CN101723989A - Method for hydrolyzing chitosan and chitin - Google Patents
Method for hydrolyzing chitosan and chitin Download PDFInfo
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- CN101723989A CN101723989A CN200810228127A CN200810228127A CN101723989A CN 101723989 A CN101723989 A CN 101723989A CN 200810228127 A CN200810228127 A CN 200810228127A CN 200810228127 A CN200810228127 A CN 200810228127A CN 101723989 A CN101723989 A CN 101723989A
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Abstract
The invention relates to a method for hydrolyzing chitosan and chitin to prepare monosaccharide and oligosaccharide by using ionic liquid as a reaction medium and using protonic acid as a catalyst under the condition of heating. Particularly, the method comprises the following steps: dissolving the chitosan or the chitin into the ionic liquid, adding acid and water into the solution, and heating the solution to perform reaction so as to obtain a hydrolysis product of which the yield reaches up to 70 percent based on total reducing sugar. The method has the advantages of mild operation condition, high reaction speed, reusability of the ionic liquid, low cost, simple process, environmental friendliness and the like, provides a new method for efficiently degrading the chitosan and the chitin, and develops a new path for preparing general oceanic chemicals and medicinal health-care products in large scale.
Description
Technical field
The present invention relates to the hydrolysis of chitosan and chitin, specifically a kind of is solvent with the ionic liquid, is catalyzer with acid, and hydrolyzing chitosan and chitin obtain the method for solubility monose and oligosaccharides.
Background technology
Chitin be by basic structural unit N-acetyl-D-glucosamine with β-1, the natural polysaccharide that the 4-glycosidic link connects and composes extensively is present in the cell walls of the shell of arthropods (as shrimp, crab) and fungi.Chitin year biosynthesizing amount reaches tens billion of tons in nature, is only second to Mierocrystalline cellulose, is the extremely abundant renewable resources of resource.Chitosan is the deacetylated product of chitin, contains D-glucosamine structural unit, is a kind of alkaline polysaccharide.Chitin and chitosan are white or faint yellow solid, water insoluble, most of organic solvents and diluted acid, but dissolve in dense mineral acid.
Degraded chitin and chitosan can obtain products such as D-glucosamine, N-acetyl-D-glucosamine and oligochitosan.The method of degraded chitin and chitosan has enzyme process, physics method and chemical method.Enzymic degradation (David P, Mark S.Carbohydr.Res., 1992,237,325) can carry out at normal temperatures, by product is few, environmental friendliness; But need the complicated pretreatment process, hydrolytic activity is low, speed is slow and enzyme costs an arm and a leg, easily inactivation, cost are very high.The mechanical degradation method mainly contains photodegradation method, radiation degradation method and sonication etc., though they have reduced the chemical reagent use, and environmental friendliness, product yield is low, and is of poor quality, is difficult to realize industrialization.
Chemical degradation method mainly contains acid degradation method and oxidation degradation method.Main concentrated hydrochloric acid hydrolysis chitin and the chitosan of using on the current industrial, the molecular weight distribution that obtains oligose is than broad (Defaye J.Adv.Carbohydr.Chem.Biochem., 1970,25,181), wherein the yield of D-glucosamine at 30～40% (Xu Yusheng, Wang Maoyuan. chemical and bonding, 2004, (4), 206).People such as Omura use phosphoric acid hydrolysis chitosan (Omura H, Uehara, K, Tanaka Y.Jpn.Patent.03-02203,1991), and obtaining principal product is that the polymerization degree is 6～8 oligosaccharides.People such as Hasegawa have proposed novel process, and acquisition water-soluble portion mean polymerisation degree is 17 oligosaccharides (Hasegawa M, Isogai A, Onabe F.Carbohydr.Polym., 1993,20,279), but hydrolysis time reached for 4～6 weeks.In addition, the vitriol oil, hydrofluoric acid and trichoroacetic acid(TCA) etc. can the catalyzed degradation chitosans.Though the concentrated acid hydrolysis can realize under lesser temps and normal pressure, also have a series of defectives: concentrated acid etching apparatus, hydrolyzed solution aftertreatment trouble, acid consume greatly, reclaim difficulty etc.
