CN1401652A - Process for industrial production of oligochitose and chitooligose - Google Patents
Process for industrial production of oligochitose and chitooligose Download PDFInfo
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- CN1401652A CN1401652A CN 01126457 CN01126457A CN1401652A CN 1401652 A CN1401652 A CN 1401652A CN 01126457 CN01126457 CN 01126457 CN 01126457 A CN01126457 A CN 01126457A CN 1401652 A CN1401652 A CN 1401652A
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- chitosan
- degrading enzyme
- acid
- lipase
- carbohydrase
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Abstract
An industrial process for preparing oligochitose or chitoligose by degradating chitosan with complex enzyme includes specifically opening the beta (1,4) glycoside bond of chitosan with complex enzyme, separating out oligothitose in alkaline condition, freezing, centrifugal dewatering, vacuum drying, superfiltering for removing enzyme, nano-filtering for dewatering and freeze drying. Its advantages are high quality of product and low cost.
Description
Technical field
The present invention relates to the suitability for industrialized production technology of low chitose and oligochitosan, relate to particularly that chitosan is degraded and separation and purification obtains the method for oligose or oligochitosan under the effect of non-specificity prozyme.
Background technology
Chitosan is the deacetylated product of chitin.Chitin extensively is present in crustacean such as shrimp, crab and insect, algae and the bacterium, is to be only second to cellulosic second largest natural high moleculer eompound in the world, and a year biosynthesizing amount reaches more than billions of tons.Chitin is because of its chemical property torpescence, and solubility property is very poor, directly uses very limited; And chitin is carried out the deacetylated chitosan of handling the back gained; but because of the existence of amino active group in the molecular structure; its dissolving properties, chemical property all greatly for a change are with a wide range of applications at aspects such as food, medicine, daily-use chemical industry, environmental protection, agriculturals.The macromolecular molecular weight of chitosan is usually about hundreds of thousands of, interaction because of inside and outside hydrogen bond in its molecule can only be dissolved in the dilute acid soln of minority, and can not be directly soluble in water, if its molecular weight is reduced, then can obtain low chitose and direct water-soluble oligochitosan by appropriate means.Low chitose and oligochitosan have many functional propertys that are better than chitosan, are one of focuses of chitosan and products thereof development research.
At present, the preparation method of low chitose and oligochitosan mainly contains acid hydrolyzation, oxidation style and enzymolysis process three major types, and several method cuts both ways.Acid hydrolyzation is the degradation of chitosan method of studying the earliest, as far back as the fifties, document Journal Am Chemistry Society (1957,79:5046) just report, also there is recent years multiple acid hydrolyzation to be seen in report, as peroxyacetic acid method, vitriol oil method, hydrofluoric acid method etc., but these method environmental pollutions are more serious, and wayward reaction end; Oxidation style is representative with the hydrogen peroxide oxidation process, mainly contains H
2O
2Method, H
2O
2-HCl method, H
2O
2-NaOCl
2Method, ClO
2Method etc. (university chemistry, 1999, Vol.14,2:36), shortcoming is easily to produce by product.Enzymolysis process is to use specificity chitoanase and non-narrow spectrum other enzyme, carries out the degraded of chitosan as proteolytic enzyme, carbohydrase, lipase etc., the various enzymes that can be used for enzymolysis process have kind more than 30 (Carbohydrate Research, 1995,268:143).Enzymolysis process reaches the degraded purpose by β (1, the 4) glycosidic link of the chitosan that ftractures specifically, does not have other reaction reagents and add in whole degradation process, does not have other byproduct of reaction and generates, and is the Perfected process of degradation of chitosan.The specificity chitoanase can be realized the specificity degraded to chitosan, but studies show that at present its degradation efficiency is not very high, causes production cost higher.Non-specificity enzymolysis is studied by many people, document " 1996 15 phases of Wuxi light industry college journal " has reported that it is several ten thousand low chitose that professor Xia Wenshui of Wuxi light industry university adopts the wheat germ Lipase-promoted Hydrolysis of Chitosan to obtain average molecular weight, document " Carbohydr.Res.1992; 237:325 " has reported that people such as Pantaleone study cellulase and papoid, dextranase under certain condition to the Degradation of chitosan, but it is several ten thousand low chitose that the result has also only obtained average molecular weight, and can not make degradation of chitosan be more low-molecular-weight oligochitosan.Therefore providing a kind of new low chitose and the production method of oligochitosan, is that people institute is very expected.
Summary of the invention
The technical issues that need to address of the present invention provide and a kind ofly adopt prozyme that chitosan is degraded and obtain the method for low chitose and oligochitosan, are the defective of more low-molecular-weight oligochitosan to overcome the degradation of chitosan that can not make that prior art exists.
Said low chitose of the present invention and oligochitosan are that a kind of average molecular weight is the zymolyte of 500～100,000 chitosan.
