CN101077893B - Method for extracting deacetylating chitin by fast hydrolyzing shrimp and crab carapace - Google Patents
Method for extracting deacetylating chitin by fast hydrolyzing shrimp and crab carapace Download PDFInfo
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- CN101077893B CN101077893B CN2006100191589A CN200610019158A CN101077893B CN 101077893 B CN101077893 B CN 101077893B CN 2006100191589 A CN2006100191589 A CN 2006100191589A CN 200610019158 A CN200610019158 A CN 200610019158A CN 101077893 B CN101077893 B CN 101077893B
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Abstract
The fast hydrolysis process of extracting deacetyl chitin from shrimp and crab shell includes the following steps: crushing fresh shrimp and crab shell and adding water to form solid-liquid mixture, eliminating protein with sodium peroxide mixture solution containing sodium ozonide, eliminating calcium carbonate with hydrochloric acid, eliminating acetyl radical with sodium hydroxide, eliminating insoluble impurity with dilute acetic acid solution, and spray drying to obtain scaly deacetyl chitin acetate product. The present invention has the advantages of simple technological process and short production period. During the production process, great amount of protein and calcium carbonate are converted into composite amino acid and calcium ion entering to the filtrate and may be used in producing feed in low cost.
Description
Technical field
The present invention relates to the method for hydrolysis extraction chitin deacetylase from shrimp and crab shells, is a kind of sodium peroxide mixing solutions application that chitin deacetylase is extracted in hydrolysis in shrimp and crab shells that contains ozonize sodium specifically.
Background technology
Chitin extensively is present in crustacean and the mushroom, is one of major ingredient in crust such as the shrimp crab structure.Its chemical name is β-acetamido Mierocrystalline cellulose.Chitin is insoluble to acid, alkali, water, must just dissolve in diluted acid or human body fluid behind the hydrolysis deacetylate, to obtain widespread use.Chitin deacetylase is a kind of natural alkaline macromolecule polysaccharide body, also be unique positively charged material in the edible fiber of present known nature, very strong activity is arranged, can strengthen body immunity, function with anti-ageing inhibition disease is a kind of ideal healthcare products.Chitin deacetylase still is the raw material of the senior slurry of textiles, regenerated fiber, plastics etc.Shrimp crab crust major ingredient is multiple proteins, lime carbonate and chitin etc., and it is bigger that its many materials composite structure has determined therefrom to extract the chitin deacetylase difficulty.
In shrimp and crab shells, there are a large amount of edible (residual) albumen, structural protein and chromoprotein, have a strong impact on chitin deacetylase and extract and quality product, must at first remove it.Old technology is taked the diluted alkaline method for hydrolysis, can only remove food protein, has increased difficulty to aftertreatment.
Chinese invention patent prospectus CN1360848A has announced a kind of " containing sodium peroxide mixing solutions of ozonize sodium and its production and application ", to the preparation of the sodium peroxide mixing solutions that contains ozonize sodium with should be used as detailed description, do not relate to the application of sodium peroxide mixing solutions in extracting chitin deacetylase that contains ozonize sodium.
Summary of the invention
The object of the present invention is to provide and a kind ofly both can remove multiple proteins in the shrimp and crab shells fast, the method for chitin deacetylase is extracted in the hydrolysis from shrimp and crab shells that can remove ethanoyl in the chitin again fast, and present method technology is simple, cost is low,
With hereinafter except that indicating all concentration mentioned and ratio be concentration expressed in percentage by weight or weight ratio.
