CN102816808A - Method for preparing chitosan by using shrimp shells - Google Patents
Method for preparing chitosan by using shrimp shells Download PDFInfo
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- CN102816808A CN102816808A CN2012102481986A CN201210248198A CN102816808A CN 102816808 A CN102816808 A CN 102816808A CN 2012102481986 A CN2012102481986 A CN 2012102481986A CN 201210248198 A CN201210248198 A CN 201210248198A CN 102816808 A CN102816808 A CN 102816808A
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- shrimp shell
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- shrimp
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 46
- 241000238557 Decapoda Species 0.000 title claims abstract description 24
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims abstract description 160
- 239000002002 slurry Substances 0.000 claims abstract description 66
- 239000008399 tap water Substances 0.000 claims abstract description 42
- 235000020679 tap water Nutrition 0.000 claims abstract description 42
- 238000011010 flushing procedure Methods 0.000 claims abstract description 21
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- 108091005804 Peptidases Proteins 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
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- 238000007654 immersion Methods 0.000 claims abstract 2
- 235000012054 meals Nutrition 0.000 claims description 96
- 239000007788 liquid Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 38
- 239000007921 spray Substances 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 102000004190 Enzymes Human genes 0.000 claims description 20
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 102000035195 Peptidases Human genes 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 108091008146 restriction endonucleases Proteins 0.000 claims description 4
- 238000012807 shake-flask culturing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000004365 Protease Substances 0.000 abstract description 11
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
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- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 102000004169 proteins and genes Human genes 0.000 abstract description 5
- 108090000623 proteins and genes Proteins 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007071 enzymatic hydrolysis Effects 0.000 abstract 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 abstract 2
- 238000004880 explosion Methods 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 13
- 238000003381 deacetylation reaction Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 11
- 230000006196 deacetylation Effects 0.000 description 11
- 229920002101 Chitin Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
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- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 238000004321 preservation Methods 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- NHNUFAASKXPOQA-UHFFFAOYSA-N (3-acetamido-2-hydroxyphenyl)arsonic acid Chemical compound C(C)(=O)NC=1C(=C(C=CC1)[As](O)(=O)O)O NHNUFAASKXPOQA-UHFFFAOYSA-N 0.000 description 1
- 241000293029 Absidia caerulea Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108010054033 Chitin deacetylase Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000122799 Scopulariopsis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- Meat, Egg Or Seafood Products (AREA)
Abstract
The invention discloses a method for preparing chitosan by using shrimp shells. The method comprises the following steps: collecting shrimp shells; successively flushing, drying and crushing the shrimp shells; adjusting water content in shrimp shell powder to 20 to 30% with tap water; carrying out extrusion explosion puffing; crushing the puffed shrimp shell powder again and adding tap water to dissolve the shrimp shell powder; adjusting a pH value of an obtained slurry to 4.0 to 5.5; carrying out enzymatic hydrolysis on the shrimp shell slurry with bio-enzyme fermentation broth so as to remove acetylenzyme; then adding protease for enzymatic hydrolysis to remove proteins; carrying out rinsing; then adding organic acid and carrying out stirring for 2 to 3 h so as to remove a calcium salt in the shrimp shells; carrying out rinsing; adding a hydrogen peroxide solution for immersion decoloring; carrying out rinsing until a product becomes white; and finally carrying out vacuum drying until water content is less than 5%. The method provided by the invention has the characteristics of a simple and mature process, simple equipment, short preparation time, convenient operation, good continuity, high production efficiency, an ideal product form, no pollution, suitability for industrial production, widely and easily available raw materials, conservation of energy and convenience in popularization and popularization.
Description
[technical field]
The present invention relates to a kind of preparation method of chitosan, relate to a kind of shrimp shell that utilizes particularly and prepare methods of chitosan, belong to food processing field.
[background technology]
Chitin has another name called chitin, and its chemical name is (1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-β-D-glucose, is the straight chain polymer compound that is formed by connecting through β → 1,4 glycosidic link by N-acetylaminohydroxyphenylarsonic acid D-Glucopyranose monomer.It is the maximum nitrogenous natural organic high-molecular material of the outer quantity of occurring in nature isolating protein; Extensively be present in crustacean and arthropods and the bacteria cell wall, be described as the 6th vital principle after protein, fat, carbohydrate, VITAMINs and inorganic salt by American-European academia.
