CN106749762A - A kind of preparation method of chitosan hydrochloride - Google Patents
A kind of preparation method of chitosan hydrochloride Download PDFInfo
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- CN106749762A CN106749762A CN201611261449.9A CN201611261449A CN106749762A CN 106749762 A CN106749762 A CN 106749762A CN 201611261449 A CN201611261449 A CN 201611261449A CN 106749762 A CN106749762 A CN 106749762A
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- shitosan
- ethanol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention discloses a kind of preparation method of chitosan hydrochloride, comprise the following steps：1) pretreatment of shitosan：Technical grade shitosan is weighed in hydrochloric acid solution, stirring, dissolving, plus aqueous slkali regulation pH separates out precipitation, added water successively respectively, organic solvent washing, obtain food-grade shitosan；2) to adding ethanol solution hydrochloride to react in food-grade shitosan while stirring, filter to get filtrate and filter residue, the filtrate is standby, wash the filter residue, drying, crushing, obtain chitosan hydrochloride.Using preparation method of the invention, production cost is reduced, save the reaction time, improve production yield.
Description
Technical field
The invention belongs to polysaccharide derivatives field, more particularly to a kind of preparation method of chitosan hydrochloride.
Background technology
Food-grade shitosan → using alcohol as medium is stirred at 50 DEG C and excessive hydrochloric acid react → be filtered to remove
Alcohol → alcohol-pickled is dried after pH once is adjusted into neutral → filtering.
Traditional law system hydrochloride has following weak point：(1) it is high to raw materials of chitosan requirement, it is low with ash content low viscosity
Food grade salt hydrochlorate.And industrial is mostly the big technical grade shitosan of ash content high viscosity, with such shitosan as former
The hydrochloride impurities that material is obtained are more, and are difficult to be dissolved in water, it is impossible to reach the index of hydrochloride.Compared to technical grade, food-grade shell
Glycan price is very high, and production cost is increased substantially.Industrial mass production cannot be applied to；In alcoholic media in tradition reaction
The middle reaction time is very long, and to be reacted in 50 DEG C of water-baths, and still not exclusively, hydrochloric acid and chitosan particle surface are reacted for reaction
Easily forming one layer of hydrochloride film obstruction reaction is carried out, and the hydrochloride that so reaction is obtained can not be dissolved completely in water, in addition it is also necessary to
Further filtering, influences production efficiency and yield；Organic solvent usage amount is big, and poor performance of keeping the safety in production, production cost is high, excessive
Hydrochloric acid discharge when can also cause environmental pollution.Because requiring that alcohol and shitosan volume are 50: 1 in the reaction, also need afterwards
With alcohol-pickled, therefore the alcohol that 1 ton of hydrochloride of production is used is 80 tons or so, and the recovered alcohol method for using at present is excessively numerous
It is trivial and dangerous.
The content of the invention
In view of the problem that above-mentioned prior art is present, it is an object of the invention to provide a kind of preparation side of chitosan hydrochloride
Method, reduces production cost, saves the reaction time, improves production yield.
The purpose of the present invention will be achieved by the following technical programs：
A kind of preparation method of chitosan hydrochloride, comprises the following steps：
1) pretreatment of shitosan：Technical grade shitosan is weighed in hydrochloric acid solution, stirring, dissolving, plus aqueous slkali regulation
PH, separates out precipitation, adds water successively respectively, organic solvent washing, obtains food-grade shitosan；
2) to step 1) add ethanol solution hydrochloride to react while stirring in the food-grade shitosan, filter to get filtrate and
Filter residue, the filtrate is standby, washs the filter residue, drying, crushing, obtains the chitosan hydrochloride.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 1) described in technical grade shitosan with it is described
The mass volume ratio of hydrochloric acid solution is 1g: 10ml.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 1) described in concentration of hydrochloric acid solution be 1%,
The aqueous slkali selects 5%NaOH, the organic solvent to select 95% ethanol.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 1) described in pH be 8-9.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 2) described in food-grade shitosan with it is described
The mass volume ratio of ethanol solution hydrochloride is 1: 4；The ethanol solution hydrochloride includes hydrochloric acid solution and ethanol, the hydrochloric acid solution
With the ethanol volume ratio 2: 5.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 2) in reaction temperature be normal temperature.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 2) the middle solvent selection for washing the filter residue
Ethanol, the filtrate and the ethanol participate in preparing again the reaction of the chitosan hydrochloride, circulate according to this.
A kind of preparation method of above-mentioned chitosan hydrochloride, wherein, step 2) described in filter residue and the ethanol matter
Amount volume ratio is 1g: 1.8ml~2.1ml.
Compared with prior art, a kind of preparation method of chitosan hydrochloride provided by the present invention, has reached following skill
Art effect：Requirement to raw material is very low, the shitosan of technical grade, and the food-grade shitosan obtained by pretreatment
Grain is smaller；By after pretreatment, the food-grade shitosan of expansion can within a short period of time under normal temperature and hydrochloric acid for technical grade shitosan
Reaction is complete, saves the reaction time, production yield is improve, while being not required to heating reduces production cost；In the preparation side
In method, step 2) in alcohol hydrochloric acid system can be allowed to be continuing with by way of adding hydrochloric acid, reach organic solvent and follow
The purpose that ring is utilized.