Realize that technical scheme of the present invention comprises following operation:
(1) preparation JHO3 operation: the preparation method of the sodium peroxide mixing solutions that contains ozonize sodium that provides by Chinese invention patent prospectus CN1360848A, preparation contains the sodium peroxide mixing solutions (hereinafter to be referred as JHO3) of ozonize sodium;
(2) remove the protein operation: it is broken that fresh shrimp and crab shells is carried out wet-milling, fineness is about 40 orders, and reactive tank is put in metering, adds water and is made into 20～40% and contains solid-liquid, under the continuous agitation condition of room temperature, in shrimp and crab shells siccative: JHO3=1: 0.1～0.8 ratio adds above-mentioned JHO3, slowly heats up, after the question response calmness, continue again to stir to boil 5～10 minutes, compound is put into pressure filter and is carried out liquid-solid separation, and filter residue is washed to pH8, and clearance rate is not all 35～65% according to raw material.
(3) remove the lime carbonate operation: will go up filter residue and put into reactive tank, water is made into 20～40% and contains solid-liquid, under the continuous agitation condition of room temperature, in shrimp and crab shells siccative: 37%HCI=1: 0.5～1.5 ratio slowly drips 1: 1HCI carries out acidolysis, continuing stirring heating after the question response calmness again boiled 15～20 minutes, compound is put into pressure filter and is carried out liquid-solid separation, and filter residue is washed to pH6, and clearance rate is not all 20～50% according to raw material;
(4) remove the ethanoyl operation: will go up filter residue and put into reactive tank, be made into 10% with 40～50%NaOH solution and contain solid-liquid, under continuous agitation condition, heated and boiled 15～20 minutes, compound is put into pressure filter and is carried out liquid-solid separation, filter residue is washed to pH8, and clearance rate is not all 4～8% according to raw material;
(5) removal of contamination operation: will go up filter residue and put into container, be made into 5% with 3～5% acetic acid and contain solid-liquid, through fully stirring warm dissolving, get the translucent viscous soln of subacidity, place or centrifugal settling, insoluble contaminant filter removes it, and viscosity filtrate is spray-dried, the acetic acid volatilization gets white to the pure product of weak coffee look flakey chitin deacetylase acetate.
Described shrimp and crab shells comprises small lobsters shell, big lobster shell, prawn shell, little native shrimp shell, prawn shell, river crab shell or sea crab shell etc.
Protein and calcium carbonate content should be removed respectively all than higher in shrimp and crab shells.The chitin deacetylase light weight easily suspends, and surfactivity is strong, and it is contaminated to adsorb impurity easily.Therefore technology to equipment anticorrosion, raw material quality and purity requirement than higher.Produce all solid retained of chitin deacetylase technique process (2)～(4), the insoluble impurity of being brought into by factors such as raw material, equipment enters solid in the lump, and the present invention is dissolved rough chitin deacetylase with dilute acetic acid and become viscous soln, removes it through (centrifugal) precipitate and separate.
Contain a large amount of aminoacids complexs, calcium chloride, sodium-acetate etc. in the filtrate that the extraction chitin deacetylase obtains, gathering neutralization is good fodder additives, similar to the nutritive value of fish meal.Produce one ton of chitin deacetylase and produce ten tons ' refuses ' approximately.A large amount of present major parts of shrimp and crab shells go out of use or as rudimentary fodder additives.Behind the inventive method extraction chitin deacetylase; protein and lime carbonate are converted into easily the aminoacids complex that absorbed by animal and calcium ion respectively and enter in the filtrate; gather neutralization by the filtrate of technology removal of contamination generation and be PH6～8; based on this; when extracting chitin deacetylase, produce feed and shrimp crab and culture deep processing formation circulation industrial chain, make full use of resource thereby reach; the conservation of nature environment, the purpose that reduces production costs.
Compared with prior art; the present invention also has following advantage: both can remove three kinds of multi-form protein in the shrimp and crab shells fast, can remove ethanoyl in the chitin fast again, technology is simple; whole technological process can be finished in 1～2 hour, shortened more than one times than prior art.With the explained hereafter chitin deacetylase that the present invention determines, purity height, solvability is good, and is cheap, only is equivalent to commercially available chitinous 1/10th.
