CN109467617B - Clean production method of chitosan with high deacetylation degree - Google Patents
Clean production method of chitosan with high deacetylation degree Download PDFInfo
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- CN109467617B CN109467617B CN201811352625.9A CN201811352625A CN109467617B CN 109467617 B CN109467617 B CN 109467617B CN 201811352625 A CN201811352625 A CN 201811352625A CN 109467617 B CN109467617 B CN 109467617B
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- chitosan
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- deacetylation degree
- chitin
- alkali liquor
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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
Abstract
The invention belongs to the technical field of ocean chemical engineering, and relates to a method for efficiently preparing chitosan with high deacetylation degree under the condition of lower alkali concentration. The invention realizes the method for preparing the chitosan with the deacetylation degree of more than 95 percent by directly adopting the chitin under the lower concentration of the alkali liquor and realizes the repeated use of the alkali liquor. Compared with the prior art, the production efficiency of the invention is improved by 2-3 times, no waste liquid is generated in the process, and clean production of chitosan is realized.
Description
Technical Field
The invention relates to a method for efficiently preparing chitosan with high deacetylation degree under the condition of lower alkali concentration, realizes reutilization of alkali liquor and clean production of chitosan, and belongs to the technical field of ocean chemical engineering.
Background
The chitosan is biological polysaccharide formed by connecting glucosamine and N-acetylglucosamine by beta-1, 4 glycosidic bond, is the only polysaccharide with positive charge in the nature, and has the characteristics of biodegradability, antibiosis, flocculation, film formation and the like. At present, chitosan is widely applied to the fields of food, medicine, environmental protection and the like. In addition, chitosan can be further degraded into chitosan oligosaccharide, and the chitosan oligosaccharide can induce crops to generate systemic resistance, improve the yield and quality of agricultural products, and has great application potential in the agricultural field.
The chitosan is a deacetylation product of chitin, generally sheet chitin is used as a raw material, and 80-90% of acetyl groups in the chitin are removed by reacting 50-60% NaOH solution at 95-100 ℃ for 6-10h to obtain the chitosan. There are three problems with this process: (1) the chitosan obtained by the process has the deacetylation degree of about 85 percent generally, and the requirement of the medical industry on the deacetylation degree of the chitosan is difficult to meet. (2) The reaction time is too long, and the production efficiency is low. (3) The reaction is generally carried out in an open container, the smell is heavy, and certain environmental pollution and occupational health risks are brought.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-efficiency, environment-friendly and simple clean production method of chitosan with high deacetylation degree.
The invention directly takes the chitin as the raw material for producing the chitosan, and compared with the preparation of the chitosan with high deacetylation degree by using the chitosan with low deacetylation degree, the invention omits the process of preparing the chitosan with low deacetylation degree by using the chitin, improves the material-liquid ratio and improves the reaction speed and the production efficiency. The chitosan deacetylation process is carried out in a vacuum reaction kettle, so that the problem of environmental protection does not exist, and the health of operators is facilitated. The removal speed and removal rate of acetyl groups of the chitin are remarkably improved under the condition of low temperature and negative pressure, and the alkali liquor after the reaction is recycled, so that the utilization rate of the alkali liquor is improved, the environmental pollution is reduced, and the aim of green pollution-free production is really achieved.
The purpose of the invention can be realized by the following technical scheme: a clean production method of chitosan with high deacetylation degree comprises the following specific steps:
(1) adding chitin into alkali liquor with the mass fraction of 10% -25% for soaking pretreatment;
(2) transferring the pretreated chitin feed liquid to a reaction kettle for negative pressure reaction, and cooling the feed liquid to room temperature after the reaction is finished;
(3) carrying out solid-liquid separation on the cooled feed liquid, washing the solid to be neutral, and drying to obtain a chitosan finished product;
the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
The inventors have found that by the soaking treatment, the subsequent deacetylation treatment can be made easier; the chitosan obtained without soaking treatment has low deacetylation degree and poor solubility in dilute acid, and the chitosan obtained after soaking treatment has good quality, which is shown in high deacetylation degree and light color. The soaking treatment can make the subsequent reaction easier and can reduce the alkali concentration required for preparing the chitosan with high deacetylation degree. On the basis of ensuring the quality of chitosan and reducing the cost, the mass ratio of chitin to alkali liquor is 1:5-1:10, the pretreatment temperature is 20-50 ℃, and the pretreatment time is 0.5-5 h.
Transferring the pretreated chitin feed liquid to a reaction kettle for negative pressure reaction, wherein in order to ensure better reaction effect, the pressure is controlled to be-0.075-0.085 MPa, the temperature is controlled to be 60-85 ℃, and the reaction time is controlled to be 60-120 min.
After the reaction is finished, cooling the feed liquid to room temperature for solid-liquid separation, washing the solid to be neutral, and drying to obtain a chitosan finished product;
in addition, the liquid in the step (3) is combined, concentrated and added with alkali to the mass fraction of 10% -25%, and the alkali can be reused in the step (1) for the next batch of chitin pretreatment and deacetylation.
