CN102086464A - Method for preparing chitin - Google Patents
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- CN102086464A CN102086464A CN2009101547626A CN200910154762A CN102086464A CN 102086464 A CN102086464 A CN 102086464A CN 2009101547626 A CN2009101547626 A CN 2009101547626A CN 200910154762 A CN200910154762 A CN 200910154762A CN 102086464 A CN102086464 A CN 102086464A
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- acid
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- shrimp shell
- enzyme
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 27
- 102000004190 Enzymes Human genes 0.000 claims abstract description 25
- 108090000790 Enzymes Proteins 0.000 claims abstract description 25
- 150000007524 organic acids Chemical class 0.000 claims abstract description 21
- 239000011575 calcium Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000002525 ultrasonication Methods 0.000 claims abstract description 5
- 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 description 27
- 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
- 230000000694 effects Effects 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 102000035101 Aspartic proteases Human genes 0.000 claims description 11
- 108091005502 Aspartic proteases Proteins 0.000 claims description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 8
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 239000000174 gluconic acid Substances 0.000 claims description 8
- 235000012208 gluconic acid Nutrition 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 235000005985 organic acids Nutrition 0.000 claims description 8
- 235000002949 phytic acid Nutrition 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 239000013505 freshwater Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000000703 high-speed centrifugation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001238 wet grinding Methods 0.000 claims description 3
- 230000003544 deproteinization Effects 0.000 claims description 2
- 235000012054 meals Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 8
- 102000004169 proteins and genes Human genes 0.000 abstract description 7
- 108090000623 proteins and genes Proteins 0.000 abstract description 7
- 159000000007 calcium salts Chemical class 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 159000000003 magnesium salts Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 108091005508 Acid proteases Proteins 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010865 sewage Substances 0.000 description 9
- 241000238557 Decapoda Species 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 206010039509 Scab Diseases 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 241000707825 Argyrosomus regius Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a novel method for preparing chitin, which belongs to the technical field of wastewater integrated utilization in the food and medicine processing process. The method for preparing chitin comprises the steps of: (1) smashing; (2) adding an organic acid aqueous solution for acidolysis to remove inorganic salt; (3) adding mixed enzyme containing an acid protease to remove protein; (4) performing ultrasonication; and (5) centrifuging the reactants at a high speed and drying the centrifuged dregs to prepare chitin. The novel method for preparing chitin can be used for removing calcium salts, magnesium salts and protein at one step so as to obtain chitin and high-quality calcium protein powder, lower the production cost and reduce the discharge of industrial wastewater.
Description
Technical field
The present invention relates to a kind of new chitin production method, belong to the technical field of the waste water comprehensive utilization in food, the medical course of processing.
Background technology
Chitin is a kind of natural high molecular substance biological polyoses, extensively is present in the cell walls of the crust of Crustacean such as crusts such as shrimp, crab, insect and plant, in nature, exist next in number only to Mierocrystalline cellulose.Chitin is that after albumen, fat, VITAMIN another kept the key element of human life.Therefore be the important source material of medicine, food, light industry, chemical industry, environmental protection etc.
The method that the production technique of utilizing shrimp head, shrimp shell or crab shell to produce chitin is continued to use always: remove inorganic minerals such as calcium, phosphorus in the shrimp crab crust with hydrochloric acid soln earlier, the water flushing is to neutral.Use in the sodium hydroxide solution hydrolysis shell then and the protein (comprising muscle, internal organ, its hetero-organization etc.) on the shell, the water flushing dehydrates at last and forms the chitin product to neutral.Though this preparation process of chitin method is simple, applicability is strong, and it is big to produce wastewater flow rate, serious environment pollution.
At present, 1 ton of chitin of the every production of cleaner preparation process of chitin will drop into 2.5-3 ton sodium hydroxide, the hydrochloric acid of 8-10 ton, and 150-200 ton fresh water, discharging contains strong acid, highly basic and organic industrial sewage 150-200 ton.So huge sewage quantity is serious and far-reaching to the pollution and the influence of environment.
