CN1891719B - Method for preparing chitin and chitosan from shell-like marine amimal shells - Google Patents
Method for preparing chitin and chitosan from shell-like marine amimal shells Download PDFInfo
- Publication number
- CN1891719B CN1891719B CN200610040197A CN200610040197A CN1891719B CN 1891719 B CN1891719 B CN 1891719B CN 200610040197 A CN200610040197 A CN 200610040197A CN 200610040197 A CN200610040197 A CN 200610040197A CN 1891719 B CN1891719 B CN 1891719B
- Authority
- CN
- China
- Prior art keywords
- chitin
- filtrate
- preparation
- edta
- chitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The preparative method of a kind of chitin and chitosan belongs to the preparing field of chitin and chitosan. The shell of tortoise feet (meat are removed) are cleaned, dried, crushed to 40 - 60 mesh, soaked in the 4%~8% HCl at room temperature till the disappearance of granular calcium, filtered, washed with water to neutral, drying, preliminary decalcifying materials are obtained. The preliminary decalcifying materials is soaked in the 6%~8%NaOH at 60~80 degree C for 4h~6h, filtered, washed with water to neutral, dried to get the deproteinized material. Dissolving EDTA into saturated solution, regulating pH at 7~8, soaking the deproteinized materials in the EDTA saturated solution for 12h~36h at room temperature, filtering, drying 50~60deg. C for 2h~3h, chitin is obtained. Soaking the chitin in the 40%~50% NaOH solution at 60~80deg. C for 10h~16h, handling with deacetylase, filtering, soaking the filter in 40%~50%NaOH at 60~80 deg. C for 10h~16h, filtering, washing the filter with water to be neutral, Drying it at 50~60deg.C for 5-6h, chitosan is obtained.
Description
Technical field
The invention belongs to the preparation manufacture field of organic high molecular compound chitin, chitosan, refer in particular to a kind of chitin of crustaceans marine animal shell, the preparation method of chitosan, is the comprehensive utilization to the crustaceans marine animal.
Background technology
The preparation of chitin generally obtains crude product by shrimp shell crab shell through HCl decalcification, NaOH deproteinated, make chitosan after taking off acetyl with concentrated base again, and such cost of material is higher, output fluctuates with seasonal variation, becomes a factor that hinders the chitosan industrial development.Use conventional sour natron bubble to handle shrimp shell crab shell among the patent CN 01117481.1, though added that squeezing is handled and the fume afterheat evolutionary approach of oven dry indirectly, but still exist the acid bubble and damage problems such as chitin molecule chain and waste liquor contamination be serious.Replace HCl with EDTA among the patent CN02134504.X, solved the damage problem and the decalcification of chitin molecule chain thoroughly, but also brought simultaneously new problem---the big disposable input height of EDTA consumption, decalcification long reaction time; Introduce new running stores again in byproduct recovery and the liquid waste disposal process, failed to reach well the purpose that reduces cost, mentions economic benefit.
The tortoise foot (has another name called: be the crustaceans marine animal stone larva of a tapeworm or the cercaria of a schistosome), be used as medicine or edible its meat of all getting that shell is only cast out as waste material, causes certain waste.Through inquiry, also do not utilize at present the shell of tortoise foot to prepare the document and the patent of chitin, chitosan.
Summary of the invention
Purpose of the present invention finds new raw material and improves the preparation method for the preparation of chitin on the one hand, has opened up new path for the comprehensive utilization of tortoise foot class marine animal on the other hand.
A kind of preparation method of chitin of crustaceans marine animal shell:
(1), the preliminary decalcification of acid treatment: the foot of the tortoise behind fleshing shell is cleaned, dried, be crushed to 40 orders～60 orders, extremely do not have granular calcium to exist substantially with 4%～8%HCl soak at room temperature, filter, the water repetitive scrubbing dries to neutral, get preliminary decalcification material, filtrate collection is standby;
(2), alkaline purification deproteinated: the material of preliminary decalcification in the acid treatment is soaked 4h～6h with 60 ℃～80 ℃ temperature of 6%～8%NaOH solution, filter, the water repetitive scrubbing dries to neutral, gets the deproteinated material; Filtrate collection is standby;
(3), EDTA handles and takes off in conjunction with calcium: dissolving EDTA makes saturated solution, and pH is 7～8 in control, and gained deproteinated material is soaked 12h～36h at normal temperatures with saturated EDTA solution, filter, dry, 50～60 ℃ of dry 2h～3h obtain flaxen chitin finished product; Filtrate collection is standby.