Chitosan (chitosan) has another name called chitosan, chitosan; Its chemical name is β-(1,4)-2-amino-2-deoxidation-D-VISOSE, and it is unformed, translucent, the slightly nacreous solid of white; Because of raw material different with the preparation method; Relative molecular mass does not wait to millions of from hundreds thousand of yet, and water insoluble and alkaline solution dissolves in mineral acid and most of organic acids such as rare hydrochloric acid, nitric acid.Chitosan is that ethanoyl in the chitin molecule is by the product after partly or entirely removing; Its solubility property is greatly improved, and is a large amount of unique alkaline polysaccharides that exist in the organic sphere, owing in the chitosan molecule a large amount of free amine groups is arranged; Molecule is positively charged; And molecular memory is easy to it is carried out various chemically modifieds in C-3 and light group of C-6 and C-2 amino groups, and reactive behavior is increased greatly.Therefore, chitosan is with a wide range of applications in fields such as food, weaving, medical treatment, health care, printing and dyeing, makeup, wastewater treatments.Chitosan is the product of chitin N-deacetylation, and generally speaking, the N-ethanoyl is sloughed and just can be referred to as chitosan more than 55%.To adopt the method for chemistry mostly be the concentrated base pyrogenic silica in the preparation of chitosan in the prior art, general in 40%～60% high alkali liquid under high temperature heterogeneous carrying out, the acetyl rate of taking off that obtains dissolving in diluted acid is the chitosan about 80% generally.But concentration of lye and temperature of reaction are high in the production process of chemical method; Reaction process can't effectively be controlled; Deacetylation under the heterogeneous conditions causes quality product because of the difference of manufacturing condition very big-difference to be arranged, unstable product quality, and range of molecular weight distributions is wide; Product is prone to degraded, and the chitosan that makes chemical process produce does not have very high using value in practical application.In addition, used concentration of lye of chemical method and temperature are high, and long reaction time has also caused problems such as energy dissipation and environmental pollution.
At present, people for address the above problem studied below several kinds prepare methods of chitosan:
1. utilize the self-control enzyme that chitin is taken off acetyl and handle, under the condition of pH value 4.5,50 ℃ of temperature and enzyme dosage 25ml, the chitin deacetylase degree that obtains is 71.49%.Though this method preparation condition comparison is gentle, the active less stable of self-control enzyme, the reaction times is longer, and reaction process is wide than difficult control, product molecular weight distribution.
2. solid state fermentation is handled the technology of Absidia coerulea, and the productive rate of chitosan is 11.6% under optimal medium, and purity is 83.5%, and deacetylation is 81.31%, and molecular weight is about 1.3 * 10
5Dalton.Come source problem though this method effectively solves deacetylase, the shrimp shell meal compact structure, percent crystallinity is higher, enzyme action time is longer.
3. utilize the microwave interrupter method under the microwave power of 320W; (quality: volume) the adding mass concentration was 50% NaOH solution in 1: 12 by solid-liquid ratio; Under microwave power 320W, handle 21min, the deacetylation of products obtained therefrom can reach 85.65%, and limiting viscosity is 394.07mL/g.Though this method has overcome long reaction time, but still adopt traditional highly basic pyroprocess, have problems such as concentration of lye and temperature of reaction are high, the difficult control of reaction process.
[summary of the invention]
The objective of the invention is to overcome the defective of traditional highly basic method, it is simple to disclose a kind of technology, safety and environmental protection, and the reaction times is short, and range of molecular weight distributions is narrow, and the shrimp shell that utilizes that product is stable prepares methods of chitosan.