The all right oxidative degradation of chitin and chitosan, the representative reactions system is hydrochloric acid-Sodium Nitrite system (Furusaki E, Ueno Y, Sakairi N, et al.Carbohydr.Polym., 1996,29,29).Control by change Sodium Nitrite consumption and reaction times, oxidation degradation method can prepare the narrower water soluble oligosaccharide of molecular weight distribution or be used to extract monose.Because oxidation degradation method reaction conditions gentleness, selectivity is good, and the oligose for preparing specified molecular weight is had special advantages; But this method has been destroyed amino in degradation process, quality product is affected.With the hydrogen peroxide oxygenant chitin and chitosan (the Tanioka S that also can degrade, Matsui Y, Irie T, et al.Biosci.Biotechnol.Biochem., 1996,60,2001), but reaction needed just can obtain low molecular weight product under comparatively high temps and concentration of hydrogen peroxide, and processing condition are difficult to be grasped, reaction stability and poor repeatability, and have safety problem.
In sum, prior art degraded chitin and chitosan exist significantly not enough, and, poor repeatability, aftertreatment complexity low as productive rate, the chemical reagent usage quantity is big, corrodibility is strong, cost is high.In addition, the degraded product molecular weight distribution that most prior art obtains is too wide, and the monose yield is low.Therefore, still need and to develop more efficient, cleaning, chitin and chitosan hydrolyzate technology that the monose yield is high.
Summary of the invention
Be to improve chitosan and chitin hydrolysis efficiency, the object of the present invention is to provide a kind of easy and simple to handle, mild condition, eco-friendly novel method.
For achieving the above object, the technical solution used in the present invention is:
At first chitosan or chitin are dissolved in the ionic liquid, at protonic acid with above in the presence of the stoichiometric water, reacting by heating obtains products such as D-glucosamine, N-acetyl-D-glucosamine and oligochitosan.After reaction finishes, with cold water cancellation reaction, with ion exchange chromatography or size exclusive chromatography separation and purification hydrolysate.
The ionic liquid that the present invention uses is for have the ionic compound of better dissolving power to chitosan or crust.Constitute ion liquid positively charged ion and include but not limited to, alkyl imidazole type positively charged ion, alkyl pyridine type positively charged ion, quaternary amine type positively charged ion, season phosphine type positively charged ion, etc., alkyl imidazole type positively charged ion preferably; And negatively charged ion includes but not limited to, halide-ions, SO
4 2-, ClO
4 -, HSO
4 -, RSO
3 -(sulfonate ion), PO
4 3-, HPO
4 2-, H
2PO
4 -, HCO
2 -, CH
3CO
2 -, HO
2CCO
2 -, CF
3SO
3 -, [BF
4]
-, NTf
2 -Deng, halide-ions preferably.
The protonic acid that the present invention uses includes but not limited to mineral acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, perchloric acid etc.; With organic acid such as formic acid, acetate, toxilic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, trichoroacetic acid(TCA) etc., preferably sulfuric acid or hydrochloric acid.
The relative consumption condition of each material of the present invention is: chitosan (or chitin) and ion liquid mass ratio are that 0.06: 1～1: 1, water consumption are 2～10 times of chitosan (or chitin) quality.When ion liquid negatively charged ion did not contain ionizable proton, sour consumption was 0.1～2 times of chitosan (or chitin) quality; When ion liquid negatively charged ion contains ionizable proton, do not need additionally to use protonic acid.
The present invention's service temperature in hydrolytic process is that 60 ℃～140 ℃, reaction times are 2 minutes～24 hours.
The present invention adopts Imoto method (Imoto T, Yagishita K.Agric.Biol.Chem., 1971,35,1154) to measure glucosamine and oligosaccharides total sugar concentration in the hydrolyzed solution, represents with total reducing sugars.
The present invention has following advantage:
1, compare with enzymatic hydrolysis process, the present invention need not preprocessing process, and the catalyzer cost is low, the concentration of substrate height that hydrolysis rate is fast, the hydrolysis operation allows.