In recent years, domesticly reported once that tens patents about administering waste water for producing crust element and comprehensive utilization several different methods ， Dan Only to handling with waste acid water, the alkali waste water produced and utilizing, can't break away from the use and the sewage emissions of highly basic, strong acid.
In actual production, be the industry of meagre profit owing to produce chitin, small business is many, the generation of large amount of sewage needs expensive cost of sewage disposal, is difficult to implement qualified discharge.Therefore the quantity of wastewater effluent that reduces in the middle of the chitin production is that chitin manufacturing enterprise is expected for a long time, does not reach the purpose that reduces quantity of wastewater effluent, zero release still more but still there is the production that economical and practical method can make chitin for a long time.
Summary of the invention
In order to solve the technological deficiency of the big serious environment pollution of wastewater flow rate in the existing preparation process of chitin, the preparation method who the purpose of this invention is to provide a kind of chitin, thereby the disposable removal calcium salt of this method, magnesium salts and protein obtain chitin, reduce production cost, reduced the industrial sewage discharging.
In order to realize above-mentioned technical purpose, the present invention has adopted following technical scheme:
A kind of preparation method of chitin, this method comprises the steps: 1. to pulverize; 2. add the aqueous solutions of organic acids acidolysis and take off inorganic salt; 3. add the mixed enzyme deproteinization that contains aspartic protease; 4. ultrasonication; 5. with the reactant high speed centrifugation, the slag drying after centrifugal is prepared into chitin.
As preferably, this method specifically comprises the steps:
1. pulverize reinforced: with the chitin raw material pulverizing, and the shrimp shell meal after will pulverizing is sent in the reactor that ultrasonic unit is housed;
2. acidolysis: add aqueous solutions of organic acids, the organic acid weight percent concentration in the aqueous solutions of organic acids is 1%～5%, is warming up to 55 ℃～65 ℃, reaction 30min～45min;
3. enzymolysis: add the mixed enzyme that contains aspartic protease, the adding weight of mixed enzyme is 0.01～0.05 of shrimp shell, reaction 30min～45min, 50 ℃～55 ℃ of temperature;
4. ultrasonication: start ultrasonic unit, temperature of reaction keeps 45 ℃～55 ℃, and ultrasonic wave action time is 30～80min;
5. with the reactant high speed centrifugation, the slag drying after centrifugal is prepared into chitin.
As preferably, above-mentioned step 1. in the granularity of chitin raw material pulverizing be 3 orders～10 orders.
As preferably, above-mentioned step 2. in the add-on of aqueous solutions of organic acids be 6～8 times of shrimp shell weight; Organic acid is selected the multiple mixing in lactic acid, formic acid, propionic acid, citric acid, oxysuccinic acid, gluconic acid and the phytic acid for use.Above-mentioned organic acid is selected relevant with the nutrition of follow-up protein powder.Form by lactic acid, formic acid, propionic acid, citric acid, oxysuccinic acid, gluconic acid and phytic acid as the 2. middle organic acid of preferred again, above-mentioned step, by weight percentage:
Lactic acid 30%～60% formic acid 2%～10% propionic acid 5%～15%
Citric acid 2%～15% oxysuccinic acid 2%～15% gluconic acid 2%～15%
Phytic acid 0.5%～1%.
As preferably, above-mentioned step in 5. the liquid after centrifugal with pulverizing activated carbon decolorizing, destainer is crossed micro-filtration, filtered liquid is crossed the chitosan resin post then, at last filtered liquid is crossed the resin anion(R.A) post, filtrate is 15%～25% through high-temperature sterilization unit vacuum concentration to solid content, and spraying drying is to powdered albumen calcium powder.
As preferably, above-mentioned step 3. in mixed enzyme form enzyme activity＞10000ul/g by aspartic protease, papoid and half fiber optics enzyme.As preferred again, above-mentioned mixed enzyme is made of following component by weight percentage: aspartic protease 30%～70%, papoid 20%～50%, half fiber optics enzyme 5%～10%.