Method of the present invention comprises the steps:
(1) preparation of low chitose:
Get chitosan and be dissolved in the acid solution, add down degrading enzyme, react 2～8 hours, add alkali and be neutralized to alkalescence at 20～80 ℃, washing, freezing, thaw, centrifugal, vacuum-drying, pulverizing promptly obtains average molecular weight and is 5000～100,000 low chitose.
Said acid can be selected from hydrochloric acid or acetic acid and composition thereof, said alkali can be selected from a kind of and composition thereof in sodium hydroxide or the potassium hydroxide, the weight ratio of degrading enzyme and chitosan is 1: 1～300, and said degrading enzyme is the mixture of lipase and carbohydrase, and its weight ratio is 0.1～10;
Preferred lipase is optional uses a kind of from the aspergillus niger, and preferred carbohydrase is optional uses a kind of from the Trichoderma;
(2) preparation of oligochitosan:
Get chitosan and be dissolved in the acid solution, add down degrading enzyme, react 2～8 hours at 20-80 ℃, be warming up to 80 ℃～100 ℃ 5～30 minutes, cooling is filtered, ultrafiltration, nanofiltration, lyophilize, pulverizing promptly obtains average molecular weight and is 500～5000 oligochitosan.
Said acid can be selected from a kind of and composition thereof in hydrochloric acid or the acetic acid, and the weight ratio of degrading enzyme and chitosan is 1: 1～300, and said degrading enzyme is the mixture of lipase and carbohydrase, and its weight ratio is 0.1～10;
Preferred lipase is optional uses a kind of from the aspergillus niger, and preferred carbohydrase is optional uses a kind of from the Trichoderma;
By above-mentioned disclosed technical scheme as seen, the present invention utilizes prozyme with chitosan β (1, the 4) glycosidic link that ftractures specifically, makes it become low chitose or oligochitosan, obtains finished product after separation and purification.And utilize the character of the water insoluble and alkaline solution of low chitose, and under alkaline condition, from the degradation of chitosan reaction solution, separate out, utilize the linkage force of freezing for destroying low chitose and water, centrifugal to deviate from moisture, vacuum-drying then.Utilize the oligochitosan molecular weight less, and the molecular weight of enzyme is bigger, dezymotizes by ultrafiltration; Utilize the perviousness of water, by the nanofiltration dehydration, lyophilize obtains finished product.Selected raw material is cheap and easy to get, and production technique is feasible, not only can obtain the product than good quality, and production cost is lower.
Embodiment
Below will elaborate to the specific embodiment of the present invention, but embodiment does not limit protection scope of the present invention by embodiment.
Embodiment 1
Getting 10 kilograms of chitosans, to be dissolved in 240 L concentration be in 1% the acetum, 250 kilograms in the colloidal solution of formation 4%, add 100 gram prozymes (lipase: amylase=1: 5, this lipase and amylase are selected from Wuxi biotechnology company limited of outstanding energy section product), reaction is 3 hours under 50 ℃, add sodium hydroxide and be neutralized to alkalescence, be refrigerated to-18 ℃, it is centrifugal to thaw, 50 ℃ of vacuum-dryings, pulverize, obtain average molecular weight and be 9 kilograms of 35000 low chitoses.
The products obtained therefrom quality index is as follows:
| Project | Low chitose |
| Deacetylation | ?93％ |
| Moisture | ?4％ |
| Ash | ?0.3％ |
| Color and luster | This white |
| Granularity | Greater than 100 orders |
| Average molecular weight | ?35000 |
| Heavy metal | The food sanitation requirement |
| Bacterium | The food sanitation requirement |
Embodiment 2
Getting 5 kilograms of chitosans, to be dissolved in 240 L concentration be in 1% the acetum, forms 250 kilograms in 2% colloidal solution, adds 100 gram prozyme (lipase: amylase=1: 10, this lipase and amylase are selected from Wuxi biotechnology company limited of outstanding energy section product), 50 ℃ of down reactions 3 hours, be warming up to more than 95 ℃ cooling 15 minutes, filter, the membrane ultrafiltration of molecular weight cut-off about 10,000, nanofiltration, lyophilize, pulverize, obtain average molecular weight and be 4 kilograms of 1000 oligochitosans.
The products obtained therefrom quality index is as follows:
| Project | Oligochitosan |
| Deacetylation | ?90％ |
| Moisture | ?6％ |
| Ash | ?0.2％ |
| Color and luster | White |
| Granularity | Greater than 100 orders |
| Average molecular weight | ?1000 |
| Tile Width | ?1.4 |
| Heavy metal | The food sanitation requirement |
| Bacterium | The food sanitation requirement |
Claims (8)
1. the industrialized preparing process of a low chitose is characterized in that, this method comprises the steps:
Get chitosan and be dissolved in the acid solution, add down degrading enzyme, react 2～8 hours, add alkali and be neutralized to alkalescence at 20～80 ℃, washing, freezing, thaw, centrifugal, vacuum-drying, pulverizing promptly obtains average molecular weight and is 5000～100,000 low chitose.