The present invention is for realizing above-mentioned purpose, and the technical scheme of employing is:
A kind of shrimp shell that utilizes prepares methods of chitosan, it is characterized in that may further comprise the steps:
A, get the raw materials ready: collect the shrimp shell,, pulverize and obtain shrimp shell meal with tap water flushing shrimp shell after drying;
B, regulate the moisture content of shrimp shell meal material: with tap water the moisture content of shrimp shell meal is adjusted to 20%-30%, this percentage composition accounts for the percentage composition of moisture and shrimp shell meal gross weight for moisture weight;
C, will regulate the shrimp shell meal material extruding spray of moisture content quick-fried carry out expanded;
D, size mixing: add the tap water dissolving again after the shrimp shell meal material secondary of Pengization is pulverized and obtain the shrimp shell meal slurry, regulate pH value of slurry to 4.0-5.5;
E, deacetylase are separated: carry out the enzymolysis deacetylase with fermented by biological enzyme liquid prawn shell powder slurry;
F, deproteinated: in taking off the shrimp shell meal slurry of acetyl, add proteolytic enzyme enzymolysis 2-4h under 50-80 ℃ hydrolysis temperature, washing;
G, decalcification: in Deproteinated shrimp shell meal slurry, add organic acid stirring 2-3h and remove the calcium salt in the shrimp shell, washing;
H, decolouring: in the shrimp shell meal slurry of decalcification, add after hydrogen peroxide solution soaks 30-60min, become white with tap water flushing 2-3 time until product again;
I, drying: in vacuum tightness less than 133pa, temperature 50-60 ℃ of following vacuum-drying 4-6h to moisture content less than 5%.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, it is characterized in that the shrimp shell meal of pulverizing among the said step a is that 40 orders sieve.
The shrimp shell that the present invention adopts is the prawn processing byproduct, and prawn head, shrimp shell are analyzed knowledge, and be moisture, protein, chitin, ash content and fat main the composition, contains metallic elements such as manganese, magnesium, copper, zinc, iron in addition, specifically sees table 1.
Table 1: the raw material composition is formed table
| Project | Moisture/% | Ash content/% | Protein/% | Total reducing sugar/% | Fat/% | Chitin/% | Total acidity/% |
| The shrimp head | 78.44 | 3.62 | 6.38 | 0.27 | 2.42 | 3.33 | 2.30 |
| The shrimp shell | 75.15 | 5.30 | 5.22 | 0.16 | 1.09 | 6.67 | 2.29 |
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan; The extruding spray that it is characterized in that said shrimp shell meal is quick-fried by the twin-screw extruder completion, and described twin-screw extruder mainly is made up of feed system, motor, heating while puffing chamber, expanded screw rod and circuit control system.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, and the input speed that it is characterized in that described twin-screw extruder is 25-30kg/h, and screw speed is 240-280r/min, and spraying quick-fried temperature is 110-130 ℃.
The technology of the twin-screw extruder that the present invention adopts and production unit are all very ripe; Main manufacturing enterprise has: the SHJ series twin screw extruder that Jie Ente dynamo-electric ltd in Nanjing produces, the FMHE of Hunan Funach Foodstuff Engineering & Technology Co., Ltd. series twin-screw extruder etc.Moisture content with the shrimp shell meal material in the puffing process is adjusted to 20%-30%; So that in the puffing process smoothly when charging and expanded outlet the flash distillation effect of moisture cause and the change of shrimp shell weave construction help to reduce shrimp shell percent crystallinity and the functioning efficiency that improves deacetylase.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, it is characterized in that the particle diameter that said steps d Prawn shell secondary is pulverized is that 80 orders sieve, and the solid content of dissolved shrimp shell meal slurry is 20%-30%.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, and the potential of hydrogen that it is characterized in that shrimp shell meal slurry in the said steps d is with Hydrocerol A and sodium hydroxide adjustment.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, and it is mould at 27 ℃ of following shake-flask culture 96h for blue colter to it is characterized in that deacetylase among the said step e is separated the fermented by biological enzyme liquid of use, and isolated strains makes the fermented liquid that is rich in deacetylase.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, and the addition that it is characterized in that fermented by biological enzyme liquid among the said step e is 100-200U/g, and it is 40-60 ℃ that deacetylase is separated temperature, enzymolysis time 6-8h.
The blue colter that the present invention adopted is mould to be purchased in Chinese industrial microbial strains preservation administrative center, bacterial strain deposit number 40910.
