CN106397631A - Chitosan oligosaccharide production method - Google Patents
Chitosan oligosaccharide production method Download PDFInfo
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- CN106397631A CN106397631A CN201610886433.0A CN201610886433A CN106397631A CN 106397631 A CN106397631 A CN 106397631A CN 201610886433 A CN201610886433 A CN 201610886433A CN 106397631 A CN106397631 A CN 106397631A
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- hydrogen peroxide
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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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- 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
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering and particularly relates to a chitosan oligosaccharide production method. Aiming at the problems of low degraded chitosan yield and poor product solubility in the prior art, the method for producing chitosan oligosaccharides through oxidation of chitosan with hydrogen peroxide is provided. The method comprises specific steps as follows: chitosan and hydrogen peroxide are subjected to a reaction at the temperature of 50-90 DEG C, filtered and dried, and white chitosan oligosaccharides are prepared. The molecular weight of the chitosan oligosaccharides produced with the method is low, and the solubility is up to 80 g per 100 g of water; degradation is performed in neutral media and a product contains no inorganic salt; reducing substances are added to a reaction solution, and residual hyperoxide can be completely eliminated; three wastes in production are prevented, the product yield is high, biological activity is high, color and luster are improved, and toxicology tests prove that the product belongs to a non-poisonous material.
Description
Technical field
The invention belongs to technical field of fine is and in particular to a kind of production method of oligo-chitosan.
Background technology
The preparation method of oligo-chitosan mainly has edman degradation Edman, synthetic method and fermentation method.At present synthetic method and fermentation method by
In there is many technical barriers, do not enable industrialization.Degraded point acid hydrolyzation, oxidative degradation and enzymatic degradation again.Acid hydrolyzation reacts
Often relatively violent, wayward, poor selectivity, and the products obtained therefrom degree of polymerization is relatively low, or even it is degraded to monosaccharide；Meanwhile, acidolysis
Product isolates and purifies difficulty, and oligopolymerization chitosan sugared content is not high, and yield is generally below 20%, therefore acid hydrolyzation typically can not be industrially
Use.Enzyme process high cost is it is also difficult to realize industrialization.
The research of prior art useful oxidizing substance Synergistic degradation shitosan, the oligo-chitosan water solublity of gained is relatively
Good, the present invention intends providing a kind of production method of oligo-chitosan, and the method yield is high, and more preferably, dissolubility is more for product dissolubility
High.
Content of the invention
The technical problem to be solved in the present invention be in prior art degraded shitosan yield is low, product dissolubility is imperfect
Problem.
The present invention solve technical problem technical scheme be：A kind of production method of oligo-chitosan is provided.The method bag
Include following steps：
A, to in stirring, the enamel reaction still of chuck and temperature measuring equipment, add the deionized water less than total measurement (volume) half,
Add the shitosan of total amount 2/3rds while stirring, add continuation stirring 10min；Then the disposable addition four in reactor
The hydrogen peroxide of/mono- amount, stirs 10min；Chuck send vapour to heat up, and is warming up to 50 DEG C of beginning timing, allows reactant liquor in reactor
2h is reacted in the range of 50 DEG C～90 DEG C；Then thereto stream plus a quarter amount hydrogen peroxide, make reactant liquor 50 DEG C～
React between 90 DEG C；Then it is alternately added the shitosan of remaining two part of 1/6th amount and the hydrogen peroxide of a quarter amount；
Hydrogen peroxide be stream plus, hydrogen peroxide adds speed controlling in 0.1kg～0.5kg/min, reaction temperature 50 DEG C～90 DEG C it
Between and can not have and emit a pot phenomenon；Add hydrogen peroxide and continue insulation, reaction is entirely molten and reactant liquor is clarified as terminal with shitosan；Reach
To after terminal, reacting liquid temperature is down to 60 DEG C, adds reducing substanceses, and keeps 2h；Chuck leads to cooling water, makes reactor interior temperature
Degree drops to less than 40 DEG C, puts into reactant liquor in storage tank in filtration；
B, 95vol% ethanol is placed in another freezing tank cooling；Take and freeze reactant liquor, slowly add while stirring in proportion
Enter in the ethanol freezing；It is gently mixed 1～10min after adding reactant liquor；Place 15～60min, filter, filter cake low temperature
The washing with alcohol of 99vol%, drains, then is dried with Circulating Air Dry Oven, pulverizes and sieves to obtain white oligo-chitosan.