2. the method for claim 1 is characterized in that, said acid can be selected from hydrochloric acid or acetic acid and composition thereof, and said alkali can be selected from a kind of and composition thereof in sodium hydroxide or the potassium hydroxide, and the weight ratio of degrading enzyme and chitosan is 1: 1～300.
3. the method for claim 1 is characterized in that, said degrading enzyme is the mixture of lipase and carbohydrase, and its weight ratio is 0.1～10.
4. as claim 1,2 or 3 described methods, it is characterized in that lipase selects for use a kind of from the aspergillus niger, carbohydrase to select a kind of from the Trichoderma for use.
5. the industrialized preparing process of an oligochitosan is characterized in that, this method comprises the steps:
Get chitosan and be dissolved in the acid solution, add down degrading enzyme, react 2～8 hours at 20-80 ℃, be warming up to 80 ℃～100 ℃ 5～30 minutes, cooling is filtered, ultrafiltration, nanofiltration, lyophilize, pulverizing promptly obtains average molecular weight and is 500～5000 oligochitosan.
6. method as claimed in claim 5 is characterized in that, said acid can be selected from a kind of and composition thereof in hydrochloric acid or the acetic acid, and the weight ratio of degrading enzyme and chitosan is 1: 1～300.
7. method as claimed in claim 5 is characterized in that, said degrading enzyme is the mixture of lipase and carbohydrase, and its weight ratio is 0.1～10.
8. as claim 5,6 or 7 described methods, it is characterized in that lipase selects for use a kind of from the aspergillus niger, carbohydrase to select a kind of from the Trichoderma for use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011264578A CN1177856C (en) | 2001-08-14 | 2001-08-14 | Process for industrial production of oligochitose and chitooligose |
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| CNB011264578A CN1177856C (en) | 2001-08-14 | 2001-08-14 | Process for industrial production of oligochitose and chitooligose |
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| CN1401652A true CN1401652A (en) | 2003-03-12 |
| CN1177856C CN1177856C (en) | 2004-12-01 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320124C (en) * | 2005-09-15 | 2007-06-06 | 武汉大学 | Preparation of low-molecular weight chitoglycan or chitooligose |
| CN1321191C (en) * | 2004-11-10 | 2007-06-13 | 中国科学院大连化学物理研究所 | Chitosn producing process with immobilized enzyme |
| CN1332984C (en) * | 2004-03-17 | 2007-08-22 | 海南大学 | Method for preparing chitosan/chitose in molecular weight narrow distributed |
| CN100386345C (en) * | 2006-06-05 | 2008-05-07 | 孝感学院 | Preparation process of chito oligosaccharace hydrochloride |
| CN100441692C (en) * | 2006-08-17 | 2008-12-10 | 孝感学院 | Chitosan oligosaccharide sulphate and preparation method thereof |
| CN100447161C (en) * | 2005-05-16 | 2008-12-31 | 海南大学 | Method of microwave assistant degradation for preparing narrow molecular weight distributed Chitosan poly oligosaccharide |
| CN100447162C (en) * | 2005-05-16 | 2008-12-31 | 海南大学 | Method of PACu-A5 adsorption microwave assistant degradation for preparing narrow molecular weight distributed Chitosan poly oligosaccharide |
| CN102993332A (en) * | 2011-12-09 | 2013-03-27 | 中国科学院大连化学物理研究所 | Preparation process of chitin oligose |
| CN103330083A (en) * | 2013-06-28 | 2013-10-02 | 句容市郭庄镇南河农庄 | Composite feed for improving immunity of herring and preparation method thereof |
| CN106367456A (en) * | 2016-08-29 | 2017-02-01 | 扬州日兴生物科技股份有限公司 | Chitosan coupling production method by virtue of microwave viscosity reduction and enzymatic degradation |
| CN106498004A (en) * | 2016-11-04 | 2017-03-15 | 扬州日兴生物科技股份有限公司 | In the method that shrimp and crab shells digest production oligochitosan as raw material acidolysis |
| CN107652373A (en) * | 2017-09-26 | 2018-02-02 | 广州华大生物科技有限公司 | A kind of preparation method of low-molecular weight chitoglycan |
| CN108552534A (en) * | 2018-04-08 | 2018-09-21 | 大连军门保健食品有限公司 | With the complex polysaccharide electuary and preparation method thereof for adjusting intestinal flora function |
