有限公司 | Health-care food with functions of improving skin moisture and reinforcing immunity |
| CN103342821A (en) * | 2013-07-10 | 2013-10-09 | 南京林业大学 | Method for preparing chitin nanofibre by using shrimp and crab shells |
| CN104788585A (en) * | 2015-03-16 | 2015-07-22 | 华东理工大学 | Method for synthesizing chitin and derivatives thereof from glucosamine |
| CN109438532A (en) * | 2018-12-25 | 2019-03-08 | 庄臣酿酒（福建）有限公司 | A method of extracting D- Glucosamine |
| CN110229250A (en) * | 2019-07-09 | 2019-09-13 | 张大庆 | A method of utilizing soda acid " three de- methods " chitin extraction |
Non-Patent Citations (1)
| Title |
|---|
| 李金林等，: ""D-氨基葡萄糖盐酸盐的制备优化研究"", 《安徽医药》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471075A (en) * | 2020-05-09 | 2020-07-31 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine potassium sulfate particles |
| CN111533769A (en) * | 2020-05-09 | 2020-08-14 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine hydrochloride granules |
| CN112279878A (en) * | 2020-12-08 | 2021-01-29 | 山东润德生物科技有限公司 | Method for preparing high-purity glucosamine potassium sulfate and application thereof |
| CN112574259A (en) * | 2020-12-25 | 2021-03-30 | 山东润德生物科技有限公司 | Process for preparing D-glucosamine hydrochloride by using biomass |
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