CN1944468A - Process for preparing high deacetylized high molecular weight chitosan - Google Patents
Process for preparing high deacetylized high molecular weight chitosan Download PDFInfo
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- CN1944468A CN1944468A CN 200610134085 CN200610134085A CN1944468A CN 1944468 A CN1944468 A CN 1944468A CN 200610134085 CN200610134085 CN 200610134085 CN 200610134085 A CN200610134085 A CN 200610134085A CN 1944468 A CN1944468 A CN 1944468A
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- chitin
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- high molecular
- chitosan
- deacetylized
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Abstract
The present invention belongs to the field of chitosan preparing technology, and is one-step immersion process for preparing high molecular weight chitosan with high deacetylation degree. The present invention features that chitin and 40-60 wt% concentration alkali solution in certain ratio are mixed to produce deacetylation reaction at 100-130 deg.c and normal pressure or low pressure for 0.5-4 hr to prepare the high molecular weight chitosan with high deacetylation degree. The present invention has the advantages of low alkali consumption, short reaction time, low cost, simple process and environment friendship, and the prepared chitosan may be used in environment protection, food, Chinese medicine purification and other fields.
Description
Technical field
The invention belongs to the preparing technical field of chitosan, relate to a kind of preparation method of high deacetylized high molecular weight chitosan, a particularly a kind of step immersion process for preparing high deacetylized high molecular weight chitosan.
Background technology
Chitosan is the product of chitin deacetylase, and generally speaking, the N-ethanoyl of chitin removes more than 55% and just can be referred to as chitosan.Its preparation raw material chitin wide material sources, renewable.Because the chitosan of high deacetylized high molecular weight not only has the diluted acid that dissolves in that general chitosan has, nontoxic, biodegradable, be difficult for causing the advantage of secondary pollution, have performances such as good flocculation, complexing, film forming simultaneously, and be widely used in fields such as environmental protection, food, Chinese medicine purification, papermaking.
At present there is following shortcoming in the technology for preparing chitosan by chitin deacetylase: at first, it is big to consume alkali number, the production cost height.The chitosan technology for preparing chitin deacetylase stirs in a large amount of concentrated alkali solutions mostly carries out, and in order to obtain high deacetylized chitosan, need take repeatedly to change the complicated technology that acetyl is taken off in fresh alkali lye segmentation, causes the multiplication of sodium hydroxide concentration.This not only causes the chitosan production cost to rise (because consumption alkali cost has occupied the major part of chitosan raw materials cost), and causes serious secondary pollution.Secondly, Preparation of Chitosan processing condition such as temperature, the reaction times etc. are opposite to the deacetylation of chitosan and the impact effect of molecular weight.High reaction temperature helps removing of ethanoyl, but the products obtained therefrom molecular rupture is serious, causes molecular weight and molecular weight; Though the low chitosan product that can obtain higher molecular weight of temperature is unfavorable for removing of ethanoyl.So the chitosan of preparation high deacetylized high molecular weight is a difficult point problem.The process using alcohol that has at present-sodium hydroxide system perhaps adds quaternary surfactant and helps strengthening deacetylation as taking off acetoinices.In order to reduce the degraded of chitosan molecule chain, adding reductive agent such as thiophenol have been taked, sodium borohydride, measures such as nitrogen protection.Its shortcoming is that the affiliation that adds of taking off the acetyl auxiliary agent on the one hand causes production cost to raise, and can cause secondary pollution on the other hand.Adopt microwave heating to take off the technology of acetyl in addition, can prepare chitosan with high deacetylation degree at short notice, its shortcoming is that microwave heating speed is very fast, is prone to local superheating, and causes microwave leakage easily.
Summary of the invention
The technology technical problem that the present invention will solve is to overcome above-mentioned the deficiencies in the prior art, provides a kind of sodium hydroxide concentration few, and the reaction times is short, and technology has concurrently high deacetylized and cost effective method high molecular quality chitosan simple can the preparation.
Technical scheme of the present invention is: with chitin and sodium hydroxide solution mixing, to neutral, drying obtains the chitosan product in 0.5-10 hour after washing of 100-130 ℃ of reaction.
Naoh concentration is 40-60% among the present invention, and chitin quality and alkali lye volume ratio are 1 gram: the 2-7 milliliter.Preferred range is 1 gram: the 3-5 milliliter.
Be reflected among the present invention under normal pressure or the low pressure and carry out, pressure range 0.1-0.35Mpa, preferable range is 0.1-0.25MPa for the reaction pressure scope.
The reaction times is 0.5-4 hour among the present invention.