As preferably, above-mentioned step 4. in hyperacoustic requirement be ultrasonic frequency 20KHZ～120KHZ, L=1～5W falls in sound.
As preferably, above-mentioned chitin raw material adopts fresh shrimp shell, new fresh shrimp shell fresh water flushing, this wash-down water is crossed the grid settling tank, advance adsorption tank, cross grid to clean water basin after grid, shrimp shell after the flushing is centrifugal, broken or the screw extrusion of shrimp shell wet-milling becomes 3～10 orders, and slurries are squeezed in the reactor, adds deionized water by 20%～50% of slurry weight.
The employing mixed organic acid makes the CaCO in the shrimp shell among the present invention
3, MgCO
3, Ca
3(PO
4)
2, Mg
3(PO
4)
2In inorganic salt under cavitation effect of ultrasonic waves, temperature breaks away from the shrimp shell than more completely in the time of 60 ℃, within a short period of time and organic acid knot and be dissolved in the solution (under the no ultrasonic wave situation, inorganic salt at normal temperatures also can with organic acid in conjunction with dissolving, but the time be about be 18h-24h).Mixed enzyme (based on the aspartic protease of aspergillus niger extraction), when pH=4～6 conditions, albumen in 45 ℃～55 ℃ prawn shells of temperature becomes low molecular peptide and each amino acid to be dissolved in the solution with the meat mincing enzymolysis on shrimp head, the shrimp shell, under the moving situation of hyperacoustic association, speed up, react more complete, the disengaging rate is greater than 95%.
In addition, the present invention adopts ultrasonic wave to separate, and calcium salt separates strengthening effect and is mainly derived from hyperacoustic cavitation effect with proteic in the ultrasonic wave prawn shell.Hyperacoustic cavitation effect is meant that the small complex in the liquid is activated under the high intense ultrasonic wave effect of low frequency, it shows as a series of dynamic processes such as vibration, growth, contraction and collapse of complex, around cavitation bubble, produce High Temperature High Pressure in the utmost point short period of time of cavitation bubble collapse, and with the intensive shockwave and the time scooter 400km microjet produce.The ultrasonic cavitation effect has caused turbulence effect, cavity effect, perturbation effect and interfacial effect, and wherein turbulence effect makes the frictional belt attenuate, increases rate of mass transfer; The perturbation effect has been strengthened the micropore diffusion; It is long-pending that interfacial effect has increased mass transfer surfaces; Cavity effect has activated the separate substance molecule.Thereby ultrasonic wave can be strengthened the rate of mass transfer and the effect of sepn process.
The present invention has been owing to adopted above-mentioned technical scheme, thereby can disposable removal calcium salt, magnesium salts and protein obtains chitin and high-quality albumen calcium powder, reduced production cost, reduced the industrial sewage discharging.
Embodiment
Embodiment 1
Dry method shrimp shell prepares the method for chitin, and this method comprises the steps:
1. the dried shrimp shell of 300Kg (moisture≤10%) is crushed to 5 orders, sucks in the 3000L enamel reaction still (6 of ultrasonic probes are housed, and ultrasonic frequency is 40KHZ) with vacuum, add deionized water 2000Kg simultaneously, stir, rotating speed is 50r/min.
2. will be warming up to 60 ℃, and slowly add organic mixing acid 60Kg, organic mixing acid is made up of following organic acid: the phytic acid of lactic acid, formic acid, propionic acid, citric acid, oxysuccinic acid, gluconic acid and trace.By weight percentage: lactic acid 55%, formic acid 8%, propionic acid 12%, citric acid 10.5%, oxysuccinic acid 9.5%, gluconic acid 4.5%, phytic acid 0.5%.