Also can adopt the other biological enzyme to make the fermented liquid that is rich in deacetylase.For example adopt short handle pears spore broom mould (Scopulariopsis breviculis); Purchase medicinal microbial strains preservation administrative center in China; Bacterial strain deposit number CPCC800032; Mould isolated strains makes the fermented liquid that is rich in deacetylase at 27 ℃ of following shake-flask culture 96h with short handle pears spore broom, and the concrete reaction conditions of this fermented by biological enzyme liquid is: fermented liquid addition 100-200U/g, hydrolysis temperature 40-60 ℃, enzymolysis time 6-8h.
Deacetylase can be selected different enzyme sources, but the best enzymolysis process condition of the deacetylase in different enzyme source can be different.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, it is characterized in that described proteolytic enzyme is the mixture of restriction endonuclease and excision enzyme, and the addition of described proteolytic enzyme is 300-600U/g.
The proteolytic enzyme that the present invention adopts is Novi's letter compound protease (Protamex), is the mixture of restriction endonuclease and excision enzyme, this protease hydrolysis mild condition; Can avoid the generation of bitter peptides in the proteolyze process to greatest extent; Effectively improve proteolyze speed, of many uses, easy to use.
Aforesaid a kind of shrimp shell that utilizes prepares methods of chitosan, it is characterized in that described organic acid is that mass concentration is 10% Hydrocerol A, and the addition of said Hydrocerol A is that material liquid volume compares 20:1-10:1.Promptly add the Hydrocerol A of shrimp shell meal slurry volume mark 5%-10%.
The decolour strong oxidizer that uses of the present invention is 10% hydrogen peroxide solution as mass concentration, presses material liquid volume and adds than the addition of 20:1-10:1.
It is 1.0% potassium permanganate solution that decolouring uses strong oxidizer can also use mass concentration, press the addition interpolation of material liquid volume than 20:1-10:1.
Drying plant among the present invention in the drying step is vacuum drying oven (the Shanghai thunder rhythm test apparatus DZF-6020 of a Manufacturing Co., Ltd type).
The present invention with respect to the advantage of prior art is:
The present invention utilizes the prawn shell powder of the quick-fried technology of extruding spray to carry out mechanical degradation; The quick-fried technology of extruding spray is the flash distillation effect of water vapour under the HTHP; Realize the degraded of prawn shell and the change of crystal formation; The quick-fried process of extruding spray is a pure physical process, and its technology is simple, degraded snap, operational safety and consume energy low; Utilize the chitin in the biological enzymolysis technology prawn shell to take off acetyl, avoided chemical process to take off acetyl, realized safety and environmental protection, pollution-free.
The present invention utilizes physics and the biotechnology chitosan with shrimp shell processing and preparing, have more high deacetylized, take off that the acetyl degree is even, range of molecular weight distributions is narrow, special taste, nutritious, and contain abundant anti-oxidant activity polypeptide.
The invention solves the defective of other similar technology to environment and severe reaction conditions, technology is simply ripe, and equipment is simple; Preparation time is short, and is easy to operate, continuity good, produces efficient; Product form is desirable, and is pollution-free, is applicable to suitability for industrialized production; Raw material sources extensively are easy to get, and have practiced thrift the energy, are convenient to popularize and promote.
[embodiment]
Below in conjunction with embodiment the present invention is done to further describe, but the present invention is not limited to following examples:
A kind of shrimp shell that utilizes is made methods of chitosan, and it may further comprise the steps:
A, get the raw materials ready: collect the shrimp shell, pulverize with tap water flushing shrimp shell after drying and obtain shrimp shell meal, the particle diameter of this shrimp shell meal is that 40 orders sieve;
B, regulate the moisture content of shrimp shell meal material: the moisture content of shrimp shell meal is adjusted to 20%-30% with tap water;
C, will regulate quick-fried the carrying out of shrimp shell meal material extruding spray of moisture content; The quick-fried equipment of extruding spray is twin-screw extruder; Mainly form by feed system, motor, heating while puffing chamber, expanded screw rod and circuit control system; The expanded input speed of extruder is 25-30kg/h, and screw speed is 240-280r/min, and spraying quick-fried temperature is 110-130 ℃;
D, size mixing: the shrimp shell meal material secondary of Pengization is crushed to adds the tap water dissolving after 80 orders sieve again and obtain the shrimp shell meal slurry that solid content is 20%-30%, adjust pH value of slurry to 4.0～5.5 with Hydrocerol A and sodium hydroxide; Turn down with Hydrocerol A when the pH value is too high, pH crosses when hanging down and heightens with sodium hydroxide.
