CN101200505B - Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell - Google Patents
Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell Download PDFInfo
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- CN101200505B CN101200505B CN2007101685735A CN200710168573A CN101200505B CN 101200505 B CN101200505 B CN 101200505B CN 2007101685735 A CN2007101685735 A CN 2007101685735A CN 200710168573 A CN200710168573 A CN 200710168573A CN 101200505 B CN101200505 B CN 101200505B
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Abstract
A preparation method of chitosan with high deacetylation degree and high viscosity through shrimp shell includes the following steps: microwave drying and fresh-keeping are carried out on the raw materials; the deproteinization reaction between the shrimp shell and alkali solution with 5 to 10 percents concentration should be heated by microwave; the deacetylation reaction between chitin and NaOH solution with 45 to 50 percents concentration should be heated by microwave. After all the reactions, ethanol solution of the chitosan and the NaOH is obtained in the present invention for further deacetylation reaction. The present invention has the advantages of less acid and alkali use, short reaction time, economy, environmental protection, etc. The chitosan prepared by the present invention is the white or light yellow powder with high deacetylation degree and high viscosity, which can be widely applied in the fields of environmental protection, food, medicine, etc.
Description
Technical field
The present invention relates to a kind of method for preparing chitosan, especially relate to a kind of shrimp shell that utilizes and prepare method high deacetylized and the high viscosity chitosan.
Background technology
Chitin is a macromolecule polysaccharide like a kind of chemical structure and the fiber-like, and it extensively is present in the cell walls of the duricrust of insect, Crustacean and mushroom.Chitin is after taking off acetyl, and its product is a chitosan.Chitosan has favorable biological degradability, biocompatibility, and has no side effect.Because chitin deacetylase degree and viscosity are high more, its functional will be strong more, as produce high-quality flocculation agent, viable cell and enzyme immobilization, make reverse osmosis membrane and ultra-filtration membrane etc. and often need use high deacetylized and full-bodied chitosan.Yet in traditional chitosan production technique, because time and temperature when being difficult to hold Deacetylation of Crab Chitin, the high deacetylized characteristic of its chitin and high viscosity characteristic are difficult to have both simultaneously, and it is big that existing technology exists consumption alkali acid consumption, need a large amount of problems such as organic solvent, so product cost is than higher.
In addition, factory is when producing above-mentioned biologically active substance in enormous quantities, owing to be subjected to the restriction of production schedule, raw material overstocks especially easily.In order not allow raw material corruption, rotten, it is fresh-keeping mostly to adopt refrigerated storage now.But refrigerated storage power consumption and fresh-keeping effect are limited, and the shrimp shell that uses refrigerated storage to cross prepares chitosan, finally can influence the quality of chitosan finished product to a certain extent.
Summary of the invention
The present invention mainly is the technical problem that utilization ratio is low, product purity is not high, production cost is high of existing shrimp shell when solving existing shrimp shell and preparing biologically active substance such as chitin.
The present invention has also solved the technical problem of the fresh-keeping difficulty of existing shrimp shell, storage difficulty etc. simultaneously.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: this method may further comprise the steps:
(1) with after new fresh shrimp shell washing and draining, place microwave oven, controlled temperature is 80 ℃, heats 10-15 minute;
(2) above-mentioned shrimp shell is broken into 30-50mm
2Behind the fritter, be 1 in the feed liquid weight ratio: it is in the NaOH solution of 5-10% that the ratio of 10-15 immerses concentration, places microwave oven then, controlled temperature is 100 ℃, heat to take out after 10-15 minute and filter, the shrimp housing is also dried to neutral with flushing with clean water, obtain Deproteinated shrimp housing;
(3) be that 1: 12 ratio immerses in the 2mol/LHCl solution and soaked 24 hours with the shrimp housing behind the above-mentioned deproteinated in the feed liquid weight ratio, filter then and dry, obtain the shrimp housing of decalcification;
(4) with the described method re-treatment of step (2) once with the shrimp housing of above-mentioned decalcification, be that 1: 12 ratio places 1mol/LHCl solution to soak 24 hours with the shrimp housing in the feed liquid weight ratio then, filter, with the shrimp housing with flushing with clean water to neutral and dry;
(5) above-mentioned shrimp housing is placed the decolouring in 6-8 hour of being exposed to the sun in the sun, obtain the chitin of white plates;
(6) be 1 with above-mentioned chitin material in the feed liquid weight ratio: the ratio of 20-30 joins in the NaOH solution that concentration is 45%-50%, puts into microwave oven then, 100 ℃ of controlled temperature, heat to take out after 15-20 minute and be chilled to room temperature, filtration, drying, be washed till neutrality with clear water again, get the chitosan crude product.