The filtrate of the preliminary decalcification of acid treatment is mixed with the Deproteinated filtrate of alkaline purification, generate Ca (OH)
2Precipitation is separated, washing, and drying gets technical grade Ca (OH)
2The solution concentration evaporate to dryness gets industrial salt.
EDTA handles the filtrate of taking off in conjunction with calcium and transfers to pH=1～2 with dense HCl, and the EDTA precipitation is separated out, sediment separate out, and dissolving makes saturated EDTA solution, and control pH=7～8 are reused.
A kind of preparation method of chitosan of crustaceans marine animal shell:
A, make chitin by the preparation described step of chitin (1), (2), (3);
B, steps A gained chitin is added in 40%～50%NaOH solution, soak 10h～16h down at 60 ℃～80 ℃, carry out deacetylation and handle, filter then, filtrate is reused;
C, with step B gained filtering medium, soak down 10h～16h with 40%～50%NaOH solution at 60 ℃～80 ℃, filter then, filtering medium washes with water to neutrality, dry, 50 ℃～60 ℃ dry 5-6h, white chitosan finished product; Filtrate cycle is used.
Filtrate cycle among the described step C is used 2 times, is used for step B then, and the filtrate cycle among the described step B is used 3 times, is mixed with the deproteinated processing that 6%～8%NaOH is used for preparing chitin technology step 2 then.
The chitin of a kind of crustaceans marine animal shell of the present invention, the preparation method of chitosan it is advantageous that:
1, found a kind of new chitin, the preparation raw material of chitosan: the preparation raw material sources instability of present chitin, chitosan, price is higher.The present invention is raw materials used to be the shell of tortoise foot class crustacean, it in China Guangdong, Fujian, Zhejiang are coastal that growth all arranged, shell is only made waste material and is handled, annual consumption is also bigger, so the acquisition of raw material is not difficult.
2, found new way for the comprehensive utilization exploitation of tortoise foot class marine animal: the edible or medicinal meat of all getting of tortoise foot, shell is all cast out as waste material, causes certain waste.The present invention is from the comprehensive utilization of marine animal, and utilization depleted shell is produced expensive chitin, chitosan as raw material.
3, the preparation method to chitin, chitosan makes improvement: HCl decalcification, NaOH deproteinated are generally adopted in the preparation of chitin, and HCl has infringement to the molecular chain of chitin; Replace HCl to carry out decalcification fully with EDTA, to the molecular chain not damaged of chitin, but the big disposable input height of EDTA consumption, decalcification long reaction time.The present invention suitably pulverizes the back to shell can slough CaCO very soon with rare HCl processing
3, use the NaOH deproteinated again, handle with EDTA at last and slough in conjunction with calcium.The benefit of Chu Liing is like this: (1) acid treatment is placed above the other things and acid inexcessive, reduced Degradation as much as possible to the chitin molecule chain; (2) the EDTA reaction temperature and, to the molecular chain not damaged of chitin, and decalcification is thorough, the consumption of the EDTA that also significantly reduces through the sour decalcification of the first step has shortened the production cycle.