Wherein, in the production method of above-mentioned oligo-chitosan, the shitosan adding described in step a is 5 for mass fraction
～35% shitosan.
Wherein, in the production method of above-mentioned oligo-chitosan, described in step a when reaching reaction end, hydrogen peroxide
The mol ratio adding with shitosan is 1.3～5.5:1.
Wherein, in the production method of above-mentioned oligo-chitosan, the reducing substances described in step a are ascorbic acid.
Wherein, in the production method of above-mentioned oligo-chitosan, the reacting liquid temperature freezing described in step b be 0～
10℃.
Wherein, in the production method of above-mentioned oligo-chitosan, the 95vol% ethanol described in step b is to cooling -30～0
℃ .
Wherein, in the production method of above-mentioned oligo-chitosan, the weight of the 95vol% ethanol described in step b and reactant liquor
Than for 1～4：1.
Wherein, in the production method of above-mentioned oligo-chitosan, the ethanol temperature of the washing filter cake described in step b is -30
DEG C～10 DEG C.
Wherein, in the production method of above-mentioned oligo-chitosan, the washing with alcohol 1 of 99vol% of the filter cake described in step b
～5 times.
Wherein, in the production method of above-mentioned oligo-chitosan, the drying temperature described in step b is 40～60 DEG C.
Wherein, in the production method of above-mentioned oligo-chitosan, the drying time described in step b is 2～8h.
Beneficial effects of the present invention are：The oligo-chitosan molecular weight that the inventive method produces is low, completely water-soluble, dissolubility
Up to 80g/100g water；The oxidative degradation of the present invention is carried out in neutral medium, and product does not contain in inorganic salts, and reactant liquor
With the addition of reducing substances, the peroxide of remaining be completely eliminated it is ensured that no peroxide is remaining in product, product is easily separated,
Non-pollutant discharge；The waste gas of the inventive method production process non-hazardous environment, waste liquid and useless solidss produce, and product is through toxicity
Learn test and belong to non-poisonous material.In addition, the present invention analyses to produce oligo-chitosan using alcohol in a low temperature of initiating, produce and obtain white
Shitosan product, more conventional faint yellow or yellow shitosan outward appearance substantially improves, and has higher biological activity, is made with it
For oligo-chitosan seed coat agent, for seed treatment, show that the biological activity of this oligo-chitosan is higher, and have good
Function that is antibacterial, sterilizing, promote germination.
Specific embodiment
The present invention provides a kind of production method of oligo-chitosan, and specific operation process is as follows：
A, to in stirring, the enamel reaction still of chuck and temperature measuring equipment, add the deionized water less than total measurement (volume) half,
Add the shitosan of total amount 2/3rds while stirring, add continuation stirring 10min；Then the disposable addition four in reactor
The hydrogen peroxide of/mono- amount, stirs 10min；Chuck send vapour to heat up, and is warming up to 50 DEG C of beginning timing, allows reactant liquor in reactor
2h is reacted in the range of 60 DEG C～80 DEG C；Then thereto stream plus a quarter amount hydrogen peroxide, make reactant liquor 60 DEG C～
React between 80 DEG C；Then it is alternately added the shitosan of remaining two part of 1/6th amount and the hydrogen peroxide of a quarter amount；
Hydrogen peroxide be stream plus, hydrogen peroxide adds speed controlling in 0.1kg～0.5kg/min, it is ensured that reaction temperature is 60 DEG C～80
Between DEG C and can not have and emit a pot phenomenon；Add hydrogen peroxide and continue insulation, its chitosan mass fraction is 5%～35%, reach anti-
When answering terminal, n (hydrogen peroxide):N (shitosan)=1.3～5.5, reaction is entirely molten and reactant liquor was clarified as end with shitosan
Point；After reaching terminal, reacting liquid temperature is down to 60 DEG C, adds reducing substanceses, to eliminate the peroxide of remaining, and keeps 2h；
Then chuck leads to cooling water, makes reactor temperature drop to less than 40 DEG C, then puts into reactant liquor in freezing tank in filtration
Cooling, reactant liquor is cooled to 0 DEG C～10 DEG C.