3. adjusting rotating speed is 20r/min, behind the reaction 30min, is cooled to 50 ℃, adds mixed enzyme 4.5Kg, and mixed enzyme is made up of following enzyme: aspartic protease, papoid, half fiber optics enzyme, its enzyme activity＞10000ul/g.By weight percentage: aspartic protease 60%, papoid 30, % half fiber optics enzyme 10%.
4. after stirring 15min, open ultrasonic wave, stop ultrasonic wave behind the 30min, continue to stir 30min, finish reaction, temperature remains 50 ℃ ± 1 ℃.
5. (behind the V＞3000r/min), centrifugal slag is entered the boiling drier drying, finished product is chitin (moisture 8%, an ash content 10.5%) to feed liquid, and dried chitin weight is 55.7Kg through supercentrifuge.
6. with centrifugate through decolorizing with activated carbon, after micro-filtration (hole order 0.1-1um removes minute impurities and sterilization), filtrate continues (to remove cl by chitosan resin post (removing heavy metal ion and harmful metal ion) and resin anion(R.A) post
-1, SO
4 2-), pump pressure is 0.3Mpa, filtrate is 15%～25% through high-temperature sterilization, vacuum concentration to solid content, spraying drying, finished product are the albumen calcium powder, and weight is 131.8Kg (moisture 5%, calcium contents 13.2%, protein content 64.6%), 70 ℃ of warm water＞85% of the solubleness of albumen calcium powder are rich in human 17 essential seed amino acids.
Further specify (to prepare 1 ton of chitin) according to table 1 pair beneficial effect of the present invention below:
| Title | Conventional | The present invention | Remarks |
| New fresh shrimp shell | The 33-35 ton | The 28-30 ton | |
| Sewage discharge | 200 tons | 0 ton | Common process produces sewage: COD＞10000, and pH＜3, pH＞10, colourity are dark red.The present invention: the treated reusable edible of water of flushing shrimp shell and ground and equipment |
| Byproduct | 1-1.2 ton | 2.5 ton | Common process: feed grade albumen calcium, price 0.2-0.4 ten thousand/ton the present invention: the food-grade albumen calcium powder, price is at 2-4 ten thousand/ton |
| Steam consumption | The 10-15 ton | The 6-8 ton | The drying that comprises chitin, albumen calcium powder |
| Power consumption | 500 kilowatt-hours | 2000 kilowatt-hours | |
| Consumption fresh water | 200 tons | 50 tons | |
| Chemical raw material consumption | Hydrochloric acid 8-9 ton, sodium hydroxide 2.5-3 ton | Organic acid 200Kg, mixed enzyme 15Kg | The industrial chemicals expense is 50% of a common process. |
| Preparation time | 24-36h | 6-8h |
Embodiment 2
The wet method fresh shrimp shell directly prepares the method for chitin, this method is washed new fresh shrimp shell fresh water (0.5-2 that this flushing fresh water amount is the shrimp shell doubly), this wash-down water is crossed the grid settling tank, advance adsorption tank (sandstone, natural zeolite, activated carbon layer, chitosan resin layer) after grid, cross grid to clean water basin (this water is reused).Shrimp shell after the flushing is centrifugal, and the broken or screw extrusion of shrimp shell wet-milling becomes the 3-10 order, and slurries are squeezed in the reactor, adds the 20%-50% of deionized water by slurry weight, and back technology is with reference to the method for embodiment 1.
Claims (10)
1. the preparation method of a chitin is characterized in that this method comprises the steps: 1. to pulverize; 2. add the aqueous solutions of organic acids acidolysis and take off inorganic salt; 3. add the mixed enzyme deproteinization that contains aspartic protease; 4. ultrasonication; 5. with the reactant high speed centrifugation, the slag drying after centrifugal is prepared into chitin.