2, compare with traditional concentrated acid hydrolysis, the present invention's acid consumption is few, the concentration of substrate height that the hydrolysis operation allows, and the operational condition gentleness, less demanding to the erosion resistance of reactor, aftertreatment is simple, environmental friendliness, extent of reaction is easy to control, and cost is low.
3, compare with oxidative degradation, the present invention is to glycosidic link selectivity height, and is amino not oxidized, easy control of technology conditions, stability and good reproducibility, product chemical purity height.
4, compare with above all methods, the present invention is solvent with the ionic liquid, is reflected under the homogeneous phase condition to carry out, and speed is fast, and hydrolysis is abundant, the efficient height.
In a word, compared with prior art, present device is less demanding, raw material need not pre-treatment, acid consumption less, speed of response is fast, technology is easy, mild condition, environmental friendliness, extent of reaction is followed the tracks of easily and control etc.The present invention has opened up new way for efficiently utilizing marine organisms matter resource, has great application prospect aspect bio-based chemical and the biological health-care product obtaining.
Embodiment
Following examples help to understand this patent, but do not limit application of the present invention in any form.
The present invention relates to the ionic liquid is reaction medium, is the method that catalyzer hydrolyzing chitosan and chitin under heating condition prepare monose and oligosaccharides with the protonic acid.Specifically chitosan or chitin are dissolved in the ionic liquid, add acid and water, reacting by heating obtains hydrolysate, can be up to 70% in the total reducing sugars productive rate.The present invention has the operational condition gentleness, speed of response is fast, ionic liquid is reusable, cost is low, technology is simple, advantages of environment protection, for efficient degradation chitosan and chitin provide novel method, for the general thalassochemistry product of mass preparation and medical health care product have been opened up new way.
Ion liquid solvent preparation: reference literature (Li C, Zhao Z, Adv.Synth.Catal., 2007,349,1847; Webb P B, Sellin M F, Kunen T E, et al.J.Am.Chem.Soc., 2003,125,15577; Noda, A, Watanabe M.Electrochimica Acta.2000,45,1265; Sheldrake G N, Schleck, D.Green Chem.2007,9,1044.) and patent (WO00/16902) preparation and purifying ionic liquid, be used for the enforcement of patent of the present invention.
Embodiment 1
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add in the 4 gramion liquid chlorinated butyl Methylimidazoles (BMImCl) heating for dissolving.Add 0.054 gram water and 0.44 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 5 hours.Reaction finishes, the cold water cancellation, and analysis revealed total reducing sugars productive rate is 53%.
Embodiment 2
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.074 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 12 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 38%.
Embodiment 3
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.37 gram 98wt% sulfuric acid again, in 80 ℃ of reactions 12 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 28%.
Embodiment 4
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.37 gram 98wt% sulfuric acid again, in 110 ℃ of reactions 3.3 hours.Reaction finishes, and with cold water cancellation reaction, analysis revealed total reducing sugars productive rate is 57%.
Embodiment 5
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.37 gram 98wt% sulfuric acid again, in 140 ℃ of reactions 0.5 hour.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 58%.Embodiment 3～5 explanations, service temperature is high more, helps quick hydrolysis more and forms reducing sugar.
Embodiment 6
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.135 gram water and 0.44 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 8 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 62%.
Embodiment 7
In 10 milliliters of round-bottomed flasks, with 0.255 gram high molecular weight chitosan (Sigma company, article number: 419419) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.44 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 5 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 63%.
Embodiment 8
In 10 milliliters of round-bottomed flasks, with 0.305 gram chitin (Sigma company, article number: C7170) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.44 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 5 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 30%.
Embodiment 9
In 10 milliliters of round-bottomed flasks, with molecular weight chitosan in 2.04 grams (Sigma company, article number: 448877) add among the 4 gramion liquid B MImCl heating for dissolving.Add 4.0 gram 36wt% hydrochloric acid again, in 100 ℃ of reactions 5 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 54%.
Embodiment 10
In 10 milliliters of round-bottomed flasks, with 4.0 gram low-molecular weight chitoglycans (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.44 gram water and 2.1 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 6 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 51%.Present embodiment explanation hydrolysis can operate under very high concentration of substrate (50%) condition and traditional concentrated acid hydrolysis ratio has significant advantage.