E, deacetylase are separated: carry out the enzymolysis deacetylase with fermented by biological enzyme liquid prawn shell powder slurry; This fermented by biological enzyme liquid is that blue colter is mould at 27 ℃ of following shake-flask culture 96h; Isolated strains makes the fermented liquid that is rich in deacetylase; Its addition is 100-200U/g, and it is 40-60 ℃ that deacetylase is separated temperature, enzymolysis time 6-8h;
F, deproteinated: in the above-mentioned shrimp shell meal slurry that has taken off acetyl, add the compound protease 300-600U/g of restriction endonuclease and excision enzyme, enzymolysis 2-4h under 50-80 ℃ hydrolysis temperature;
G, decalcification: in Deproteinated shrimp shell meal slurry, add organic acid stirring 2-3h than 20:1-10:1 and remove the calcium salt in the shrimp shell by material liquid volume; This organic acid is that mass concentration is 10% Hydrocerol A;
H, decolouring: in the shrimp shell meal of decalcification, adding mass concentration by material liquid volume than 20:1-10:1 is after 10% hydrogen peroxide solution soaks 30-60min, becomes white with tap water flushing 2-3 time until product again;
I, drying: less than 133pa, temperature 50-60 ℃ of following vacuum-drying 4-6h promptly gets chitosan less than 5% to moisture content in vacuum tightness.
Can dried chitosan powder be broken to 100 orders when packing at last, be packaged into finished product.
Embodiment one:
Collect 100kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 25kg is adjusted to 20% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 25kg/h, and screw speed is 240r/min; Spray 110 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 20%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 4.0; Add blue colter enzymic fermentation liquid 100U/g; Prawn shell powder slurry carries out enzymolysis 6h under 40 ℃ hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, adds compound protease 300U/g, enzymolysis 2h under 50 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 20:1 is that 10% Hydrocerol A stirs 2h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 20:1 by material liquid volume soak 60min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 50 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 7.6kg less than 5% to moisture content.
Through detecting, the chitosan sample moisture content that makes is 4.8%, deacetylation is 88.4%, range of molecular weight distributions is 80-110 ten thousand dalton.
Embodiment two:
Collect 100kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 31.6kg is adjusted to 24% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 28kg/h, and screw speed is 260r/min; Spray 120 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 25%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 5.0; Add blue colter enzymic fermentation liquid 150U/g; Carry out enzymolysis 7h at 50 ℃ of following prawn shell powder slurries of hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, add compound protease 600U/g, enzymolysis 3h under 60 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 15:1 is that 10% Hydrocerol A stirs 2h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 15:1 by material liquid volume soak 50min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 55 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 7.8kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.6%, deacetylation is 85.6%, range of molecular weight distributions is 90-120 ten thousand dalton.
Embodiment three:
Collect 100kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 39kg is adjusted to 28% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 25kg/h, and screw speed is 240r/min; Spray 130 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 30%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 5.5; Add blue colter enzymic fermentation liquid 200U/g; Carry out enzymolysis 8h at 50 ℃ of following prawn shell powder slurries of hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, add compound protease 400U/g, enzymolysis 4h under 60 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 12:1 is that 10% Hydrocerol A stirs 2h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 12:1 by material liquid volume soak 40min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 55 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 7.2kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.9%, deacetylation is 87.6%, range of molecular weight distributions is 80-100 ten thousand dalton.
