CN104327129A - Method for preparing glucosamine hydrochloride by taking crab shells as raw materials - Google Patents
Method for preparing glucosamine hydrochloride by taking crab shells as raw materials Download PDFInfo
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- CN104327129A CN104327129A CN201410690708.4A CN201410690708A CN104327129A CN 104327129 A CN104327129 A CN 104327129A CN 201410690708 A CN201410690708 A CN 201410690708A CN 104327129 A CN104327129 A CN 104327129A
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- hydrochloric acid
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Abstract
The invention discloses a method for preparing glucosamine hydrochloride by taking crab shells as raw materials. The method comprises the following steps: performing treatment on the crab shells with concentrated hydrochloric acid and a 50% sodium hydroxide solution to obtain chitin after removal of calcium and proteins and acetyl; adding chitin after crushing into a reaction kettle, slowly adding hydrochloric acid while stirring and performing reflux reaction for 4-6h under the conditions that the temperature is 100-130 DEG C and the pressure is 0.1-0.2MPa; and adding activated carbon to perform decolorization treatment after the reaction, then filtering to remove solid impurities, adding anhydrous ethanol the volume of which is 5 times of that filtrate into filtrate, fully stirring, then standing, precipitating a white precipitate, filtering and drying to obtain a glucosamine hydrochloride crude product; and further washing the crude product with anhydrous ethanol and drying to obtain a purified product. The method is obtained by performing improvement innovation on reaction conditions on the basis of the existing process, has the advantages of reducing the concentration of hydrochloric acid, reducing reaction waste liquid and improving production efficiency and is more suitable for industrial production.
Description
Technical field
The present invention relates to a kind of with crab shell for the method for glucosamine hydrochloride prepared by raw material.
Background technology
Chitin is that a kind of nature exists in a large number, reproducible native biopolymer polymkeric substance, and main composition unit is N-acetylamino-D-Glucose.In hydrochloric acid, chitin slowly can be hydrolyzed and generate D-Glucosamine Hydrochloride (GAH).Glucosamine hydrochloride is a kind of odorlessness but slightly pained white crystalline powder, soluble in water, is slightly soluble in methyl alcohol, is insoluble to the organic solvents such as ethanol.Utilize the chitin extracted from the arthropodan shells such as shrimp, crab and insect to be placed in the abundant hydrolysis of hydrochloric acid soln and can obtain D-Glucosamine Hydrochloride (GAH).
The multiple physiological actions such as D-Glucosamine Hydrochloride has antibacterial, anti-inflammatory, protects liver, antitumor, anti-oxidant, are also the important foundation raw materials synthesizing many medicines simultaneously, have development and application values in chemical industry, food and medicine and other fields.
At present, D-Glucosamine Hydrochloride is obtained primarily of chitin hydrolysis, and its preparation method mainly contains microwave irradiation, the hydrolysis of chitin gradient increased temperature, concentrated hydrochloric acid hydrolysis method etc.No matter but which kind of method, topmost defect is all concentration of hydrochloric acid requirement higher (12mol/mL), and strong to the corrodibility of equipment, wastewater treatment difficulty increases.
Summary of the invention
In order to overcome the defect that in existing method, used salt acid concentration is higher, the object of the present invention is to provide a kind of with crab shell for the method for glucosamine hydrochloride prepared by raw material, the method prepares D-Glucosamine Hydrochloride with the hydrochloric acid hydrolysis chitin of low concentration under an increased pressure.
Object of the present invention is achieved through the following technical solutions:
With crab shell for the method for glucosamine hydrochloride prepared by raw material, comprise the following steps:
(1) by the crab shell after cleaning up, in concentrated hydrochloric acid (concentration 37%), 1-2h is soaked, calcareous with what remove in crab shell; Leach concentrated hydrochloric acid, then soak with the sodium hydroxide solution that massfraction is 50%, being incubated 1.5-2.5h at 95 DEG C, fully stirring therebetween, is deproteinated and deacetylation process; Then leach alkali lye, be washed to neutrality, dry, obtain the chitin of white plates;
(2) chitin after pulverizing is added in reactor, under stirring, slowly add hydrochloric acid, at 100-130 DEG C, back flow reaction 4-6h under 0.1-0.2MPa; After reaction terminates, add gac and carry out desolventing technology, then filter and remove solid impurity, add the dehydrated alcohol of 5 times of volumes in filtrate, leave standstill, separate out white precipitate after abundant stirring, filtration, drying, obtain white glucosamine hydrochloride crude product; Thick product, again through absolute ethanol washing, obtains purified product after drying, productive rate 66%;
In step (2), the concentration of hydrochloric acid is 6mol/L, and the consumption 6-10 of hydrochloric acid is doubly to chitin quality;
In step (2), the temperature of back flow reaction preferably 120 DEG C, the preferred 0.2MPa of pressure.