Embodiment 11
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add in the 4 gramion liquid butyl methyl imidazoles acetate (BMImOAc) heating for dissolving.Add 0.15 gram 36wt% hydrochloric acid again, in 100 ℃ of reactions 8 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 52%.
Embodiment 12
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.45 gram 36wt% hydrochloric acid again, in 100 ℃ of reactions 6 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 64%.
Embodiment 13
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.37 gram 65wt% nitric acid again, in 100 ℃ of reactions 9 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 58%.
Embodiment 14
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.18 gram acetate again, in 100 ℃ of reactions 24 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 25%.
Embodiment 15
In 10 milliliters of round-bottomed flasks, with 0.305 gram chitin (Sigma company, article number: 22720) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.45 gram 36wt% hydrochloric acid, in 100 ℃ of reactions 8 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 28%.
Embodiment 16
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add in the 4 gramion liquid bromination butyl methyl imidazoles (BMImBr) heating for dissolving.Add 0.45 gram 36wt% hydrochloric acid again, in 100 ℃ of reactions 6 hours.Reaction finishes, and with cold water cancellation reaction, analysis revealed total reducing sugars productive rate is 70%.
Embodiment 17
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add 4 gramion liquid butyl methyl imidazole bisulfate (BMImHSO
4) in, heating for dissolving.Add 0.054 gram water again, in 100 ℃ of reactions 5 hours.Reaction finishes, and with cold water cancellation reaction, analysis revealed total reducing sugars productive rate is 40%.Because present embodiment has used the strongly-acid ionic liquid, solvent itself promptly possesses the function of protonic acid, therefore need not additionally to use protonic acid.
Embodiment 18
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add 4 gramion liquid chlorinated butyl pyridine ([C
4Py] Cl) in, heating for dissolving.Add 0.054 gram water and 0.44 gram 98wt% sulfuric acid again, in 100 ℃ of reactions 5 hours.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 51%.
Embodiment 19
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.15 gram 36wt% hydrochloric acid again, under 200W microwave radiation (frequency 2450MHz) condition, reacted 5 minutes.Reaction finishes, cold water cancellation reaction, and analysis revealed total reducing sugars productive rate is 50%.
Embodiment 20
In 10 milliliters of round-bottomed flasks, with 0.255 gram low-molecular weight chitoglycan (Sigma company, article number: 448869) add among the 4 gramion liquid B MImCl heating for dissolving.Add 0.054 gram water and 0.44 gram 98wt% sulfuric acid again, under 400W microwave radiation (frequency 2450MHz) condition, reacted 2 minutes.Reaction finishes, the cold water cancellation, and analysis revealed total reducing sugars productive rate is 47%.By embodiment 19 and embodiment 20 experimental results as can be seen, use microwave heating, can significantly shorten hydrolysis time, this is because ionic liquid dielectricity height, energy rapid absorption microwave energy, realize the body heat phase, cause reaction system to be heated quickly and evenly, thereby be better than traditional conduction heating mode.
Embodiment 21
Get the hydrolyzed solution of embodiment 4, transferring pH with 0.5mol/L NaOH is 8, with the good NH of activation
4 +The type Zeo-karb carries out sugar and separates H with ionic liquid
2The O wash-out detects sugar with aniline-pentanoic-phosphoric acid method.Collect the leacheate that only contains sugar, concentrate, record total reducing sugars concentration, calculating isolated yield is 52%.
Claims (8)
1. the method for hydrolyzing chitosan and chitin, it is characterized in that: being solvent with the ionic liquid, is raw material with chitosan or chitin, is in the presence of the water of 0.1～1.5 times of raw materials quality in quality, will be heated to 30 ℃～140 ℃ the reaction 2 minutes～24 hours, obtain hydrolysate.