Embodiment four:
Collect 100kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 43kg is adjusted to 30% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 30kg/h, and screw speed is 280r/min; Spray 130 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 30%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 5.5; Add blue colter enzymic fermentation liquid 200U/g; Carry out enzymolysis 8h at 60 ℃ of following prawn shell powder slurries of hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, add compound protease 500U/g, enzymolysis 4h under 80 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 10:1 is that 10% Hydrocerol A stirs 3h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 10:1 by material liquid volume soak 30min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 60 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 7.4kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.6%, deacetylation is 86.9%, range of molecular weight distributions is 90-110 ten thousand dalton.
Embodiment five:
Collect 50kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 12.5kg is adjusted to 20% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 25kg/h, and screw speed is 240r/min; Spray 110 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 20%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 4.0; Add blue colter enzymic fermentation liquid 100U/g; Carry out enzymolysis 6h at 40 times prawn shell powder of hydrolysis temperature slurry, in the shrimp shell meal slurry of deacetylase, add compound protease 300U/g, enzymolysis 2h under 50 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 20:1 is that 10% Hydrocerol A stirs 2h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 20:1 by material liquid volume soak 30min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 50 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 3.5kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.8%, deacetylation is 87.6%, range of molecular weight distributions is 80-110 ten thousand dalton.
Embodiment six:
Collect 80kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 27kg is adjusted to 25% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 28kg/h, and screw speed is 260r/min; Spray 120 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 25%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 5.0; Add blue colter enzymic fermentation liquid 150U/g; Carry out enzymolysis 7h at 50 ℃ of following prawn shell powder slurries of hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, add compound protease 600U/g, enzymolysis 3h under 60 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 12:1 is that 10% Hydrocerol A stirs 2h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 12:1 by material liquid volume soak 40min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 55 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 5.8kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.9%, deacetylation is 87.2%, range of molecular weight distributions is 80-120 ten thousand dalton.
Embodiment seven:
Collect 30kg shrimp shell; Obtain the shrimp shell meal that 40 orders sieve with the pulverizing of tap water flushing shrimp shell after drying; Adding tap water 13kg is adjusted to 30% with the moisture content of shrimp shell meal, and the shrimp shell meal that mixes up moisture is put into the quick-fried equipment of extruding spray with expanded input speed 30kg/h, and screw speed is 280r/min; Spray 130 ℃ of quick-fried temperature push the spray quick-fried expanded; Expanded shrimp shell meal material secondary is crushed to adds tap water after 80 orders sieve again to be dissolved to solid content be 30%, obtain the shrimp shell meal slurry, using Hydrocerol A and sodium hydroxide adjusting pH value of slurry is 5.5; Add blue colter enzymic fermentation liquid 200U/g; Carry out enzymolysis 8h at 60 ℃ of following prawn shell powder slurries of hydrolysis temperature, in the shrimp shell meal slurry of deacetylase, add compound protease 500U/g, enzymolysis 4h under 80 ℃ hydrolysis temperature; In Deproteinated shrimp shell meal slurry, adding mass concentration by material liquid volume than 10:1 is that 10% Hydrocerol A stirs 3h and removes the calcium salt in the shrimp shell; Again with mass concentration be 10% hydrogen peroxide solution add than 10:1 by material liquid volume soak 60min in the shrimp shell meal slurry of decalcification after, again with the tap water flushing after product becomes white, put into for 2-3 time vacuum drying oven in vacuum tightness less than 133pa, 60 ℃ of following vacuum-drying 4-6h of temperature promptly get powdery chitosan 2.2kg less than 5% to moisture content.
Through detecting, the moisture content that makes the chitosan sample is 4.6%, deacetylation is 87.5%, range of molecular weight distributions is 80-110 ten thousand dalton.
The chitosan that the present invention obtains is full powdery, also can process the particle of different shape through mould, and product is different according to chitosan content and sanitation degree, can be used as functional ingredient and is respectively applied for food, medicine and feedstuff industry.