Its production stage of raw materials used chitin is followed successively by among the present invention: with shrimp, crab shell is raw material, after washing drying, is crushed to the 5-60 order, dry to neutrality with the HCl solution soaking after washing of 5-7wt%, obtains taking off the chitin of inorganic salt; With the soda boiling of 3-7wt% sodium hydroxide solution, washing and drying obtains taking off inorganic salt and proteinic chitin.
The raw material chitin can be to take off the chitin of inorganic salt or take off inorganic salt and proteinic chitin among the present invention.
The effect and the benefit of this law are:
(1) can prepare height and take off acetyl high-molecular weight chitosan
In the chitosan production process, the high deacetylized and high molecular of chitosan often can not have simultaneously.The chitosan of this law preparation has high molecular weight when assurance is high deacetylized.The deacetylating degree of chitosan 75%-93% of this law preparation, molecular weight 4.0 * 10
5-1.1 * 10
6
(2) reduce production costs
This law is taken off acetyl with minimum alkali lye with the chitin dipping and is prepared chitosan, and the 1g chitin only needs the sodium hydroxide solution of 3-5mL, carries out deacetylation one time, has significantly reduced sodium hydroxide concentration; It is short that this law is taken off the acetyl time, only needs 0.5-4h, and technology is simple, has reduced energy consumption, has shortened the production cycle; Need not other reaction promoters, reduced raw material consumption.
(3) environment, social benefit have been improved
This law alkali charge is few; Need not to carry out segmentation and take off acetyl, thereby omitted the intermediary water washing process; Need not to add other and take off the acetyl auxiliary agent.Thereby reduced alkali pollution, reduce water consumption has reduced secondary pollution.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Example 1
To wash exsiccant crab leg shell and be crushed to the 5-60 order, and claim 25g to add the hydrochloric acid soln 150mL of 6wt%, stirring at normal temperature 2 hours is washed to neutrality.Dry back adds 5wt% sodium hydroxide solution 100mL, 90 ℃ of stirring reaction 3h after washing dryings.Take by weighing the sodium hydroxide solution 10mL of dried material 2g adding 45wt%, keep reaction system pressure 0.1MPa (gauge pressure), 120 ℃ of reactions of temperature 1h.Product is washed to neutrality, and drying obtains the chitosan product, deacetylation 90%-93%, molecular weight 1.0 * 10
6-1.1 * 10
6
Example 2
To wash exsiccant crab leg shell and be crushed to the 5-60 order, and claim 25g to add the hydrochloric acid soln 150mL of 6wt%, stirring at normal temperature 2 hours, tap water is washed till neutrality, drying.Take by weighing the sodium hydroxide solution 6mL of dried material 2g adding 50wt%, keep reaction system pressure 0.1MPa (gauge pressure), 120 ℃ of reactions of temperature 1h.Product is washed to neutrality, and drying obtains the chitosan product, deacetylation 85%-89%, molecular weight 4.0 * 10
5-4.8 * 10
5
Example 3
To wash exsiccant crab leg shell and be crushed to the 5-60 order, and claim 25g to add the hydrochloric acid soln 150mL of 6wt%, stirring at normal temperature 2 hours, tap water is washed till neutrality.Dry back adds 5wt% sodium hydroxide solution 100mL, 90 ℃ of stirring reaction 3h after washing dryings.Take by weighing the sodium hydroxide solution 10mL of dried material 2g adding 47wt%, in 118 ℃ of synthesis under normal pressure 4h.Product is washed to neutrality, and drying obtains the chitosan product, deacetylation 75%-84%, molecular weight 7.0 * 10
5-8.4 * 10
5
Claims (6)
1. the preparation method of a high deacetylized high molecular weight chitosan is characterized in that may further comprise the steps:
(1) with chitin and sodium hydroxide solution mixing, to neutral, drying obtains the chitosan product in 0.5-10 hour after washing of 100-130 ℃ of reaction;
(2) naoh concentration is 40-60wt%, and chitin quality and alkali lye volume ratio are 1 gram: the 2-7 milliliter;
(3) being reflected at pressure range 0.1-0.35MPa carries out.
2. the preparation method of a kind of high deacetylized high molecular weight chitosan according to claim 1, its feature is that also the reaction times is 0.5-4 hour.
3. the preparation method of a kind of high deacetylized high molecular weight chitosan according to claim 1, its feature is that also naoh concentration is 40-60wt%, chitin quality and alkali lye volume ratio are 1 gram: the 3-5 milliliter.