B, volume fraction is placed in another freezing tank for 95% ethanol it is cooled to -30 DEG C～0 DEG C, take freeze certain
The reactant liquor of amount, by m (ethanol)：M (reactant liquor)=1～4 ratio slowly adds in the ethanol freezing while stirring；When plus
It is gently mixed 1～10min after complete reactant liquor；Place 15～60min, most of material separating out will sink to bottom, and filter, filter cake
The washing with alcohol being 99% with low temperature volume fraction 1～5 time, drains, and filter cake 40 DEG C～60 DEG C drying 2h of Circulating Air Dry Oven～
8h.Pulverize and sieve to obtain white oligo-chitosan.
Below by embodiment, explanation is further explained to the specific embodiment of the present invention, but is not protected model
Enclose and be limited in scope described in embodiment.
Embodiment 1
To in the enamel reaction still with stirring, chuck and temperature measuring equipment for the 500L, adding 200kg deionized water, starting stirring, while stirring
Mix side and add 20kg 100 mesh shitosan, add continuation stirring 10min.Then disposably addition mass fraction is thereto
27.5% hydrogen peroxide 20kg, stirs 10min.The mass fraction of hydrogen peroxide added by this reaction is 27.5%.Chuck send vapour
Heat up, be warming up to 60 DEG C of beginning timing in reactor, allow reactant liquor in 60 DEG C～70 DEG C scope inside holding 2h.Then thereto
Stream plus 20kg hydrogen peroxide, make reactant liquor react between 60 DEG C～70 DEG C.Hydrogen peroxide adds 5kg shitosan after adding.Continue
Afterflow adds 20kg hydrogen peroxide, adds 5kg shitosan after adding.Stream plus remaining 20kg hydrogen peroxide, hydrogen peroxide adds
Speed controlling is in 0.1kg～0.5kg/min it is ensured that reaction temperature and can not have and emits a pot phenomenon between 60 DEG C～70 DEG C.Add
So that reacting liquid temperature is down to 60 DEG C and add 1kg ascorbic acid after hydrogen peroxide 1h, and keep 3h.Then chuck leads to cooling water,
Make reactor temperature drop to 40 DEG C, then in filtration, reactant liquor is put into freezing tank and lower the temperature 5 DEG C.Volume fraction is 95%
Ethanol is placed in another freezing tank lowers the temperature -5 DEG C.The volume fraction freezing is that 95% ethanol 120kg moves in Settling tanks, takes
The reactant liquor 60kg freezing, slowly adds in the ethanol freezing while stirring.It is gently mixed after adding reactant liquor
1min.Place 15min, most of material separating out will sink to bottom, and filter, and filter cake is 99% with -10 DEG C of volume fraction
Washing with alcohol twice, is drained, and filter cake Circulating Air Dry Oven dries 6h at 60 DEG C, pulverizes and sieves to obtain 80 whitish eye color oligo-chitosan
（Oligochitosan）17.472kg.
Embodiment 2
To in the enamel reaction still with stirring, chuck and temperature measuring equipment for the 500L, adding 250kg deionized water, starting stirring, while stirring
Mix side and add 25kg 100 mesh shitosan, add continuation stirring 10min.Then disposably add 25kg hydrogen peroxide thereto,
Stirring 10min.The mass fraction of hydrogen peroxide added by this reaction is 27.5%.Chuck send vapour to heat up, and is warming up to 60 in reactor
DEG C start timing, allow reactant liquor in 70 DEG C～80 DEG C scope inside holding 2h.Then stream adds 25kg hydrogen peroxide thereto, makes anti-
Liquid is answered to react between 70 DEG C～80 DEG C.Hydrogen peroxide adds 6.25kg shitosan after adding.Continue stream plus 25kg hydrogen peroxide,
6.25kg shitosan is added after adding.Stream plus remaining 20kg hydrogen peroxide, hydrogen peroxide add speed controlling 0.1kg～
0.5kg/min is it is ensured that reaction temperature and can not have and emits a pot phenomenon between 70 DEG C～80 DEG C.Reaction is made after adding hydrogen peroxide 1h
Liquid temp is down to 60 DEG C and is added 1.5kg ascorbic acid, and keeps 3h.Then chuck leads to cooling water, so that reactor temperature is dropped to
40 DEG C, then in filtration, reactant liquor is put into freezing tank and lower the temperature 5 DEG C.Volume fraction is placed in another freezing tank for 95% ethanol
- 5 DEG C of middle cooling.The volume fraction freezing is that 95% ethanol 180kg moves in Settling tanks, takes the reactant liquor freezing
60kg, slowly adds in the ethanol freezing while stirring.It is gently mixed 1min after adding reactant liquor.Place 15min, greatly
The material that part separates out will sink to bottom, filter, -10 DEG C of volume fraction of filter cake be 99% washing with alcohol twice, drain,
Filter cake Circulating Air Dry Oven dries 6h at 60 DEG C, pulverizes and sieves to obtain 80 whitish eye color oligo-chitosan（Oligochitosan）.Remaining reaction
Liquid is pressed above-mentioned ratio and is separated out, and by said process operation, there are white oligo-chitosan 20.647kg.