2. in accordance with the method for claim 1, its feature also is: described ionic liquid is for to have better dissolving power to chitosan or crust, the ionic compound that constitutes by zwitterion, wherein positively charged ion be alkyl imidazole type positively charged ion, alkyl pyridine type positively charged ion, quaternary amine type positively charged ion and/or season phosphine type positively charged ion; Described ion liquid negatively charged ion is halide-ions, SO
4 2-, ClO
4 -, RSO
3 -(sulfonate ion), PO
4 3-, HCO
2 -, CH
3CO
2 -, CF
3SO
3 -, [BF
4]
-And/or NTf
2 -
3. according to claim 1 or 2 described methods, its feature also is: described ion liquid negatively charged ion is the polyprotonic acid acid ion HSO that contains ionizable proton
4 -, HPO
4 2-, H
2PO
4 -And/or HO
2CCO
2 -
4. in accordance with the method for claim 1, its feature also is: chitosan or chitin and ion liquid mass ratio are 0.06: 1～1: 1.
5. according to claim 1 and the described method of claim 2, its feature also is: add also in the reaction system that consumption is arranged is the protonic acid of 0.1～2 times of chitosan or chitin quality.
6. in accordance with the method for claim 5, its feature also is: described protonic acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and/or the perchloric acid in the mineral acid; Or the formic acid in the organic acid, acetate, toxilic acid, trifluoromethanesulfonic acid, trifluoroacetic acid and/or trichoroacetic acid(TCA).
7. in accordance with the method for claim 1, its feature also is: after hydrolysis reaction finished, with cold water cancellation reaction, the utilization ion exchange chromatography separated hydrolysate, obtains glucosamine and oligosaccharides.
8. in accordance with the method for claim 1, its feature also is: hydrolysis temperature is 60～140 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| CN102276663A (en) * | 2011-05-30 | 2011-12-14 | 南京工业大学 | Preparation method of glucosamine sulfate |
| CN104072634A (en) * | 2014-07-16 | 2014-10-01 | 中国科学院海洋研究所 | Preparation method for chitin oligosaccharides |
| CN104262506A (en) * | 2014-09-03 | 2015-01-07 | 大连泓业海洋生物科技有限公司 | Method for preparing chitosan by degrading chitin with ionic liquid |
| CN104497170A (en) * | 2014-12-26 | 2015-04-08 | 常州大学 | Method for preparing chitin oligosaccharide via homogeneous phase |
| CN105063135A (en) * | 2015-07-30 | 2015-11-18 | 重庆工商大学 | Chitosan hydrolysis method |
| CN106432538A (en) * | 2015-08-13 | 2017-02-22 | 中国科学院金属研究所 | Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides |
| CN110590870A (en) * | 2019-10-09 | 2019-12-20 | 山东润德生物科技有限公司 | Preparation method of high-purity N-acetylglucosamine |
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2008
- 2008-10-17 CN CN200810228127A patent/CN101723989A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| CN102276663A (en) * | 2011-05-30 | 2011-12-14 | 南京工业大学 | Preparation method of glucosamine sulfate |
| CN102276663B (en) * | 2011-05-30 | 2013-09-25 | 南京工业大学 | Preparation method of glucosamine sulfate |
| CN104072634A (en) * | 2014-07-16 | 2014-10-01 | 中国科学院海洋研究所 | Preparation method for chitin oligosaccharides |
| CN104072634B (en) * | 2014-07-16 | 2016-10-05 | 中国科学院海洋研究所 | A kind of chitin oligose preparing process |
| CN104262506A (en) * | 2014-09-03 | 2015-01-07 | 大连泓业海洋生物科技有限公司 | Method for preparing chitosan by degrading chitin with ionic liquid |
| CN104497170A (en) * | 2014-12-26 | 2015-04-08 | 常州大学 | Method for preparing chitin oligosaccharide via homogeneous phase |
| CN105063135A (en) * | 2015-07-30 | 2015-11-18 | 重庆工商大学 | Chitosan hydrolysis method |
| CN106432538A (en) * | 2015-08-13 | 2017-02-22 | 中国科学院金属研究所 | Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides |
| CN110590870A (en) * | 2019-10-09 | 2019-12-20 | 山东润德生物科技有限公司 | Preparation method of high-purity N-acetylglucosamine |
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