(7) NaOH is dissolved in the ethanol, being configured to concentration is the NaOH ethanolic soln of 13%-23%, is 1 with the chitosan crude product in the feed liquid weight ratio: the ratio of 2-4 joins in the NaOH ethanolic soln, under the condition of continuously stirring, control reaction temperature is 78 ℃ of backflow 2-3 hours, filter then, with the chitosan washing, the drying that obtain, pulverized 80 orders at last, promptly get the chitosan finished product.
2. the shrimp shell that utilizes according to claim 1 prepares method high deacetylized and the high viscosity chitosan, it is characterized in that in step (7), and when preparing the ethanolic soln of NaOH, used alcoholic acid concentration expressed in percentage by volume is 75-85%.
The present invention by increasing the technology that dries together, can further improve production efficiency and reduces the loss of soda acid in each filtration step and washing step, is beneficial to environmental protection simultaneously.
The present invention has the technology that adopts microwave to handle three times, is that raw material is carried out the microwave drying Preservation Treatment for the first time.Because microwave treatment time is short, the efficient height does not have influence to the constituent of raw material, through the shrimp shell of microwave treatment, and its freshness height, the shelf-time is long, therefore can large batch of satisfied production needs.And have characteristics such as utilization ratio height, the active substance separation is easy, consumption acid consumption alkali lacks through the shrimp shell that microwave treatment is crossed, so can make high viscosity, relatively the high-molecular weight chitin.For the second time be shrimp housing and concentration be the deproteinated of 5-10% alkaline solution when reacting applied microwave heat.Adopt microwave heating, the reaction times of its shrimp housing and alkali lye is short, and deproteinated is thorough.Be for the third time when chitin and concentration are the deacetylation of 45%-50%NaOH solution, utilize microwave that it is heated.By microwave temperature control reaction, just can allow each reactant molecule motion aggravates in the reaction system, intermolecular collision is frequent, thus the deacetylation that can make chitin is near 90%.Simultaneously, microwave heating can be shortened the time of chitin and alkaline reaction greatly, and the shortening reaction times then helps improving the chitosan viscosity.
After above-mentioned chitin and concentration are the 45%-50%NaOH solution reaction, in order further to obtain high-quality chitosan, the present invention proceeds deacetylation with the chitosan that obtains and the ethanolic soln of NaOH, because ethanol form with sodium alkoxide in alkali lye participates in deacetylation, its perviousness to chitin molecule is stronger, can destroy the hydrogen bond of chitin molecule inside, therefore obtained further raising through chitin deacetylase degree after the above-mentioned reaction, finally allowed the chitin deacetylase degree reach 95%.Simultaneously, the ethanol in the alkali lye also has certain extraction to the pigment of chitosan, thereby makes the quality of product perfect more.
In addition, the present invention utilizes sunlight exposure decolouring, need not consumes energy, and good decolorizing effect, and avoided adopting in the traditional method destruction of strong oxidizer such as potassium permanganate simultaneously, thereby laid the first stone for next step prepares full-bodied chitosan to glycosidic link.
In sum, the present invention has the acid of using, alkali number is few, and advantages such as reaction times weak point, economic environmental protection adopt the chitosan of the inventive method preparation to be white in color or the yellow powder powder, have than high viscosity and high deacetylized, can be widely used in environmental protection, food, medicine and other fields.