With reference to embodiment, specific embodiment of the invention is described in further detail, so that the technology of the present invention side
Case is more readily understood, grasps.
Specific embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this.Following realities
Experimental technique described in example is applied, unless otherwise specified, conventional method is；The reagent and material, unless otherwise specified,
Obtain from commercial channels.
Embodiment 1
1) pretreatment of shitosan：400g technical grade shitosans are weighed, is added in the hydrochloric acid solutions of 4000ml 1%, constantly
Stirring, dissolves 6 hours, adds 5%NaOH solution regulation pH to 8-9, now there is a large amount of Precipitations, and press filtration obtains careful breast
White shitosan, plus deionized water 1000ml washing by soaking is secondary, then adds 95% ethanol 400ml washing by soaking once, must eat
Grade shitosan 392g；
2) grade shitosan 392g is taken food, 1568ml ethanol solution hydrochloride (salt is added while stirring thereto at normal temperatures
Acid solution and ethanol volume ratio 2: 5), normal-temperature reaction 2 hours, filtering obtains filtrate 1150ml and filter residue 525g, and reserved filtrate is standby,
Filter residue is washed with ethanol 1000ml, is placed in 65 DEG C of vacuum drying chambers and is dried, be crushed to 80 mesh, obtain chitosan hydrochloride
438g；Because filtrate includes hydrochloric acid and alcohol, appropriate hydrochloric acid and alcohol are added by situation, for industrial production shitosan next time
Hydrochloride is used, and reaches the purpose that excessive hydrochloric acid and alcohol are recycled.
The conversion ratio that the food-grade shitosan of the present embodiment 1 is converted into chitosan hydrochloride is 99%, chitosan hydrochloride
Yield be 112% (yield by 100g shitosans produce how many grams of hydrochlorides in terms of).
The food-grade shitosan that draws is prepared in the present embodiment 1 shell can in batches be prepared according to actual production appointed condition and gathered
Sugared hydrochloride, it is also possible to which pretreated food-grade shitosan is disposably prepared into chitosan hydrochloride.
With technical grade shitosan as raw material, the property of water is dissolved in acid condition using shitosan, shitosan is dissolved in
Among 1% dilute hydrochloric acid solution, then adjusting pH to 8-9 with 5%NaOH again separates out it, is washed with deionized secondary, then uses
The ethanol organic solvent immersion rinsing of low concentration, before contrasting degraded, ash content is greatly lowered, and reaches food-grade shitosan and refers to
Mark is required, and the reacted food-grade shitosan expands, can at normal temperatures and hydrochloric acid reaction, for subsequent production provides guarantor
Card, course of dissolution is also degraded to shitosan, makes up to the physical and chemical index of chitosan hydrochloride.
Ethanol is used to react stirring 2 hours at normal temperatures as medium, plus excessive hydrochloric acid in the present invention, filtering drying is obtained
To chitosan hydrochloride, toward filtrate and ethanol supplement hydrochloric acid and can continuously add pretreated shitosan and reach and recycle
Purpose.
Embodiment 2
Food-grade shitosan manufactured in the present embodiment detection, testing result are shown in Table 1,
The food-grade shitosan testing result of table 1
As shown in Table 1：The technical grade shitosan ash content that embodiment 1 is used is high, and viscosity is big, by the present embodiment preparation method
Obtained food-grade shitosan reaches food-grade chitosan mass standard.
Embodiment 3
By food-grade shitosan (abbreviation A) of the present embodiment 1, commercially available food-grade shitosan (abbreviation B, the source in Shandong sea
Biological products Co., Ltd, product batch number：150808)；
1) 2 100ml graduated cylinders are taken, A and B is taken respectively and is put into wherein, appropriateness is tapped and is filled up at 100ml scales, it is accurate to claim
Amount 3 times, A product are respectively 74.95,75.03,75.04g, namely mean specific gravity is 0.75g/ml, and B product are respectively：29.83、
30.03rd, 30.05g, namely mean specific gravity is 0.3g/ml.
2) each 1g of A and B are taken respectively, and normal temperature is dissolved in the acetic acid aqueous solution of 100ml 1%, stirs, used after half an hour
NDJ--1E rotary viscosity design determinings its viscosity.
A product 3 times：84.59th, 85.19,85.20, namely average viscosity 85.30mpds；
B product 3 times：216.30th, 216.28,216.32 namely average viscosity 216.30mpds.