In the invention, after the alkali liquor is recycled for 10-13 times, the alkali liquor needs to be concentrated and filtered, then crystallization treatment is carried out, and crystallization is carried out for 2-3 times repeatedly to obtain alkali solid with higher purity, and the alkali solid is continuously used together with new alkali.
The invention firstly adopts the alkali liquor to pretreat the chitin, so that part of the alkali liquor enters the chitin, the subsequent reaction can be easier, and under the same reaction condition, the deacetylation degree of the chitosan obtained by pretreatment is higher than that of the chitosan obtained without pretreatment, the deacetylation degree is greatly improved, and the production efficiency is effectively improved. In addition, the reaction is carried out in a vacuum reaction kettle, the reaction temperature can be reduced under the condition of negative pressure, the deacetylation reaction is more thorough under the same temperature, the whole process is carried out in the vacuum reaction kettle, no smell is emitted, and the environmental pollution is reduced; the alkali liquor recovered in the reaction is used repeatedly, and after the alkali liquor is used to a certain extent, the alkali liquor is crystallized and purified, the purified and crystallized alkali solid can be continuously used together with new alkali, no waste liquid is generated, the purposes of environmental protection and no pollution are really achieved, and the method is a clean production method of the chitosan with high deacetylation degree. Compared with the prior art, the chitosan with the deacetylation degree of more than 95% can be obtained by adopting the alkali liquor with lower mass fraction, and the requirements of the fields of medical treatment and the like on the chitosan with high deacetylation degree can be met.
Detailed Description
Example 1
Weighing 500g of chitin, adding the chitin into 2.5L of NaOH solution with the mass fraction of 15%, and soaking for 3h at 40 ℃. Then transferring the materials into a 5L vacuum reaction pressure kettle, wherein the vacuum pressure is-0.078 MPa, and the temperature is 70 ℃ for reaction for 2 h. After the reaction, 2.0L of NaOH solution was recovered by suction filtration. The chitosan is washed to be neutral by tap water and dried for 4 hours at 105 ℃ to obtain 408g of chitosan. And (3) concentrating the washing liquor to 300mL in vacuum, combining and recovering the alkali liquor and the concentrated alkali liquor to obtain 2.3L (the concentration is 15%) of NaOH alkali liquor, and supplementing 30g of solid NaOH and 200mL of water to obtain 2.5L of NaOH solution with the mass fraction of 15%, wherein the NaOH solution is used for preparing the next batch of chitosan.
The quality index of the chitosan sample is detected according to GB29941-2013, and the result is as follows:
example 2
Weighing 500g of chitin, adding the chitin into 2.5L of KOH solution with the mass fraction of 20%, and soaking for 3h at 50 ℃. Then the materials are transferred to a 5L vacuum reaction kettle, the vacuum pressure is-0.080 MPa, and the temperature is 73 ℃ for reaction for 2 h. After the reaction, 2.1L of KOH solution was recovered by suction filtration. Washing chitosan with tap water to neutrality, and drying at 105 deg.C for 4 hr to obtain 400g chitosan. And (3) concentrating the washing solution to 300mL in vacuum, combining the recovered alkali solution and the concentrated alkali solution to obtain 2.4L (the concentration is 19%) of KOH alkali solution, and supplementing 44g of solid KOH and 100mL of water to obtain 2.5L of KOH solution with the mass fraction of 20% for preparing the next batch of chitosan. Through detection, the deacetylation degree of the chitosan is 95.6%, and other indexes meet the requirements of GB 29941-2013.
Example 3
Weighing 500g of chitin, adding the chitin into 2.5L of KOH solution with the mass fraction of 25%, and soaking for 1h at 50 ℃. Then the material is transferred to a 5L vacuum reaction kettle, the vacuum pressure is-0.085 MPa, and the temperature is 80 ℃ for reaction for 1.5 h. After the reaction, 2.1L of KOH solution was recovered by suction filtration. Washing chitosan with tap water to neutrality, and drying at 105 deg.C for 4 hr to obtain 397g chitosan. And (3) concentrating the washing solution to 300mL in vacuum, combining the recovered alkali solution and the concentrated alkali solution to obtain 2.4L of KOH alkali solution (with the concentration of 23%), adding 73g of solid KOH and 100mL of water to obtain 2.5L of KOH solution with the mass fraction of 45%, and using the KOH solution in the next batch of chitosan preparation. Through detection, the deacetylation degree of the chitosan is 97.6%, and other indexes meet the requirements of GB 29941-2013.
