CN1911967A - Preparation method of chitin - Google Patents
Preparation method of chitin Download PDFInfo
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- CN1911967A CN1911967A CN 200610045058 CN200610045058A CN1911967A CN 1911967 A CN1911967 A CN 1911967A CN 200610045058 CN200610045058 CN 200610045058 CN 200610045058 A CN200610045058 A CN 200610045058A CN 1911967 A CN1911967 A CN 1911967A
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Abstract
The process of extracting chitosan from the waste Aspergillus terreus mycelium from itaconic acid producing process includes: pre-treating to eliminate impurity and water from the waste Aspergillus terreus mycelium, eliminating protein with dilute alkali solution at controlled temperature to obtain solid mycelium and water washing to neutrality, treating with concentrated alkali solution at controlled temperature to eliminate acetyl radical and water washing to neutrality, dissolving the neutral mycelium in dilute acid solution at controlled temperature, time and solid/liquid ratio to obtain clear solution, decolorizing with hydrogen peroxide at controlled temperature, regulating the pH value of the clear solution with alkali and separating out precipitate, dewatering the precipitate with organic solvent, and drying to obtain chitosan product. The present invention has simple technological process, high purity of the product, low power consumption and no pollution.
Description
Technical field:
The present invention relates to extract in a kind of waste aspergillus terreus filament from the methylene-succinic acid production process method for preparing chitosan.
Technical background:
Chitin has another name called chitin, chitin, extensively is present in the cell walls of the epidermises of the shells of crustaceans such as crab, shrimp and various insects and molluscan bone such as cuttlefish, shellfish and shell and mushroom and mushroom etc.Chitin is to be only second to cellulosic second largest natural resources, also is the nitrogenous natural organic-compound (secondly being protein) of quantity maximum on the earth.Chitosan is obtained by the chitin deacetylase base, is unique alkaline polysaccharide of occurring in nature.Because chitin, chitosan have physiological compatibility, multiple excellent properties such as decomposability, polyfunctional reactant, three-dimensional arrangement and chirality, recyclability and wetting ability fully, caused the numerous scientific workers' of different field such as industrial trade such as chemical boundary, biological educational circles, medical circle, chemical industry, medicine, food and agricultural very big research interest.Along with going deep into of research, its importance becomes increasingly conspicuous, and its range of application is also more and more wide.Chitin/chitosan and derivative thereof can be used as lipopenicillinase, decreasing cholesterol, prevent and treat atherosclerosis, the medicine of enhance immunity power, antitumor, sterilization, pharmacological action such as antibacterial and medical fibre and artificial tissue material, pharmaceutical carrier are applied to the medical and health aspect; , noresidue nontoxic because of it and good flocculation, bacteriostasis, preservation effect are applied to foodstuffs industry as liquid treating agent, foodstuff additive and food and fruit and vegetable fresh-keeping agent; Green feed additive and biological pesticide as a kind of Nantural non-toxic are applied to agricultural; Can be used for making the functional material such as fixation support, liquid crystal, intelligent material of film, catalyzer and enzyme and cell.In addition, chitin/chitosan and derivative thereof also can be used fields such as daily use chemicals, chemical fibre, papermaking, printing and dyeing and environmental protection because of its good physiologically active and functional property.At present, chitin/chitosan is necessary the 6th vital principle of human body outside " biomaterial of 21st century " and isolating protein, fat, sugar, VITAMIN, the mineral substance by many scholar's analogies.