Embodiment 3
To in the enamel reaction still with stirring, chuck and temperature measuring equipment for the 1000L, add 500kg deionized water, start stirring, side
Stirring side adds 40kg 100 mesh shitosan, adds continuation stirring 10min.Then disposably add 40kg peroxidating thereto
Hydrogen, stirs 10min.Chuck send vapour to heat up, and is warming up to 60 DEG C of beginning timing, allows reactant liquor in 60 DEG C～70 DEG C scopes in reactor
Inside holding 2h.Then stream adds 40kg hydrogen peroxide thereto, so that reactant liquor is reacted between 60 DEG C～70 DEG C.Hydrogen peroxide adds
10kg shitosan is added after complete.Continue stream plus 40kg hydrogen peroxide, after adding, add 10kg shitosan.Stream plus remaining 40kg
Hydrogen peroxide, hydrogen peroxide adds speed controlling in 0.1kg～0.5kg/min it is ensured that reaction temperature is between 60 DEG C～70 DEG C
And can not have and emit a pot phenomenon.So that reacting liquid temperature is down to 60 DEG C and add 2Kg ascorbic acid after adding hydrogen peroxide 1h, and keep
3h.Then chuck leads to cooling water, makes reactor temperature drop to 40 DEG C, then in filtration, reactant liquor is put into freezing tank fall
5 DEG C of temperature.Volume fraction is placed in another freezing tank for 95% ethanol and lowers the temperature -5 DEG C.The volume fraction freezing is 95% ethanol
120kg moves in Settling tanks, takes the reactant liquor 60kg freezing, slowly adds in the ethanol freezing while stirring.When plus
It is gently mixed 1min after complete reactant liquor.Place 15min, most of material separating out will sink to bottom, and filter, and filter cake uses -10 DEG C
Volume fraction be 99% washing with alcohol twice, drain, filter cake Circulating Air Dry Oven 50 DEG C dry 7h, pulverize and sieve
80 whitish eye color oligo-chitosan（Oligochitosan）, remaining reaction liquid is pressed aforesaid operations and is processed, and there are 36.571kg white oligopolymerization chitosan
Sugar（Oligochitosan）.
Compliance test result
The mensure of dissolubility
Add 100mL distilled water in the 200mL there-necked flask equipped with reflux condensing tube, be separately added into 90g embodiment 1～3 institute
The oligo-chitosan obtaining.Flask is placed on magnetic stirrer, is stirred and heated to 50 DEG C, keep 5min, be then cooled to 20
Under conditions of DEG C, place 2h, now beaker bottom should have a little precipitation, otherwise should adjust the addition of oligo-chitosan.With moving
Liquid pipe draws the saturated solution of about 10mL top clarification, is placed in the weighing botle of known quality, weighs weighing botle and saturated solution
Weight, then passes through heating and totally and dries to constant weight solvent volatilization.
Calculate the dissolubility of oligo-chitosan by following formula：
In formula：
S dissolubility, unit is gram (g)；
m0The numerical value of weighing botle quality, unit is gram (g)；
m1Saturated solution and the numerical value of weighing botle quality, unit is gram (g)；
m2Solute and the numerical value of weighing botle quality, unit is gram (g).
The oligo-chitosan that the above embodiment of the present invention is produced is measured by said method, and dissolubility is respectively
82.33g, 80.26g, 81.74g, all more than 80g/100g water, dissolubility is high for dissolubility.
Biological activity determination
The oligo-chitosan that application embodiments of the invention 1～3 are produced is prepared for oligo-chitosan seed coat agent, by this seed coat agent
Soaking corn Nongda108 seed, observes after placing 10 d, the surface of the seed biofilm is intact, has no and substantially comes off.10 are used after 15 d
Amplify its physical behavior of sem observation again（Particularly filming performance）No significant change.The corn seed being processed with this seed coat agent, 4 d
Germinating energy is 97%；7 d germination percentages are 98%, and blank sample 4 d germinating energy is 74%, and 7 d germination percentages are only 77%.