Embodiment
Embodiment 1
(1) preparation JHO3: in 1: 0.8 ratio, with alcohol dilute 30% hydrogen peroxide, be mixed even; Ethanol aqueous solution with 45% is the sodium hydroxide solution of solvent preparation 20%, is cooled to room temperature; Under agitation condition, 1: 1 by volume ratio is slowly mixed above-mentioned two kinds of solution mutually, stop to stir allowing it cool off static phase-splitting, on take out recovered alcohol mutually and utilize again, be the sodium peroxide mixing solutions (hereinafter to be referred as JHO3) that contains ozonize sodium down mutually.JHO3 less stable, normal temperature can be stablized tens hours, used appropriate to the occasion matching while using, and the existence of alcohol does not influence the performance of JHO3.Hydrogen peroxide 〉=30% that present embodiment is used, sodium hydroxide 〉=96%, alcohol 〉=95.5%.
(2) remove protein: it is broken that fresh small lobsters shell is carried out wet-milling, fineness is 40 orders, it is some to take by weighing wet feed, put into the stainless steel reaction groove, adding water is made into 30% and contains solid-liquid, under the continuous agitation condition of room temperature, in small lobsters shell siccative: JHO3=1: 0.3 ratio adds above-mentioned JHO3, slowly heats up, and notices that controls reaction speed does not allow foam overflow reactive tank, after the question response calmness, continue to stir to boil 8 minutes, compound is put into pressure filter and is carried out liquid-solid separation again, and filtrate deals with in addition, it is about 8 that filter residue is washed to pH, and clearance rate is about 45%.
(3) remove lime carbonate: will go up filter residue and put into the enamel reactive tank, water is made into 30% and contains solid-liquid, under the continuous agitation condition of room temperature, in small lobsters shell siccative: 37%HCI=1: 1 ratio slowly drips 1: 1HCI carries out acidolysis, notes controls reaction speed, continues stirring heating after the question response calmness again and boils 20 minutes, compound is put into pressure filter and is carried out liquid-solid separation, filtrate deals with in addition, and it is about 6 that filter residue is washed to pH, and clearance rate is 35%.
(4) remove ethanoyl: will go up filter residue and put into the stainless steel reaction groove, and be made into 10% with 45%NaOH solution and contain solid-liquid, under continuous agitation condition; heated and boiled 18 minutes, compound are put into pressure filter and are carried out liquid-solid separation, and filtrate deals with in addition; it is about 8 that filter residue is washed to pH, and clearance rate is about 7%.
(5) removal of contamination: will go up filter residue and put into container, and be made into 5% with 5% acetic acid and contain solid-liquid, and through fully stirring warm dissolving, get the translucent viscous soln of subacidity, and place or centrifugal settling, insoluble contaminant filter removes it.Viscosity filtrate is spray-dried, and the acetic acid volatilization gets the pure product of weak coffee look flakey chitin deacetylase acetate.The chitin deacetylase extraction yield is 10.5% in the small lobsters shell.
Embodiment 2
According to the scheme of embodiment 1, from the river crab shell, extract and remove the acetate chitin.In river crab shell material: JHO3=1: 0.2 ratio, remove protein with JHO3, removing the protein heated and boiled time is 7 minutes, clearance rate～40%.In river crab shell siccative: 37%HCL=1: 1.5 ratio, remove lime carbonate with HCL, removing the lime carbonate heated and boiled time is 20 minutes, clearance rate is about 45%.Remove ethanoyl with 45%NaOH, removing the ethanoyl boiling time is 20 minutes, and clearance rate is about 6%.Dissolve rough chitin deacetylase with 5%HAC and separate insoluble impurity.Dry white flakey chitin deacetylase acetate.The chitin deacetylase extraction yield is 7.0% in the river crab shell.