The present invention utilizes the extruding quick-fried technology of spray and biological enzymolysis technology prawn shell powder carries out mechanical degradation, biology takes off acetyl and prepares chitosan; Have that technology is simple, snap, operational safety and the low characteristics of power consumption; Not only improve the stability of chitosan production technique; Effectively reduce chitin percent crystallinity, improve and take off acetyl efficient, shorten the chitosan production cycle.That the chitosan of the present invention preparation has is more high deacetylized, take off that the acetyl degree is even, range of molecular weight distributions is narrow, special taste, and the product yield is more than 7%, and deacetylation is more than 85%, and molecular weight is between 80-120 ten thousand dalton.Simultaneously, the present invention effectively reduces the percent crystallinity of chitin, and the chitosan of preparation not only readily digested absorbs, and also has certain nourishing function, in the production of chitosan, has great application prospect.
Claims (10)
1. one kind is utilized the shrimp shell to prepare methods of chitosan, it is characterized in that may further comprise the steps:
A, get the raw materials ready: collect the shrimp shell,, pulverize and obtain shrimp shell meal with tap water flushing shrimp shell after drying;
B, regulate the moisture content of shrimp shell meal material: the moisture content of shrimp shell meal is adjusted to 20%-30% with tap water;
C, will regulate the shrimp shell meal material extruding spray of moisture content quick-fried carry out expanded;
D, size mixing: add the tap water dissolving again after expanded shrimp shell meal material secondary is pulverized and obtain the shrimp shell meal slurry, regulate pH value of slurry to 4.0-5.5;
E, deacetylase are separated: carry out the enzymolysis deacetylase with fermented by biological enzyme liquid prawn shell powder slurry;
F, deproteinated: in taking off the shrimp shell meal slurry of acetyl, add proteolytic enzyme enzymolysis 2-4h under 50-80 ℃ hydrolysis temperature, washing;
G, decalcification: in Deproteinated shrimp shell meal slurry, add organic acid stirring 2-3h and remove the calcium salt in the shrimp shell, washing;
H, decolouring: after in the shrimp shell meal slurry of decalcification, adding hydrogen peroxide solution immersion 30-60min, become white with the tap water flushing until product again;
I, drying: in vacuum tightness less than 133pa, temperature 50-60 ℃ of following vacuum-drying 4-6h to moisture content less than 5%.
2. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, it is characterized in that the shrimp shell meal of pulverizing among the said step a is that 40 orders sieve.
3. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan; The extruding spray that it is characterized in that said shrimp shell meal is quick-fried by the twin-screw extruder completion, and described twin-screw extruder mainly is made up of feed system, motor, heating while puffing chamber, expanded screw rod and circuit control system.
4. a kind of shrimp shell that utilizes according to claim 3 prepares methods of chitosan, and the input speed that it is characterized in that described twin-screw extruder is 25-30kg/h, and screw speed is 240-280r/min, and spraying quick-fried temperature is 110-130 ℃.
5. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, it is characterized in that the particle diameter that said steps d Prawn shell secondary is pulverized is that 80 orders sieve, and the solid content of dissolved shrimp shell meal slurry is 20%-30%.
6. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, and the potential of hydrogen that it is characterized in that shrimp shell meal slurry in the said steps d is with Hydrocerol A and sodium hydroxide adjustment.
7. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan; It is mould at 27 ℃ of following shake-flask culture 96h for blue colter to it is characterized in that deacetylase among the said step e is separated the fermented by biological enzyme liquid of use, and isolated strains makes the fermented liquid that is rich in deacetylase.
8. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, and the addition that it is characterized in that fermented by biological enzyme liquid among the said step e is 100-200U/g, and it is 40-60 ℃ that deacetylase is separated temperature, enzymolysis time 6-8h.
9. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, it is characterized in that described proteolytic enzyme is the mixture of restriction endonuclease and excision enzyme, and the addition of described proteolytic enzyme is 300-600U/g.
10. a kind of shrimp shell that utilizes according to claim 1 prepares methods of chitosan, it is characterized in that described organic acid is that mass concentration is 10% Hydrocerol A, and described Hydrocerol A addition is that material liquid volume compares 20:1-10:1.
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| CN103718803A (en) * | 2013-12-23 | 2014-04-16 | 广西南宁碧湾园林工程有限公司 | Method for using chitin to promote rooting of vegetable seedlings |
| CN104046669A (en) * | 2013-09-29 | 2014-09-17 | 天津天狮生物发展有限公司 | Method for preparing chitosan through two-stage calcium removal |
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