Example 4
Weighing 500g of chitin, adding the chitin into 2.5L of NaOH solution with the mass fraction of 25%, and soaking for 1h at 50 ℃. Then the material is transferred to a 5L vacuum reaction kettle, the vacuum pressure is-0.085 MPa, and the temperature is 83 ℃ for reaction for 2 h. After the reaction, 2.0L of NaOH solution was recovered by suction filtration. Washing chitosan with tap water to neutrality, and drying at 105 deg.C for 4 hr to obtain 395g chitosan. The washings were concentrated to 300mL in vacuo. And combining the recovered alkali liquor and the concentrated alkali liquor to obtain 2.4L (the concentration is 23%) of KOH alkali liquor, and supplementing 73g of solid NaOH and 100mL of water to obtain 2.5L of NaOH solution with the mass fraction of 45%, wherein the NaOH solution is used for preparing the next batch of chitosan. Through detection, the deacetylation degree of the chitosan is 98.1%, and other indexes meet the requirements of GB 29941-2013.
Claims (3)
1. A clean production method of chitosan with high deacetylation degree is characterized by comprising the following specific steps:
(1) adding chitin into alkali liquor with the mass fraction of 10% -25% for soaking pretreatment;
(2) transferring the pretreated chitin feed liquid to a reaction kettle for negative pressure reaction, and cooling the feed liquid to room temperature after the reaction is finished;
(3) carrying out solid-liquid separation on the cooled feed liquid, washing the solid to be neutral, and drying to obtain a chitosan finished product;
the mass ratio of the chitin to the alkali liquor is 1:5-1: 10; the pretreatment temperature is 20-50 ℃, and the pretreatment time is 0.5-5 h; during the negative pressure reaction, the pressure is controlled to be-0.075-0.085 MPa, the temperature is controlled to be 60-85 ℃, and the reaction time is controlled to be 60-120 min.
2. The clean production method of chitosan with high deacetylation degree as claimed in claim 1, wherein the method further comprises the following steps:
(4) and (4) combining the liquid obtained in the step (3), concentrating and adding alkali until the mass fraction is 10% -25%, and reusing the liquid obtained in the step (1).
3. The clean production method of chitosan with high deacetylation degree as claimed in claim 1, wherein: the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
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Citations (7)
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| WO2005019272A1 (en) * | 2003-07-25 | 2005-03-03 | Universite Lyon 1 Claude Bernard | Method of producing totally-desacetylated chitosan with a high molecular weight |
| US7074612B2 (en) * | 2002-03-06 | 2006-07-11 | National Institute Of Agrobiological Sciences | Insect cell primary culture medium, extracellular matrix, and process of preparing an insect culture cell line in a short period of time using the medium and matrix |
| CN1944468A (en) * | 2006-10-24 | 2007-04-11 | 大连理工大学 | Process for preparing high deacetylized high molecular weight chitosan |
| CN101289518A (en) * | 2008-06-06 | 2008-10-22 | 石勇 | Method for preparing chitin and process for preparing chitosan by using chitin |
| CN101717455A (en) * | 2009-12-15 | 2010-06-02 | 武汉大学 | Method for preparing heparinoid polysaccharide |
| 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 |
| CN105837708A (en) * | 2016-05-16 | 2016-08-10 | 南京理工大学泰州科技学院 | Method for preparing chitosan with shrimp and crab shells as raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215084C (en) * | 2002-03-19 | 2005-08-17 | 周家武 | Technology for producing high chitosan, microcrystall chitosan and water-soluble low molecular chitosan |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7074612B2 (en) * | 2002-03-06 | 2006-07-11 | National Institute Of Agrobiological Sciences | Insect cell primary culture medium, extracellular matrix, and process of preparing an insect culture cell line in a short period of time using the medium and matrix |
| WO2005019272A1 (en) * | 2003-07-25 | 2005-03-03 | Universite Lyon 1 Claude Bernard | Method of producing totally-desacetylated chitosan with a high molecular weight |
| CN1944468A (en) * | 2006-10-24 | 2007-04-11 | 大连理工大学 | Process for preparing high deacetylized high molecular weight chitosan |
| CN101289518A (en) * | 2008-06-06 | 2008-10-22 | 石勇 | Method for preparing chitin and process for preparing chitosan by using chitin |
| CN101717455A (en) * | 2009-12-15 | 2010-06-02 | 武汉大学 | Method for preparing heparinoid polysaccharide |
| 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 |
| CN105837708A (en) * | 2016-05-16 | 2016-08-10 | 南京理工大学泰州科技学院 | Method for preparing chitosan with shrimp and crab shells as raw material |
Non-Patent Citations (2)
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| The effect of reaction time and temperature during heterogenous alkali deacetylation on degree of deacetylation and molecular weight of resulting chitosan;Tsaih ML et al.;《JOURNAL OF APPLIED POLYMER SCIENCE》;20031231;第88卷(第13期);第2917-2923页 * |
| 甲壳质制壳聚糖脱乙酰度条件研究;王运生等;《化工生产与技术》;20070630;第14卷(第3期);第23-26页 * |
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