4. the preparation method of a kind of high deacetylized high molecular weight chitosan according to claim 1, its feature is that also the reaction pressure scope is 0.1-0.25MPa.
5. according to the preparation method of claim 1,2,3 or 4 described a kind of high deacetylized high molecular weight chitosans, it is characterized in that described chitin is to take off the chitin of inorganic salt or take off inorganic salt and proteinic chitin.
6. the preparation method of a kind of high deacetylized high molecular weight chitosan according to claim 5, it is characterized in that described chitin production stage is: with shrimp, crab shell is raw material, through washing crushed after being dried to the 5-60 order, hydrochloric acid soln with 5-7wt% soaks after washing to neutral dry, obtains taking off the chitin of inorganic salt; With the soda boiling of 3-7wt% sodium hydroxide solution, washing and drying obtains taking off inorganic salt and proteinic chitin.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101340858A CN100560607C (en) | 2006-10-24 | 2006-10-24 | A kind of preparation method of high deacetylized high molecular weight chitosan |
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| CNB2006101340858A CN100560607C (en) | 2006-10-24 | 2006-10-24 | A kind of preparation method of high deacetylized high molecular weight chitosan |
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| CN1944468A true CN1944468A (en) | 2007-04-11 |
| CN100560607C CN100560607C (en) | 2009-11-18 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524635B (en) * | 2009-03-28 | 2010-09-08 | 大连理工大学 | Method for preparing chitosan/organo montmorillonite nanometer composite material |
| CN102090514A (en) * | 2010-11-22 | 2011-06-15 | 国家海洋局第一海洋研究所 | Compound immunopotentiator for left-eye and right-eye flounders and preparation method thereof |
| CN101492543B (en) * | 2008-01-25 | 2011-09-07 | 上海工程技术大学 | Process for preparing granule chitosan |
| CN102352568A (en) * | 2011-10-26 | 2012-02-15 | 芜湖南翔羽绒有限公司 | Arrangement method for down feathers with antibacterial function |
| CN103709269A (en) * | 2013-12-27 | 2014-04-09 | 中国科学院海洋研究所 | Method for preparing chitosan with ultrahigh deacetylation degree |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| CN109467617A (en) * | 2018-11-14 | 2019-03-15 | 黄河三角洲京博化工研究院有限公司 | A kind of clean preparation method of chitosan with high deacetylation degree |
| CN111320711A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Chitosan with high deacetylation degree and high molecular weight and preparation method thereof |
-
2006
- 2006-10-24 CN CNB2006101340858A patent/CN100560607C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492543B (en) * | 2008-01-25 | 2011-09-07 | 上海工程技术大学 | Process for preparing granule chitosan |
| CN101524635B (en) * | 2009-03-28 | 2010-09-08 | 大连理工大学 | Method for preparing chitosan/organo montmorillonite nanometer composite material |
| CN102090514A (en) * | 2010-11-22 | 2011-06-15 | 国家海洋局第一海洋研究所 | Compound immunopotentiator for left-eye and right-eye flounders and preparation method thereof |
| CN102090514B (en) * | 2010-11-22 | 2012-11-21 | 国家海洋局第一海洋研究所 | Compound immunopotentiator for flounders and preparation method thereof |
| CN102352568A (en) * | 2011-10-26 | 2012-02-15 | 芜湖南翔羽绒有限公司 | Arrangement method for down feathers with antibacterial function |
| CN102352568B (en) * | 2011-10-26 | 2013-06-19 | 芜湖南翔羽绒有限公司 | Arrangement method for down feathers with antibacterial function |
| CN103709269A (en) * | 2013-12-27 | 2014-04-09 | 中国科学院海洋研究所 | Method for preparing chitosan with ultrahigh deacetylation degree |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| CN108940373B (en) * | 2018-07-16 | 2021-07-09 | 广东石油化工学院 | Organic reaction catalyst based on shrimp and crab wastes and preparation method and application thereof |
| CN109467617A (en) * | 2018-11-14 | 2019-03-15 | 黄河三角洲京博化工研究院有限公司 | A kind of clean preparation method of chitosan with high deacetylation degree |
| CN109467617B (en) * | 2018-11-14 | 2020-10-23 | 黄河三角洲京博化工研究院有限公司 | Clean production method of chitosan with high deacetylation degree |
| CN111320711A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Chitosan with high deacetylation degree and high molecular weight and preparation method thereof |
| CN111320711B (en) * | 2020-04-28 | 2022-05-06 | 东华大学 | Chitosan with high deacetylation degree and high molecular weight and preparation method thereof |
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| CN100560607C (en) | 2009-11-18 |
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