4, the recovery of the processing of waste liquid and byproduct: the acid solution of decalcification and Deproteinated alkali lye are the big main waste liquids of two in the chitin production process, can pollute environment if deal with improperly.The present invention directly mixes two waste liquids, generates Ca (OH)
2Precipitation and NaCl solution obtain two first mate's products C a (OH) after the simple process
2And industrial salt, both handled waste liquid, reclaim byproduct, and do not added any new running stores, reduced cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment one:
1, the preparation of chitin
The sufficient shell of tortoise behind the fleshing is cleaned, dried, be crushed to about 60 orders, to there not being granular calcium to exist substantially, filter, dry, get preliminary decalcification material with 4%HCl soak at room temperature 6h.Filtrate for later use.The preliminary decalcification material of gained soaks 6h with 80 ℃ of temperature of 6%NaOH solution, filters, and precipitation is washed to neutrality repeatedly, dries, and gets the deproteinated material.Filtrate is mixed with previous step filtrate, generates Ca (OH)
2Precipitation, precipitation separation, washing, drying get technical grade Ca (OH)
2(as this technology first byproduct); The solution concentration evaporate to dryness gets industrial NaCl (as this technology second byproduct).Dissolving EDTA makes saturated solution, and pH is 7 in control, and the deproteinated material is soaked 12h at normal temperatures with saturated EDTA solution, filters, dries, and 50 ℃ of ℃ of forced air drying 2h obtain flaxen chitin finished product.Filtrate transfers to pH=1 with dense HCl, and the EDTA precipitation is separated out, sediment separate out, and dissolving makes saturated EDTA solution, and control pH=8 reuses.
2, the preparation of chitosan
The gained chitin adds in the 50%NaOH solution, soaks 10h down at 60 ℃, carries out deacetylation and handles, and filters then; Filtrate is reused about 3 times, is mixed with the deproteinated processing that 6%NaOH is used to prepare chitin technology then.The gained filtering medium is soaked 10h with newly joining 50%NaOH solution down at 60 ℃ again, filter then; Filtrate cycle is used 2 times, and the acetyl that takes off that is used for back is handled.Filtering medium washes with water to neutrality, dries, and 50 ℃ of forced air drying 6h get white chitosan finished product.
Embodiment two:
1, the preparation of chitin
The sufficient shell of tortoise behind the fleshing is cleaned, dried, be crushed to about 40 orders,, filter, dry, get preliminary decalcification material with extremely there not being granular calcium to exist behind the about 4h of 8%HCl soak at room temperature substantially.Filtrate for later use.
The preliminary decalcification material of gained soaks 4h with 60 ℃ of temperature of 8%NaOH solution, filters, and precipitation is washed to neutrality repeatedly, dries, and gets the deproteinated material.Filtrate is mixed with previous step filtrate, generates Ca (OH)
2Precipitation, precipitation separation, washing, drying get technical grade Ca (OH)
2(as this technology first byproduct); The solution concentration evaporate to dryness gets industrial NaCl (as this technology second byproduct).
Dissolving EDTA makes saturated solution, and pH is 8 in control, and the deproteinated material is soaked 24h at normal temperatures with saturated EDTA solution, filters, dries, and 60 ℃ of forced air drying 3h obtain flaxen chitin finished product.Filtrate transfers to pH=2 with dense HCl, and the EDTA precipitation is separated out, sediment separate out, and dissolving makes saturated EDTA solution, and control pH=7 reuses.
2, the preparation of chitosan
The gained chitin adds in the 40%NaOH solution, soaks 12h down at 80 ℃, carries out deacetylation and handles, and filters then; Filtrate is reused about 3 times, is mixed with the deproteinated processing that 8%NaOH is used to prepare chitin technology then.The gained filtering medium is soaked 12h with newly joining 40%NaOH solution down at 80 ℃ again, filter then; Filtrate cycle is used 2 times, and the acetyl that takes off that is used for back is handled.Filtering medium washes with water to neutrality, dries, and 60 ℃ of forced air drying 5h get white chitosan finished product.
Claims (5)
1. the preparation method of the chitin of tortoise foot shell is characterized in that:
(1), the preliminary decalcification of acid treatment: the foot of the tortoise behind fleshing shell is cleaned, dried, be crushed to 40 orders～60 orders, extremely do not have granular calcium to exist substantially with 4%～8%HCl soak at room temperature, filter, the water repetitive scrubbing dries to neutral, get preliminary decalcification material, filtrate collection is standby;
(2), alkaline purification deproteinated: the material of preliminary decalcification in the acid treatment is soaked 4h～6h with 60 ℃～80 ℃ temperature of 6%～8%NaOH solution, filter, the water repetitive scrubbing dries to neutral, gets the deproteinated material; Filtrate collection is standby;
(3), EDTA handles and takes off in conjunction with calcium: dissolving EDTA makes saturated solution, and pH is 7～8 in control, and gained deproteinated material is soaked 12h～36h at normal temperatures with saturated EDTA solution, filter, dry, 50～60 ℃ of dry 2h～3h obtain flaxen chitin finished product; Filtrate collection is standby.