The industrial production chitosan mainly is that employing is a raw material with shrimp, crab shell at present, adopts hydrochloric acid to remove inorganic salt, the production technique of organism such as diluted alkaline deproteinated, concentrated base deacetylation.There is not easily collecting of raw materials for production in this technology, is subjected to the influence in the season and the place of production bigger, production cost according to height not down, products obtained therefrom ash oontent height, deacetylation is lower and be subjected to the influence of factors such as kind, the place of production, vegetative period of raw material and distinct disadvantage such as instability.This patent adopt in the methylene-succinic acid production process waste---the aspergillus terreus filament is a production feedstock production chitosan.Methylene-succinic acid, formal name used at school is propylenedicarboxylic acid, methylene-succinic acid, is the bigger important biochemical industry product that is widely used in a plurality of fields such as chemical industry, medicine, coating, lightization, synthetic resins, agricultural chemicals of a kind of consumption.At present industrial mostly is to prepare methylene-succinic acid with biological fermentation process, isolate aspergillus terreus filament after the methylene-succinic acid and further utilized as yet but discharge as refuse.The waste mycelia of discharging not only takies a large amount of places, and time one long can be putrid and deteriorated, give off an unpleasant smell, that gives surrounding environment and direct labor healthyly all brings very big harm.The enforcement of this patent both can make the higher chitosan product of added value, can solve methylene-succinic acid simultaneously again and produce the pollution problem of waste to environment, in addition, had also enriched the preparation method of chitosan, was the patented invention of " achieving many things at one stroke ".
Summary of the invention:
The shortcoming that purpose of the present invention exists in overcoming prior art is sought to design and a kind ofly waste in the methylene-succinic acid production process is recycled the processing method of extracting effective components, the i.e. preparation method of chitosan from aspergillus terreus filament wherein.
The present invention is by extracting chitosan in the methylene-succinic acid waste mycelia; its main technique step comprises pre-treatment; deproteinated; washing; deacetylation; secondary water washing; acid is molten; decolouring; alkali is heavy; dehydrate etc.; after earlier methylene-succinic acid being produced waste aspergillus terreus filament and removing the pre-treatment of impurity and moisture; under the temperature control condition, slough albumen with diluted alkaline and get the mycelium solid; and wash with water to neutrality and get neutral mycelium solid; with the high alkali liquid temp-controlling and time-controlling to neutral mycelium solid carry out deacetylation handle after again secondary water washing to neutral the neutral mycelium solid of secondary; again with diluted acid to the neutral mycelium of secondary at temp-controlling and time-controlling control solid-to-liquid ratio (weight percent meter; below all with) carry out under the condition acid after molten clear liquid; and with hydrogen peroxide to clear liquid after decolouring under the temp-controlling and time-controlling condition; regulate the potential of hydrogen of decolouring back clear liquid again with alkali; make precipitation separate out throw out, with organic solvent throw out is dewatered then and vacuum-drying after white to faint yellow chitosan product.The condition and the function of its each processing step are as follows:
Pre-treatment: will separate methylene-succinic acid aspergillus terreus filament afterwards through washing, settlement separate, remove the impurity such as flocculating aids that wherein are mingled with, and centrifuge dehydration gets mycelium.
Deproteinated: the diluted alkaline with 1%～15% (sodium hydroxide or potassium hydroxide) is at 60 ℃～120 ℃ mycelium of handling down after dewatering, and solid-to-liquid ratio is 1: 0.5～1: 20, and the time is 1～12 hour.Filter (or centrifugal) and separate, gained mycelium solid is used for subsequent handling to be handled.
Washing: wash mycelium solid behind the deproteinated with water to neutral, filter (or centrifugal) and separate, the neutral mycelium solid of gained is used for subsequent handling to be handled.
Deacetylation: the concentrated base with 30%～60% (sodium hydroxide or potassium hydroxide) is handled and has been washed to the neutral mycelium, and temperature is 50 ℃～150 ℃, and solid-to-liquid ratio is 1: 0.5～1: 30, and the time is 1～12 hour.Filter (or centrifugal) and separate, gained deacetylation mycelium solid is used for subsequent handling to be handled.
Secondary water washing: the mycelium solid that washes with water after deacetylation is handled is extremely neutral, filters (or centrifugal) and separates, and the neutral mycelium solid of gained secondary is used for the subsequent handling processing.
Acid is molten: the mycelium after deacetylation and secondary water washing processing descends molten soaking 1-24 hour, solid-to-liquid ratio 1: 0.5～1: 30 with 1%～30% diluted acid (hydrochloric acid, nitric acid or acetic acid, formic acid) at 50 ℃～150 ℃.Filter (or centrifugal) and separate, the gained clear liquid is used for subsequent handling to be handled.