Additionally, being tested to cotton planting process with this seed coat agent, experimental result see table.
Table 1 distinct methods are to cotton seed application effect synopsis
As seen from the above table, the oligo-chitosan that the inventive method is produced has high biological activity.Using the inventive method
The seed coat agent of the oligo-chitosan preparation being produced has good antibacterial, sterilization, promotes germination effect, with blank
Group is compared, and improves corn seed germination rate 21%；In addition, this seed coat agent can effectively preventing disease pest control, strong sprout of keeping a full stand of seedings, thus promoting to plant
Seedling healthy growth, improves crop yield.The seed coat agent of the oligo-chitosan preparation being produced using the inventive method processes Cotton Gossypii
Seed, compared with conventional seed dressing, every 100 m2Yield can increase by 4.8 kg.
Claims (10)
1. a kind of production method of oligo-chitosan is it is characterised in that comprise the following steps：
A, to in stirring, the enamel reaction still of chuck and temperature measuring equipment, add the deionized water less than total measurement (volume) half,
Add the shitosan of total amount 2/3rds while stirring, add continuation stirring 10min；Then the disposable addition four in reactor
The hydrogen peroxide of/mono- amount, stirs 10min；Chuck send vapour to heat up, and is warming up to 50 DEG C of beginning timing, allows reactant liquor in reactor
2h is reacted in the range of 50 DEG C～90 DEG C；Then thereto stream plus a quarter amount hydrogen peroxide, make reactant liquor 50 DEG C～
React between 90 DEG C；Then it is alternately added the shitosan of remaining two part of 1/6th amount and the hydrogen peroxide of a quarter amount；
Hydrogen peroxide be stream plus, hydrogen peroxide adds speed controlling in 0.1kg～0.5kg/min, reaction temperature 50 DEG C～90 DEG C it
Between and can not have and emit a pot phenomenon；Add hydrogen peroxide and continue insulation, reaction is entirely molten and reactant liquor is clarified as terminal with shitosan；Reach
To after terminal, reacting liquid temperature is down to 60 DEG C, adds reducing substanceses, and keeps 2h；Chuck leads to cooling water, makes reactor interior temperature
Degree drops to less than 40 DEG C, puts into reactant liquor in storage tank in filtration；
B, 95vol% ethanol is placed in another freezing tank cooling；Take and freeze reactant liquor, slowly add while stirring in proportion
Enter in the ethanol freezing；It is gently mixed 1～10min after adding reactant liquor；Place 15～60min, filter, filter cake low temperature
The washing with alcohol of 99vol%, drains, then is dried with Circulating Air Dry Oven, pulverizes and sieves to obtain white oligo-chitosan.
2. oligo-chitosan according to claim 1 production method it is characterised in that：The shell adding described in step a
The shitosan that polysaccharide is 5～35% for mass fraction.
3. oligo-chitosan according to claim 1 production method it is characterised in that：Reaching described in step a is anti-
When answering terminal, the mol ratio that hydrogen peroxide is added with shitosan is 1.3～5.5:1.
4. oligo-chitosan according to claim 1 production method it is characterised in that：Reduzate described in step a
Matter is ascorbic acid.
5. oligo-chitosan according to claim 1 production method it is characterised in that：Freezing described in step b
Reacting liquid temperature be 0～10 DEG C.
6. oligo-chitosan according to claim 1 production method it is characterised in that：95vol% described in step b
Ethanol is to -30～0 DEG C of cooling.
7. oligo-chitosan according to claim 1 production method it is characterised in that：95vol% described in step b
The weight of ethanol and reactant liquor is than for 1～4：1.
8. oligo-chitosan according to claim 1 production method it is characterised in that：Washing filter described in step b
The ethanol temperature of cake is -30 DEG C～10 DEG C.
9. oligo-chitosan according to claim 1 production method it is characterised in that：Filter cake described in step b is used
The washing with alcohol of 99vol% 1～5 time.
10. oligo-chitosan according to claim 1 production method it is characterised in that：Drying temperature described in step b
Spend for 40～60 DEG C, drying time is 2～8h.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180993A (en) * | 2011-05-05 | 2011-09-14 | 大连鑫蝶泓祥甲壳素有限公司 | Production method of chitooligosaccharide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180993A (en) * | 2011-05-05 | 2011-09-14 | 大连鑫蝶泓祥甲壳素有限公司 | Production method of chitooligosaccharide |
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Application publication date: 20170215 |