The present invention has following advantage and effect relative to prior art:
1, the present invention is that have reduction concentration of hydrochloric acid, reduce waste reaction solution, the advantage of enhancing productivity, is more suitable for suitability for industrialized production to the improvement innovation that reaction conditions carries out on existing Process ba-sis.
2, D-glucosamine that the inventive method the obtains inhibit activities to sucrase and maltin is measured according to literature method.Result shows, D-glucosamine has certain restraining effect to alpha-glucosidase, and it can be applicable to the development of glycemic control class medicine.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
With crab shell for the method for glucosamine hydrochloride prepared by raw material, comprise the following steps:
(1) the crab shell 50Kg will cleaned up, add water 200L and 40L concentrated hydrochloric acid, fully stirs 2h, calcareous in removing crab shell; Filtering hydrochloric acid, then be that 50% sodium hydroxide solution 250L carries out deproteinated and deacetylation process with massfraction, under the condition of 95 DEG C, be incubated 1.5h, fully stir therebetween, then leach alkali lye, be washed to neutrality, dry, obtain the chitin 15Kg of white plates.
(2) the chitin 15Kg after pulverizing is got, join in the reactor that stirring, temperature control and reflux condensing tube are housed, under agitation slowly add the hydrochloric acid that concentration is 6mol/L, the mass ratio of hydrochloric acid and chitin is 8:1, at 120 DEG C, keep the pressure in reactor to be 0.2MPa, back flow reaction 4h.Add the gac accounting for chitin quality 25% after hydrolysis reaction terminates, heated and stirred at 80 DEG C, cooling, filter and remove impurity, then in filtrate, add the dehydrated alcohol of 5 times of volumes, after fully stirring, hold over night, adularescent Precipitation, filters, obtains white mass.Drying is glucosamine hydrochloride crude product, and thick product, again through absolute ethanol washing, obtains purified product after drying.
The inhibit activities of glucosamine to sucrase and maltin measures
Substrate (sucrose 56mmol/L, 0.2mL or maltose 3.5mmol/L, 0.35mL) be dissolved in 0.1mol/L potassium phosphate buffer (pH 7.0,0.2mL), the 50%DMSO aqueous solution of 0.1mL sample (glucosamine hydrochloride that sample and the present embodiment obtain) mixes with it, after 37 DEG C of insulation 5min, 0.4mL sucrase solution is joined (maltin mixed solution is standby with legal system) in mixed solution; Using the DMSO solution of 0.1mL as blank sample.After abundant mixing, sample and blank sample are at 37 DEG C of insulation 15min, and then add 1.5mL 2mol/L Tris-HCl buffered soln (pH 6.9) stopped reaction, reaction mixture removes impurity by silicagel column (diameter 6mm, long 35mm).The glucose amount of release adopts determination of glucose oxidase, and the mixture of filtrate and glucose test agent after 30 minutes 37 DEG C of insulations, is measured each sample liquid in 490nm optical density value, is calculated as follows the Inhibiting enzyme activity of each material.
Inhibit activities (%)=(OD
control sample– OD
test specimens)/OD
control sample× 100
The inhibit activities of glucosamine hydrochloride to alpha-glucosidase (comprising sucrase and maltin) is as shown in the table.Experimental result shows that the glucosamine hydrochloride that the inventive method obtains has certain inhibit activities to alpha-glucosidase.
* inhibiting rate represents with mean value ± standard deviation that three times measure; Test sample concentration is 1.5mg/ml.
Embodiment 2
With crab shell for the method for glucosamine hydrochloride prepared by raw material, comprise the following steps:
(1) the crab shell 50Kg will cleaned up, add water 200L and 40L concentrated hydrochloric acid, fully stirs 1.5h, calcareous in removing crab shell; Filtering hydrochloric acid, then be that 50% sodium hydroxide solution 250L carries out deproteinated and deacetylation process with massfraction, under the condition of 95 DEG C, be incubated 1.5h, fully stir therebetween, then leach alkali lye, be washed to neutrality, dry, obtain the chitin 15Kg of white plates.
(2) the crab shell 15Kg after pulverizing is got, join in the reactor that stirring, temperature control and reflux condensing tube are housed, under agitation slowly add the hydrochloric acid that concentration is 6mol/L, the mass ratio of hydrochloric acid and crab shell is 10:1, at 130 DEG C, keep the pressure in reactor to be 0.1MPa, back flow reaction 6h.Add the gac accounting for crab outer cover quality 25% after hydrolysis reaction terminates, heated and stirred at 80 DEG C, cooling, filter and remove impurity, then in filtrate, add the dehydrated alcohol of 5 times of volumes, after fully stirring, hold over night, adularescent Precipitation, filters, obtains white mass.Drying is glucosamine hydrochloride crude product, and thick product, again through absolute ethanol washing, obtains purified product after drying.