Decolouring: with hydrogen peroxide clear liquid is decoloured, temperature is 30 ℃～120 ℃, and the time is 0.5～10 hour.
Alkali is heavy: the potential of hydrogen of the clear liquid after decolouring with the alkali adjusting separates out precipitation to pH 〉=9 fully.Filter (or centrifugal) and separate, gained precipitation matter is used for subsequent handling and handles.
Dehydration: precipitation matter is further dewatered with organic solvent.Filter (or centrifugal) and separate, gained dehydration postprecipitation matter is used for subsequent handling and handles.
Dry: vacuum-drying (or oven dry below 80 ℃) precipitation matter promptly gets white to faint yellow chitosan product.
The inventive method compared with prior art, its processing step is simple, principle is reliable, it is pure to extract product, saving power and preventing pollution dyes.
Embodiment:
Take by weighing 500 gram weight through pretreated methylene-succinic acid waste mycelia, diluted alkaline with 10% (sodium hydroxide or potassium hydroxide) is handled under 80 ℃, and solid-to-liquid ratio (weight percent meter, below all with) is 1: 10, time is 6 hours, filters (or centrifugal) then and separates.Press identical operations mode and condition re-treatment once again.Washing mycelium solid filters (or centrifugal) and separates to neutral, and filter cake is handled with 50% concentrated base (sodium hydroxide or potassium hydroxide), and temperature is 90 ℃, and solid-to-liquid ratio is 1: 20, and the time is 8 hours, filters (or centrifugal) then and separates.The washing filter cake filters (or centrifugal) and separates to neutral.Descended molten leaching cakes 15 hours, solid-to-liquid ratio 1: 20 with 10% diluted acid (hydrochloric acid, nitric acid or acetic acid, formic acid) at 90 ℃.Filtering (or centrifugal) separates.With hydrogen peroxide the gained clear liquid is decoloured, temperature is 30 ℃～120 ℃, and the time is 6 hours.Regulate clear liquid after the decolouring to pH=9 with alkali, treat that precipitation is separated out fully after, filter (or centrifugal) and separate, the gained precipitation is further dewatered with organic solvent.The solid that filtration (or centrifugal) separation is removed behind the organic solvent carries out vacuum-drying, or in oven dry below 80 ℃, promptly gets white or faint yellow chitosan product 74 grams.Yield reaches 14.5% (in mycelium dry weight).
The present invention is when implementing, and reaction process will fully stir; Can reuse 2～3 times behind the sig water deproteinated for the second time; Dense waste lye can reuse 4～5 times, or is used for the deproteinated processing after dilution; Because terreus raw material color is darker, so decolouring is wanted thoroughly just can make the chitosan product color more shallow; Dehydrated organic solvent can reuse after distillation; The waste mycelia that extracts chitosan can be used for other purposes such as bio-feritlizer after simple process.
Claims (6)
1. the preparation method of a chitosan; comprise pre-treatment; deproteinated; washing; deacetylation; secondary water washing; acid is molten; decolouring; alkali is heavy; dehydrate; after it is characterized in that earlier methylene-succinic acid being produced waste aspergillus terreus filament removes the pre-treatment of impurity and moisture; under the temperature control condition, slough albumen with diluted alkaline and get the mycelium solid; and wash with water to neutrality and get neutral mycelium solid; with the high alkali liquid temp-controlling and time-controlling to neutral mycelium solid carry out deacetylation handle after again secondary water washing to neutral the neutral mycelium solid of secondary; again with diluted acid to the neutral mycelium of secondary carry out acid under the temp-controlling and time-controlling control solid-to-liquid ratio condition must clear liquid after molten; and with hydrogen peroxide to clear liquid after decolouring under the temp-controlling and time-controlling condition; regulate the potential of hydrogen of decolouring back clear liquid again with alkali; make the precipitation separate out throw out, after with organic solvent throw out being dehydrated then the chitosan product.