Embodiment 3
According to the scheme of embodiment 1, from little native shrimp shell, extract and remove the acetate chitin.In little native shrimp shell material: JHO3=1: 0.5 ratio, remove protein with JHO3, removing the protein heated and boiled time is 10 minutes, clearance rate about 60%.In little native shrimp shell siccative: 35%HCL=1: 0.8 ratio, remove lime carbonate with HCL, removing the lime carbonate heated and boiled time is 18 minutes, clearance rate is about 25%.Remove ethanoyl with 40%NaOH, removing the ethanoyl boiling time is 18 minutes, and clearance rate is about 4%.Dissolve rough chitin deacetylase with 5%HAC and separate insoluble impurity.Dry white flakey chitin deacetylase acetate.The chitin deacetylase extraction yield is 7.9% in the little native shrimp shell.
Embodiment 4
According to the scheme of embodiment 1, from the prawn shell, extract and remove the acetate chitin.In prawn shell material: JHO3=1: 0.2 ratio, remove protein with JHO3, removing the protein heated and boiled time is 7 minutes, clearance rate about 45%.In prawn shell siccative: 37%HCL=1: 1 ratio, remove lime carbonate with HCL, removing the lime carbonate heated and boiled time is 20 minutes, clearance rate is about 38%.Remove ethanoyl with 45%NaOH, removing the ethanoyl boiling time is 20 minutes, and clearance rate is about 8%.Dissolve rough chitin deacetylase with 5%HAC and separate insoluble impurity.The dry weak coffee look flakey chitin deacetylase acetate that gets.The chitin deacetylase extraction yield is 6.5% in the prawn shell.
Claims (1)
- One kind from shrimp and crab shells fast hydrolysis extract the method for chitin deacetylase, it is characterized in that: comprise following operation, below except that indicating all concentration of mentioning and ratio be concentration expressed in percentage by weight or weight ratio:(1) preparation contains the sodium peroxide mixing solutions JHO3 of ozonize sodium: in 1: 0.8 ratio, with alcohol dilute 30% hydrogen peroxide, be mixed even; Ethanol aqueous solution with 45% is the sodium hydroxide solution of solvent preparation 20%, is cooled to room temperature; Under agitation condition, 1: 1 by volume ratio is slowly mixed above-mentioned two kinds of solution mutually, stop to stir allowing it cool off static phase-splitting, on take out recovered alcohol mutually and utilize again, be the sodium peroxide mixing solutions JHO3 that contains ozonize sodium down mutually;(2) remove protein: it is broken that fresh small lobsters shell is carried out wet-milling, fineness is 40 orders, it is some to take by weighing wet feed, put into the stainless steel reaction groove, adding water is made into 30% and contains solid-liquid, under the continuous agitation condition of room temperature, in small lobsters shell siccative: JHO3=1: 0.3 ratio adds above-mentioned JHO3, slowly heats up, and notices that controls reaction speed does not allow foam overflow reactive tank, after the question response calmness, continue to stir to boil 8 minutes, compound is put into pressure filter and is carried out liquid-solid separation again, and filtrate deals with in addition, it is 8 that filter residue is washed to pH, and clearance rate is 45%;(3) remove lime carbonate: will go up filter residue and put into the enamel reactive tank, water is made into 30% and contains solid-liquid, under the continuous agitation condition of room temperature, in small lobsters shell siccative: 37%HCl=1: 1 ratio slowly drips HCl and carries out acidolysis, notes controls reaction speed, continues stirring heating after the question response calmness again and boils 20 minutes, compound is put into pressure filter and is carried out liquid-solid separation, filtrate deals with in addition, and it is 6 that filter residue is washed to pH, and clearance