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: after new fresh shrimp shell washing and draining, place microwave oven, controlled temperature is 80 ℃, heats 15 minutes; To be that to immerse concentration be in 10% the NaOH solution for 1: 15 ratio in the feed liquid weight ratio after the fragmentation of shrimp shell then, place microwave oven again, controlled temperature is 100 ℃, heats to take out after 10 minutes and filters, the shrimp housing is also dried to neutral with flushing with clean water, obtain Deproteinated shrimp housing; Be that 1: 12 ratio immerses in the 2mol/L HCl solution and soaked 24 hours with it in the feed liquid weight ratio then, refilter and dry, obtain the shrimp housing of decalcification; Be that 1: 15 ratio is handled the shrimp housing of above-mentioned decalcification once with 10% NaOH solution again then in the feed liquid weight ratio, filter, extremely neutral with flushing with clean water, in the feed liquid weight ratio is that 1: 12 ratio places 1mol/L HCL solution, soak after 24 hours, filter, the flushing of shrimp housing is also dried to neutral; With the decolouring in 6-8 hour of being exposed to the sun in the sun of above-mentioned shrimp housing, obtain the chitin of white; With chitin in the feed liquid ratio of mixture be 1: 25 ratio to join concentration be in 48% the NaOH solution, put into microwave oven then, heat to take out after 15 minutes and be chilled to room temperature, be washed till neutrality with clear water again, filter also and dry, the chitosan crude product; It is in 80% ethanol that NaOH is dissolved in concentration expressed in percentage by volume, be configured to concentration and be 13% NaOH ethanolic soln, be that 1: 2 ratio joins in the NaOH ethanolic soln with the chitosan crude product in the feed liquid weight ratio then, under the condition of continuously stirring, control reaction temperature is 78 ℃ and refluxed 2 hours, filter then, with the chitosan washing, the drying that obtain, pulverized 80 orders at last, promptly get the chitosan finished product.
Embodiment 2:
After new fresh shrimp shell washing and draining, place microwave oven, controlled temperature is 80 ℃, heats 10 minutes; To be that to immerse concentration be in 5% the NaOH solution for 1: 10 ratio in the feed liquid weight ratio after the fragmentation of shrimp shell then, place microwave oven again, controlled temperature is 100 ℃, heats to take out after 15 minutes and filters, the shrimp housing is also dried to neutral with flushing with clean water, obtain Deproteinated shrimp housing; Be that 1: 12 ratio immerses in the 2mol/LHCl solution and soaked 24 hours with it in the feed liquid weight ratio then, refilter and dry, obtain the shrimp housing of decalcification; With the shrimp housing of above-mentioned decalcification is that 1: 10 ratio is handled once with 5% NaOH solution again in the feed liquid weight ratio, filter, extremely neutral with flushing with clean water, in the feed liquid weight ratio is that 1: 12 ratio places 1mol/LHCL solution, soak after 24 hours, filter, the flushing of shrimp housing is also dried to neutral; With the decolouring in 6-8 hour of being exposed to the sun in the sun of above-mentioned shrimp housing, obtain the chitin of white; Is that 1: 20 ratio joins in the solution that concentration is 50% NaOH with chitin in the feed liquid ratio of mixture, puts into microwave oven then, heats to take out after 18 minutes to be chilled to room temperature, is washed till neutrality with clear water again, filter also to dry, the chitosan crude product; It is in 85% ethanol that NaOH is dissolved in concentration expressed in percentage by volume, be configured to concentration and be 17% NaOH ethanolic soln, be that 1: 4 ratio joins in the NaOH ethanolic soln with the chitosan crude product in the feed liquid weight ratio then, under the condition of continuously stirring, control reaction temperature is 78 ℃ and refluxed 3 hours, filter then, with the chitosan washing, the drying that obtain, pulverized 80 orders at last, promptly get the chitosan finished product.
Specific embodiment 3:
After new fresh shrimp shell washing and draining, place microwave oven, controlled temperature is 100 ℃, heats 12 minutes; To be that to immerse concentration be in 8% the NaOH solution for 1: 12 ratio in the feed liquid weight ratio after the fragmentation of shrimp shell then, place microwave oven again, controlled temperature is 100 ℃, heats to take out after 12 minutes and filters, the shrimp housing is also dried to neutral with flushing with clean water, obtain Deproteinated shrimp housing; Be that 1: 12 ratio immerses in the 2mol/LHCl solution and soaked 24 hours with it in the feed liquid weight ratio then, refilter and dry, obtain the shrimp housing of decalcification; With the shrimp housing of above-mentioned decalcification is that 1: 12 ratio is handled once with 8% NaOH solution again in the feed liquid weight ratio, filter, extremely neutral with flushing with clean water, in the feed liquid weight ratio is that 1: 12 ratio places 1mol/LHCL solution, soak after 24 hours, filter, the flushing of shrimp housing is also dried to neutral; With the decolouring in 6-8 hour of being exposed to the sun in the sun of above-mentioned shrimp housing, obtain the chitin of white; With chitin in the feed liquid ratio of mixture be 1: 30 ratio to join concentration be in 46% the NaOH solution, put into microwave oven then, heat to take out after 20 minutes and be chilled to room temperature, be washed till neutrality with clear water again, filter also and dry, the chitosan crude product; It is in 75% ethanol that NaOH is dissolved in concentration expressed in percentage by volume, be configured to concentration and be 23% NaOH ethanolic soln, be that 1: 3 ratio joins in the NaOH ethanolic soln with the chitosan crude product in the feed liquid weight ratio then, under the condition of continuously stirring, control reaction temperature is 78 ℃ and refluxed 2 hours, filter then, with the chitosan washing, the drying that obtain, pulverized 80 orders at last, promptly get the chitosan finished product.