Embodiment 3
With crab shell for the method for glucosamine hydrochloride prepared by raw material, comprise the following steps:
(1) the crab shell 50Kg will cleaned up, add water 200L and 40L concentrated hydrochloric acid, fully stirs 2h, calcareous in removing crab shell; Filtering hydrochloric acid, then be that 50% sodium hydroxide solution 250L carries out deproteinated and deacetylation process with massfraction, under the condition of 95 DEG C, be incubated 1.5h, fully stir therebetween, then leach alkali lye, be washed to neutrality, dry, obtain the chitin 15Kg of white plates.
(2) the chitin 15Kg after pulverizing is got, join in the reactor that stirring, temperature control and reflux condensing tube are housed, under agitation slowly add the hydrochloric acid that concentration is 6mol/L, the mass ratio of hydrochloric acid and chitin is 6:1, at 100 DEG C, keep the pressure in reactor to be 0.2MPa, back flow reaction 5h.Add the gac accounting for chitin quality 25% after hydrolysis reaction terminates, heated and stirred at 80 DEG C, cooling, filter and remove impurity, then in filtrate, add the dehydrated alcohol of 5 times of volumes, after fully stirring, hold over night, adularescent Precipitation, filters, obtains white mass.Drying is glucosamine hydrochloride crude product, and thick product, again through absolute ethanol washing, obtains purified product after drying.
The obtained glucosamine hydrochloride of embodiment 2-3 is similar to the inhibit activities experimental result of alpha-glucosidase (comprising sucrase and maltin) and embodiment 1, repeats no more.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (2)
1. with crab shell for the method for glucosamine hydrochloride prepared by raw material, it is characterized in that comprising the following steps:
(1) by the crab shell after cleaning up, in concentrated hydrochloric acid, 1-2h is soaked; Leach concentrated hydrochloric acid, then soak with the sodium hydroxide solution that massfraction is 50%, be incubated 1.5-2.5h at 95 DEG C, fully stir therebetween; Then leach alkali lye, be washed to neutrality, dry, obtain the chitin of white plates;
(2) chitin after pulverizing is added in reactor, under stirring, slowly add hydrochloric acid, at 100-130 DEG C, back flow reaction 4-6h under 0.1-0.2MPa; After reaction terminates, add gac and carry out desolventing technology, then filter and remove solid impurity, add the dehydrated alcohol of 5 times of volumes in filtrate, leave standstill, separate out white precipitate after abundant stirring, filtration, drying, obtain glucosamine hydrochloride crude product; Thick product, again through absolute ethanol washing, obtains purified product after drying;
In step (2), the concentration of hydrochloric acid is 6mol/L, and the consumption 6-10 of hydrochloric acid is doubly to chitin quality.
2. according to claim 1 with crab shell for the method for glucosamine hydrochloride prepared by raw material, it is characterized in that: in step (2), the temperature of back flow reaction is 120 DEG C, and pressure is 0.2MPa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106235307A (en) * | 2016-07-28 | 2016-12-21 | 福建万亿店中店电子商务有限责任公司 | A kind of chondroitin sulfate miscellaneous grain crops thick soup of scapulohumeral periarthritis patient |
| CN109438532A (en) * | 2018-12-25 | 2019-03-08 | 庄臣酿酒（福建）有限公司 | A method of extracting D- Glucosamine |
| 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 |
| CN112521426A (en) * | 2020-12-15 | 2021-03-19 | 山东润德生物科技有限公司 | Method for preparing glucosamine |
| 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106235307A (en) * | 2016-07-28 | 2016-12-21 | 福建万亿店中店电子商务有限责任公司 | A kind of chondroitin sulfate miscellaneous grain crops thick soup of scapulohumeral periarthritis patient |
| CN109438532A (en) * | 2018-12-25 | 2019-03-08 | 庄臣酿酒（福建）有限公司 | A method of extracting D- Glucosamine |
| CN109438532B (en) * | 2018-12-25 | 2020-06-30 | 庄臣酿酒（福建）有限公司 | Method for extracting D-glucosamine |
| 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 |
| CN112521426A (en) * | 2020-12-15 | 2021-03-19 | 山东润德生物科技有限公司 | Method for preparing glucosamine |
| CN112521426B (en) * | 2020-12-15 | 2022-01-11 | 山东润德生物科技有限公司 | Method for preparing glucosamine |
| 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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