rate is 35%;(4) remove ethanoyl: will go up filter residue and put into the stainless steel reaction groove, and be made into 10% with 45%NaOH solution and contain solid-liquid, under continuous agitation condition, heated and boiled 18 minutes, compound are put into pressure filter and are carried out liquid-solid separation, and filtrate deals with in addition, it is 8 that filter residue is washed to pH, and clearance rate is 7%;(5) removal of contamination: will go up filter residue and put into container, and be made into 5% with 5% acetic acid and contain solid-liquid, and through fully stirring warm dissolving, get the translucent viscous soln of subacidity, and place or centrifugal settling, insoluble contaminant filter removes it; Viscosity filtrate is spray-dried, and the acetic acid volatilization gets the pure product of weak coffee look flakey chitin deacetylase acetate; The chitin deacetylase extraction yield is 10.5% in the small lobsters shell.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006100191589A CN101077893B (en) | 2006-05-24 | 2006-05-24 | Method for extracting deacetylating chitin by fast hydrolyzing shrimp and crab carapace |
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| CN2006100191589A CN101077893B (en) | 2006-05-24 | 2006-05-24 | Method for extracting deacetylating chitin by fast hydrolyzing shrimp and crab carapace |
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| CN101077893A CN101077893A (en) | 2007-11-28 |
| CN101077893B true CN101077893B (en) | 2010-11-10 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199496A (en) * | 1974-09-05 | 1980-04-22 | Johnson Edwin L | Process for the recovery of chemicals from the shells of crustacea |
| US4293098A (en) * | 1979-04-20 | 1981-10-06 | Systems Consultants, Inc. | Recovery of active chitin and enhanced protein meal |
| US4536207A (en) * | 1983-07-26 | 1985-08-20 | Igi Biotechnology, Inc. | Nematocidally active chitin-protein complex |
| CN1210867A (en) * | 1998-07-02 | 1999-03-17 | 许光庭 | New deacetylation of chitin |
| CN1360848A (en) * | 2000-12-23 | 2002-07-31 | 黄正华 | Mixed sodium peroxide solution containing sodium ozonide and its prepn and application |
| CN1384121A (en) * | 2001-04-27 | 2002-12-11 | 薛雄生 | Natural chitin extracting technology |
| CN1463988A (en) * | 2002-06-05 | 2003-12-31 | 王广祥 | Process for producing chitosan, astaxanthin and protein using fresh shrimp shell |
-
2006
- 2006-05-24 CN CN2006100191589A patent/CN101077893B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199496A (en) * | 1974-09-05 | 1980-04-22 | Johnson Edwin L | Process for the recovery of chemicals from the shells of crustacea |
| US4293098A (en) * | 1979-04-20 | 1981-10-06 | Systems Consultants, Inc. | Recovery of active chitin and enhanced protein meal |
| US4536207A (en) * | 1983-07-26 | 1985-08-20 | Igi Biotechnology, Inc. | Nematocidally active chitin-protein complex |
| CN1210867A (en) * | 1998-07-02 | 1999-03-17 | 许光庭 | New deacetylation of chitin |
| CN1360848A (en) * | 2000-12-23 | 2002-07-31 | 黄正华 | Mixed sodium peroxide solution containing sodium ozonide and its prepn and application |
| CN1384121A (en) * | 2001-04-27 | 2002-12-11 | 薛雄生 | Natural chitin extracting technology |
| CN1463988A (en) * | 2002-06-05 | 2003-12-31 | 王广祥 | Process for producing chitosan, astaxanthin and protein using fresh shrimp shell |
Non-Patent Citations (5)
| Title |
|---|
| Keisuke Kurita, et al..Synthesis and some PropertiesofNonnaturalAminoPolysaccharides: Branched ChitinandChitosan.macromolecules33.2000,334711-4716. * |
| 凌沛学 等.脱乙酰甲壳质的制备工艺改进.中国生化药物杂志26 1.2005,26(1),34-35. |
| 凌沛学等.脱乙酰甲壳质的制备工艺改进.中国生化药物杂志26 1.2005,26(1),34-35. * |
| 管明荣.可溶性甲壳质的提取方法和应用的研究.济南大学学报4 4.1994,4(4),73-77. |
| 管明荣.可溶性甲壳质的提取方法和应用的研究.济南大学学报4 4.1994,4(4),73-77. * |
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