2. according to the preparation method of the described chitosan of claim 1, it is characterized in that deproteinated is to handle mycelium with 1%～15% sodium hydroxide or potassium hydroxide down at 60 ℃～120 ℃, solid-to-liquid ratio is 1: 0.5～1: 20, and the time is 1～12 hour.
3. according to the preparation method of the described chitosan of claim 1; it is characterized in that deacetylation is sodium hydroxide or the neutral mycelium of potassium hydroxide treatment with 30%～60%; temperature is 50 ℃～150 ℃, and solid-to-liquid ratio is 1: 0.5～1: 30, and the time is 1～12 hour.
4. according to the preparation method of the described chitosan of claim 1; it is characterized in that acid molten be mycelium after deacetylation and second dehydration are handled with 1%～30% hydrochloric acid or nitric acid or acid or glacial acetic acid in 50 ℃～150 ℃ times molten soaking, solid-to-liquid ratio 1: 0.5～1: 30.
5. according to the preparation method of the described chitosan of claim 1, it is characterized in that decolouring is with hydrogen peroxide clear liquid to be decoloured, temperature is 30 ℃～120 ℃, and the time is 0.5～10 hour.
6. according to the preparation method of the described chitosan of claim 1, it is characterized in that it is the potential of hydrogen of regulating the clear liquid after decolouring with alkali that alkali sinks, precipitation is separated out fully, filtration or centrifugation must precipitate matter.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100450583A CN100396703C (en) | 2006-06-20 | 2006-06-20 | Preparation method of chitin |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100450583A CN100396703C (en) | 2006-06-20 | 2006-06-20 | Preparation method of chitin |
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| CN1911967A true CN1911967A (en) | 2007-02-14 |
| CN100396703C CN100396703C (en) | 2008-06-25 |
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| CNB2006100450583A Expired - Fee Related CN100396703C (en) | 2006-06-20 | 2006-06-20 | Preparation method of chitin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134461A (en) * | 2010-12-23 | 2011-07-27 | 青岛琅琊台集团股份有限公司 | Method for manufacturing adhesive by using itaconic acid mycelia |
| CN104892795A (en) * | 2015-06-16 | 2015-09-09 | 中国水产科学研究院黄海水产研究所 | Chitosan and seaweed fertilizer joint production method |
| CN106868076A (en) * | 2017-03-02 | 2017-06-20 | 杭州垚信生物科技有限公司 | A kind of method that bacteria residue prepares chitosan oligosaccharide |
| CN109021145A (en) * | 2018-06-19 | 2018-12-18 | 南京理工大学泰州科技学院 | The method for preparing chitosan as raw material using thick chitin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085215C (en) * | 1998-07-20 | 2002-05-22 | 北京化工大学 | Method for preparing chitosan and low polymerized chitosan |
| CN1317497A (en) * | 2001-04-27 | 2001-10-17 | 张伟 | Process for preparing chitosan |
| CN1260253C (en) * | 2004-10-19 | 2006-06-21 | 武汉大学 | Method for extracting and separating chitosan from waste citric acid mycelium |
-
2006
- 2006-06-20 CN CNB2006100450583A patent/CN100396703C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134461A (en) * | 2010-12-23 | 2011-07-27 | 青岛琅琊台集团股份有限公司 | Method for manufacturing adhesive by using itaconic acid mycelia |
| CN102134461B (en) * | 2010-12-23 | 2013-04-03 | 青岛琅琊台集团股份有限公司 | Method for manufacturing adhesive by using itaconic acid mycelia |
| CN104892795A (en) * | 2015-06-16 | 2015-09-09 | 中国水产科学研究院黄海水产研究所 | Chitosan and seaweed fertilizer joint production method |
| CN106868076A (en) * | 2017-03-02 | 2017-06-20 | 杭州垚信生物科技有限公司 | A kind of method that bacteria residue prepares chitosan oligosaccharide |
| CN109021145A (en) * | 2018-06-19 | 2018-12-18 | 南京理工大学泰州科技学院 | The method for preparing chitosan as raw material using thick chitin |
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| Publication number | Publication date |
|---|---|
| CN100396703C (en) | 2008-06-25 |
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Granted publication date: 20080625 |