Claims (2)
1. one kind is utilized the shrimp shell to prepare method high deacetylized and the high viscosity chitosan, it is characterized in that may further comprise the steps in this method:
(1) with after new fresh shrimp shell washing and draining, place microwave oven, controlled temperature is 80 ℃, heats 10-15 minute;
(2) above-mentioned shrimp shell is broken into fritter after, be 1 in the feed liquid weight ratio: it is in the NaOH solution of 5-10% that the ratio of 10-15 immerses concentration, places microwave oven then, controlled temperature is 100 ℃, heat to take out after 10-15 minute and filter, the shrimp housing is cleaned and dries, obtain Deproteinated shrimp housing;
(3) be that 1: 12 ratio immerses in the 2mol/LHCl solution and soaked 24 hours with the shrimp housing behind the above-mentioned deproteinated in the feed liquid weight ratio, filter then and dry, obtain the shrimp housing of decalcification;
(4) with the described method re-treatment of step (2) once with the shrimp housing of above-mentioned decalcification, be that 1: 12 ratio places 1mol/LHCl solution to soak 24 hours with the shrimp housing in the feed liquid weight ratio then, filter, the shrimp housing is cleaned and dries;
(5) above-mentioned shrimp housing is placed the decolouring in 6-8 hour of being exposed to the sun in the sun, obtain the chitin of white plates;
(6) be 1 with above-mentioned chitin material in the feed liquid weight ratio: the ratio of 20-30 joins in the NaOH solution that concentration is 45%-50%, puts into microwave oven then, 100 ℃ of controlled temperature, heat to take out after 15-20 minute and be chilled to room temperature, filtration, drying, be washed till neutrality with clear water again, get the chitosan crude product;
(7) NaOH is dissolved in the ethanol, being configured to concentration is the NaOH ethanolic soln of 13%-23%, is 1 with the chitosan crude product in the feed liquid weight ratio: the ratio of 2-4 joins in the NaOH ethanolic soln, under the condition of continuously stirring, control reaction temperature is 78 ℃ of backflow 2-3 hours, filter then, with the chitosan washing, the drying that obtain, pulverized 80 orders at last, promptly get the chitosan finished product.
2. the shrimp shell that utilizes according to claim 1 prepares method high deacetylized and the high viscosity chitosan, it is characterized in that in step (7), and when preparing the ethanolic soln of NaOH, used alcoholic acid concentration expressed in percentage by volume is 75-85%.
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| CN2007101685735A CN101200505B (en) | 2007-11-29 | 2007-11-29 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
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| CN2007101685735A CN101200505B (en) | 2007-11-29 | 2007-11-29 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
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| CN101200505B true CN101200505B (en) | 2011-01-19 |
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| CN101560270B (en) * | 2009-06-09 | 2012-07-04 | 杨甫进 | Chitin production method with energy-saving and emission-reduction |
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| CN109627356A (en) * | 2018-12-12 | 2019-04-16 | 扬州日兴生物科技股份有限公司 | A kind of preparation method based on shrimp shell production chitosan |
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| 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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| CN1158335A (en) * | 1996-02-26 | 1997-09-03 | 张建东 | Method for prepn. of chitose |
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| CN1320643A (en) * | 2001-03-21 | 2001-11-07 | 广东梅县梅雁蓝藻有限公司 | Process for preparing chitosan |
| CN1548461A (en) * | 2003-05-07 | 2004-11-24 | 吴汉民 | Production process and apparatus of high quality chitosan |
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- 2007-11-29 CN CN2007101685735A patent/CN101200505B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158335A (en) * | 1996-02-26 | 1997-09-03 | 张建东 | Method for prepn. of chitose |
| CN1280104A (en) * | 2000-06-23 | 2001-01-17 | 清华大学 | Method for preparing flocculent for treatment of chitosan water |
| CN1320643A (en) * | 2001-03-21 | 2001-11-07 | 广东梅县梅雁蓝藻有限公司 | Process for preparing chitosan |
| CN1548461A (en) * | 2003-05-07 | 2004-11-24 | 吴汉民 | Production process and apparatus of high quality chitosan |
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