2. the preparation method of the chitin of a kind of tortoise foot shell according to claim 1 is characterized in that: the Deproteinated filtrate of filtrate and alkaline purification of the preliminary decalcification of acid treatment is mixed, generate Ca (OH)
2Precipitation is separated, washing, and drying gets technical grade Ca (OH)
2The solution concentration evaporate to dryness gets industrial salt.
3. the preparation method of the chitin of a kind of tortoise foot shell according to claim 1, it is characterized in that: EDTA handles the filtrate of taking off in conjunction with calcium and transfers to pH=1～2 with dense HCl, and the EDTA precipitation is separated out, sediment separate out, dissolving makes saturated EDTA solution, and control pH=7～8 are reused.
4. the chitin that adopts the described preparation method of claim 1 to obtain prepares the preparation method of chitosan, it is characterized in that:
A, make chitin by the preparation described step of chitin (1), (2), (3);
B, steps A gained chitin is added in 40%～50%NaOH solution, soak 10h～16h down at 60 ℃～80 ℃, carry out deacetylation and handle, filter then, filtrate is reused;
C, with step B gained filtering medium, soak down 10h～16h with 40%～50%NaOH solution at 60 ℃～80 ℃, filter then, filtering medium washes with water to neutrality, dry, 50 ℃～60 ℃ dry 5-6h, white chitosan finished product; Filtrate cycle is used.
5. the preparation method of chitosan according to claim 4: it is characterized in that: the filtrate cycle among the step C is used 2 times, be used for step B then, filtrate cycle among the step B is used 3 times, is mixed with the deproteinated processing that 6%～8%NaOH is used for preparing chitin technology step 2 then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610040197A CN1891719B (en) | 2006-05-11 | 2006-05-11 | Method for preparing chitin and chitosan from shell-like marine amimal shells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610040197A CN1891719B (en) | 2006-05-11 | 2006-05-11 | Method for preparing chitin and chitosan from shell-like marine amimal shells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1891719A CN1891719A (en) | 2007-01-10 |
| CN1891719B true CN1891719B (en) | 2010-05-12 |
Family
ID=37596941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610040197A Expired - Fee Related CN1891719B (en) | 2006-05-11 | 2006-05-11 | Method for preparing chitin and chitosan from shell-like marine amimal shells |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1891719B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2010010181A (en) * | 2008-03-19 | 2011-05-25 | Agratech International Inc | Chitosan manufacturing process. |
| CN105199010A (en) * | 2014-06-28 | 2015-12-30 | 李锦梁 | Preparation method for chitosan |
| CN105085707A (en) * | 2015-05-13 | 2015-11-25 | 浙江海洋学院 | Production method of chitin by using shrimp shell |
| CN107151276B (en) * | 2017-06-23 | 2019-06-28 | 武汉理工大学 | The method of chitin extraction nanometer fento from marine biomass |
| CN109042660A (en) * | 2018-08-15 | 2018-12-21 | 山东泰诺药业有限公司 | A kind of chitosan oligosaccharide derivative pesticide preparation and its processing technology |
| CN110746520A (en) * | 2019-12-03 | 2020-02-04 | 扬州日兴生物科技股份有限公司 | Novel efficient preparation method for chitosan production |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862122A (en) * | 1972-02-16 | 1975-01-21 | Quintin P Peniston | Method of recovering chitosan and other by-products from shellfish waste and the like |
| RU2073017C1 (en) * | 1995-04-27 | 1997-02-10 | Фрайман Давид Борисович | Method of preparing chitosan |
| CN1243836A (en) * | 1998-07-30 | 2000-02-09 | 司信 | Process for preparing chitin from abacterial fly maggot |
| CN1262280A (en) * | 1999-02-05 | 2000-08-09 | 唐耿吉 | Process for extracting chitin by secondary degreasing and decalcification |