Table 2 A, B testing result table
| Index | A | B |
| Proportion | 0.75mg/ml | 0.3mg/ml |
| Viscosity | 85.20mpds | 216.30mpds |
From table 1, table 2, the food-grade shitosan that the preparation method of the pretreatment shitosan according to the present embodiment 1 is obtained
Quality has not only reached national standard, and the more commercially available proportion of the food-grade shitosan for preparing of the present embodiment 1 is high, and viscosity is low,
Reacted food-grade shitosan outward appearance expansion, shows to make in the presence of highly basic the food-grade shitosan of the present embodiment 1 to become
Property, its internal three, quaternary structure destruction causes high molecular food-grade shitosan to be easy to be reacted with hydrochloric acid, and be
The generation of high yield chitosan hydrochloride can be completed under normal temperature condition.
Embodiment 4 takes delicatessen food level shitosan 196g, and using the preparation method of embodiment 1, (specific steps refer to implementation
The step 2 of example 1)~step 5)) 204.50g chitosan hydrochlorides are prepared, yield is 104.3%.
The productivity ratio of the chitosan hydrochloride obtained with embodiment 4 is compared with the chitosan hydrochloride yield that embodiment 1 is obtained
Height, illustrates that the food-grade shitosan that the present embodiment 1 is obtained after pre-processing is complete with hydrochloric acid reaction, saves the reaction time, improves
Production yield.
Described above has shown and described some preferred embodiments of the invention, but as previously described, it should be understood that the present invention
Be not limited to form disclosed herein, be not to be taken as the exclusion to other embodiment, and can be used for various other combinations,
Modification and environment, and can be in invention contemplated scope described herein, by above-mentioned teaching or the technology or knowledge of association area
It is modified.And the change and change that those skilled in the art are carried out do not depart from the spirit and scope of the present invention, then all should be in this hair
In the protection domain of bright appended claims.
Claims (8)
1. a kind of preparation method of chitosan hydrochloride, it is characterised in that comprise the following steps：
1) pretreatment of shitosan：Technical grade shitosan is weighed in hydrochloric acid solution, stirring, dissolving, plus aqueous slkali regulation pH, analysis
Go out precipitation, add water successively respectively, organic solvent washing, obtain food-grade shitosan；
2) to step 1) add ethanol solution hydrochloride to react while stirring in the food-grade shitosan, filter to get filtrate and filter
Slag, the filtrate is standby, washs the filter residue, drying, crushing, obtains the chitosan hydrochloride.
2. a kind of preparation method of chitosan hydrochloride according to claim 1, it is characterised in that step 1) in, it is described
Technical grade shitosan is 1g: 10ml with the mass volume ratio of the hydrochloric acid solution.
3. a kind of preparation method of chitosan hydrochloride according to claim 2, it is characterised in that step 1) described in salt
Acid solutions are 1%, and the aqueous slkali selects 5%NaOH, the organic solvent to select 95% ethanol.
4. a kind of preparation method of chitosan hydrochloride according to claim 3, it is characterised in that step 1) described in pH
It is 8-9.
5. a kind of preparation method of chitosan hydrochloride according to claim 1, it is characterised in that step 2) described in eat
Grade shitosan is 1: 4 with the mass volume ratio of the ethanol solution hydrochloride；The ethanol solution hydrochloride include hydrochloric acid solution and
Ethanol, the hydrochloric acid solution and the ethanol volume ratio 2: 5.
6. a kind of preparation method of chitosan hydrochloride according to claim 5, it is characterised in that step 2) in reaction
Temperature is normal temperature.
7. a kind of preparation method of chitosan hydrochloride according to claim 6, it is characterised in that step 2) in washing institute
The solvent for stating filter residue selects ethanol, the filtrate and the ethanol to participate in preparing again the reaction of the chitosan hydrochloride, according to
This circulation.
8. a kind of preparation method of chitosan hydrochloride according to claim 7, it is characterised in that step 2) described in filter
Slag is 1g: 1.8ml~2.1ml with the mass volume ratio of the ethanol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154011A (en) * | 2020-02-25 | 2020-05-15 | 江西师范大学 | Method for preparing chitosan hydrochloride with extremely low viscosity |
| CN112675718A (en) * | 2020-12-08 | 2021-04-20 | 深圳先进技术研究院 | Water-soluble gel film with virus enrichment function and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029094A (en) * | 2007-04-12 | 2007-09-05 | 武汉大学 | Production of chitin chloride |
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2016
- 2016-12-30 CN CN201611261449.9A patent/CN106749762A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029094A (en) * | 2007-04-12 | 2007-09-05 | 武汉大学 | Production of chitin chloride |
Non-Patent Citations (1)
| Title |
|---|
| 侯春林等: "《几丁质与医学》", 28 February 2001, 上海科学技术出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154011A (en) * | 2020-02-25 | 2020-05-15 | 江西师范大学 | Method for preparing chitosan hydrochloride with extremely low viscosity |
| CN111154011B (en) * | 2020-02-25 | 2021-10-08 | 江西师范大学 | Method for preparing chitosan hydrochloride with extremely low viscosity |
| CN112675718A (en) * | 2020-12-08 | 2021-04-20 | 深圳先进技术研究院 | Water-soluble gel film with virus enrichment function and preparation method and application thereof |
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Application publication date: 20170531 |