| CN108913735A (en) * | 2018-08-03 | 2018-11-30 | 广东药科大学 | A method of chitosan oligosaccharide is prepared using lipase |
| CN109438103A (en) * | 2019-01-10 | 2019-03-08 | 江苏心实肥业集团有限公司 | A kind of chitosan oligosaccharide crop nutrition spray fertilizer and preparation method thereof |
| WO2020037866A1 (en) * | 2018-08-20 | 2020-02-27 | 广东药科大学 | Low molecular weight chitooligosaccharide and preparation method therefor |
| CN111718972A (en) * | 2020-07-27 | 2020-09-29 | 安亦臣(武汉)健康科技有限公司 | Preparation method of chitosan oligosaccharide with specific polymerization degree |
-
2001
- 2001-08-14 CN CNB011264578A patent/CN1177856C/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332984C (en) * | 2004-03-17 | 2007-08-22 | 海南大学 | Method for preparing chitosan/chitose in molecular weight narrow distributed |
| CN1321191C (en) * | 2004-11-10 | 2007-06-13 | 中国科学院大连化学物理研究所 | Chitosn producing process with immobilized enzyme |
| CN100447161C (en) * | 2005-05-16 | 2008-12-31 | 海南大学 | Method of microwave assistant degradation for preparing narrow molecular weight distributed Chitosan poly oligosaccharide |
| CN100447162C (en) * | 2005-05-16 | 2008-12-31 | 海南大学 | Method of PACu-A5 adsorption microwave assistant degradation for preparing narrow molecular weight distributed Chitosan poly oligosaccharide |
| CN1320124C (en) * | 2005-09-15 | 2007-06-06 | 武汉大学 | Preparation of low-molecular weight chitoglycan or chitooligose |
| CN100386345C (en) * | 2006-06-05 | 2008-05-07 | 孝感学院 | Preparation process of chito oligosaccharace hydrochloride |
| CN100441692C (en) * | 2006-08-17 | 2008-12-10 | 孝感学院 | Chitosan oligosaccharide sulphate and preparation method thereof |
| CN102993332A (en) * | 2011-12-09 | 2013-03-27 | 中国科学院大连化学物理研究所 | Preparation process of chitin oligose |
| CN102993332B (en) * | 2011-12-09 | 2016-02-03 | 中国科学院大连化学物理研究所 | A kind of method preparing chitin oligo saccharide |
| CN103330083A (en) * | 2013-06-28 | 2013-10-02 | 句容市郭庄镇南河农庄 | Composite feed for improving immunity of herring and preparation method thereof |
| CN106367456A (en) * | 2016-08-29 | 2017-02-01 | 扬州日兴生物科技股份有限公司 | Chitosan coupling production method by virtue of microwave viscosity reduction and enzymatic degradation |
| CN106498004A (en) * | 2016-11-04 | 2017-03-15 | 扬州日兴生物科技股份有限公司 | In the method that shrimp and crab shells digest production oligochitosan as raw material acidolysis |
| CN107652373A (en) * | 2017-09-26 | 2018-02-02 | 广州华大生物科技有限公司 | A kind of preparation method of low-molecular weight chitoglycan |
| CN107652373B (en) * | 2017-09-26 | 2018-11-27 | 广州华大生物科技有限公司 | A kind of preparation method of low-molecular weight chitoglycan |
| CN108552534A (en) * | 2018-04-08 | 2018-09-21 | 大连军门保健食品有限公司 | With the complex polysaccharide electuary and preparation method thereof for adjusting intestinal flora function |
| CN108913735A (en) * | 2018-08-03 | 2018-11-30 | 广东药科大学 | A method of chitosan oligosaccharide is prepared using lipase |
| CN108913735B (en) * | 2018-08-03 | 2019-09-03 | 广东药科大学 | A method of chitosan oligosaccharide is prepared using lipase |
| WO2020024374A1 (en) * | 2018-08-03 | 2020-02-06 | 广东药科大学 | Method for preparing chitosan oligosaccharide by using lipase |
| WO2020037866A1 (en) * | 2018-08-20 | 2020-02-27 | 广东药科大学 | Low molecular weight chitooligosaccharide and preparation method therefor |
| CN109438103A (en) * | 2019-01-10 | 2019-03-08 | 江苏心实肥业集团有限公司 | A kind of chitosan oligosaccharide crop nutrition spray fertilizer and preparation method thereof |
| CN111718972A (en) * | 2020-07-27 | 2020-09-29 | 安亦臣(武汉)健康科技有限公司 | Preparation method of chitosan oligosaccharide with specific polymerization degree |
| CN111718972B (en) * | 2020-07-27 | 2023-07-04 | 安亦臣(武汉)健康科技有限公司 | Preparation method of chitosan oligosaccharide with specific polymerization degree |
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| Publication number | Publication date |
|---|---|
| CN1177856C (en) | 2004-12-01 |
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