| JP3139291B2 (en) * | 1994-07-11 | 2001-02-26 | 富士通株式会社 | Display control means and display panel driving device |
| CN1401664A (en) * | 2002-08-01 | 2003-03-12 | 湛江海洋大学 | Method for preparing high relative molecular mass chitin and chitosan, and comprehensive utilization |
-
2006
- 2006-05-11 CN CN200610040197A patent/CN1891719B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862122A (en) * | 1972-02-16 | 1975-01-21 | Quintin P Peniston | Method of recovering chitosan and other by-products from shellfish waste and the like |
| JP3139291B2 (en) * | 1994-07-11 | 2001-02-26 | 富士通株式会社 | Display control means and display panel driving device |
| RU2073017C1 (en) * | 1995-04-27 | 1997-02-10 | Фрайман Давид Борисович | Method of preparing chitosan |
| CN1243836A (en) * | 1998-07-30 | 2000-02-09 | 司信 | Process for preparing chitin from abacterial fly maggot |
| CN1262280A (en) * | 1999-02-05 | 2000-08-09 | 唐耿吉 | Process for extracting chitin by secondary degreasing and decalcification |
| CN1401664A (en) * | 2002-08-01 | 2003-03-12 | 湛江海洋大学 | Method for preparing high relative molecular mass chitin and chitosan, and comprehensive utilization |
Non-Patent Citations (4)
| Title |
|---|
| 赵明 等.高相对分子质量甲壳素、壳聚糖的制备.药物生物技术11 4.2004,33(4),全文. |
| 赵明等.高相对分子质量甲壳素、壳聚糖的制备.药物生物技术11 4.2004,33(4),全文. * |
| 钱丹 等.制备脱乙酰甲壳素的研究.福州大学学报（自然科学版）33 4.2005,33(4),全文. |
| 钱丹等.制备脱乙酰甲壳素的研究.福州大学学报(自然科学版)33 4.2005,33(4),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1891719A (en) | 2007-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1891719B (en) | Method for preparing chitin and chitosan from shell-like marine amimal shells | |
| CN103113496A (en) | Clean chitosan production technology | |
| CN104277141A (en) | Method for extracting chitin from dried shrimp shells | |
| CN105348411B (en) | A method of preparing β-chitin using squid sector bone | |
| CN1775816A (en) | Environment-protection low-consumption process for preparing chitin from shrimp shell and for extracting bioactivity substance | |
| CN103665191A (en) | Preparation method of chitosan and immersion device for preparing chitosan | |
| CN101804330A (en) | Heavy metal ion adsorbent and preparation and application method thereof | |
| CN101560270A (en) | Chitin production method with energy-saving and emission-reduction | |
| CN101176549A (en) | Low energy- wasting and environment protection method for extracting chitin as well as biologically active substance thereof from shrimp shell | |
| CN101003581A (en) | Rtechnique for extracting chitin in high molecular weight | |
| CN104592417A (en) | Enzyme-process extraction technology for chitin | |
| CN101134786A (en) | Method for producing chitosan-shitosan | |
| CN102161714A (en) | Process for preparing chitosan and calcium citrate | |
| CN103846080A (en) | Active carbon regeneration method | |
| JP2017504697A (en) | Cleaning product and preparation method thereof | |
| CN1085564A (en) | A kind of preparation method of chitin | |
| CN108516567A (en) | A kind of processing method of leather anti-corrosion abraum salt | |
| CN105536716A (en) | Orange peel modified adsorbent material and preparation method thereof | |
| CN1176950C (en) | Method for preparing high relative molecular mass chitin and chitosan, and comprehensive utilization | |
| CN206318909U (en) | A kind of glyphosate powder reclaiming device | |
| CN100491314C (en) | Method of purifying immersed liquid in extraction process of algin, iodine and mannitol | |
| CN205152021U (en) | PTA activated sludge uses multipurposely system | |
| CN104892795B (en) | A kind of chitosan and alga fertilizer combine production method | |
| CN106565853A (en) | Method for preparing raw materials of liquid fertilizer by using shrimp and crab shell-containing wastes | |
| CN108239183A (en) | A kind of clean preparation process of chitin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100512 Termination date: 20130511 |