2. the preparation method of a kind of chitin according to claim 1 is characterized in that this method specifically comprises the steps:
1. pulverize reinforced: with the chitin raw material pulverizing, and the shrimp shell meal after will pulverizing is sent in the reactor that ultrasonic unit is housed;
2. acidolysis: add aqueous solutions of organic acids, the organic acid weight percent concentration in the aqueous solutions of organic acids is 1%～5%, is warming up to 55 ℃～65 ℃, reaction 30min～45min;
3. enzymolysis: add the mixed enzyme that contains aspartic protease, the adding weight of mixed enzyme is 0.01～0.05 of shrimp shell, reaction 30min～45min, 50 ℃～55 ℃ of temperature;
4. ultrasonication: start ultrasonic unit, temperature of reaction keeps 45 ℃～55 ℃, and ultrasonic wave action time is 30～80min;
5. with the reactant high speed centrifugation, the slag drying after centrifugal is prepared into chitin.
3. the preparation method of a kind of chitin according to claim 1 and 2 is characterized in that: step 1. in the granularity of chitin raw material pulverizing be 3 orders～10 orders.
4. the preparation method of a kind of chitin according to claim 2 is characterized in that: step 2. in the add-on of aqueous solutions of organic acids be 6～8 times of shrimp shell weight; Organic acid is selected the multiple mixing in lactic acid, formic acid, propionic acid, citric acid, oxysuccinic acid, gluconic acid and the phytic acid for use.
5. the preparation method of a kind of chitin according to claim 4 is characterized in that: step 2. in organic acid form by lactic acid, formic acid, propionic acid, citric acid, oxysuccinic acid, gluconic acid and phytic acid, by weight percentage:
Lactic acid 30%～60% formic acid 2%～10% propionic acid 5%～15%
Citric acid 2%～15% oxysuccinic acid 2%～15% gluconic acid 2%～15%
Phytic acid 0.5%～1%.
6. according to the preparation method of claim 1 or 2 or 4 or 5 described a kind of chitins, it is characterized in that: step in 5. the liquid after centrifugal with pulverizing activated carbon decolorizing, destainer is crossed micro-filtration, filtered liquid is crossed the chitosan resin post then, at last filtered liquid is crossed the resin anion(R.A) post, filtrate is 15%～25% through high-temperature sterilization unit vacuum concentration to solid content, and spraying drying is to powdered albumen calcium powder.
7. the preparation method of a kind of chitin according to claim 1 and 2 is characterized in that: step 3. in mixed enzyme form enzyme activity＞10000ul/g by aspartic protease, papoid and half fiber optics enzyme.
8. the preparation method of a kind of chitin according to claim 7 is characterized in that mixed enzyme is made of following component by weight percentage:
Aspartic protease 30%～70%
Papoid 20%～50%
Half fiber optics enzyme 5%～10%.
9. the preparation method of a kind of chitin according to claim 1 and 2 is characterized in that: step 4. in hyperacoustic requirement be ultrasonic frequency 20KHZ～120KHZ, L=1～5W falls in sound.
10. the preparation method of a kind of chitin according to claim 1 and 2, it is characterized in that: the chitin raw material adopts fresh shrimp shell, new fresh shrimp shell fresh water flushing, this wash-down water is crossed the grid settling tank, advance adsorption tank, cross grid to clean water basin after grid, shrimp shell after the flushing is centrifugal, broken or the screw extrusion of shrimp shell wet-milling becomes 3～10 orders, and slurries are squeezed in the reactor, adds deionized water by 20%～50% of slurry weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154762.6A CN102086464B (en) | 2009-12-02 | 2009-12-02 | Method for preparing chitin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154762.6A CN102086464B (en) | 2009-12-02 | 2009-12-02 | Method for preparing chitin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102086464A true CN102086464A (en) | 2011-06-08 |
| CN102086464B CN102086464B (en) | 2014-07-30 |
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| CN103755834A (en) * | 2014-01-26 | 2014-04-30 | 扬州日兴生物科技股份有限公司 | Methods for preparing active peptide powders and chitins from shrimp and crab by-products |
| CN103931735A (en) * | 2014-04-23 | 2014-07-23 | 昆山市富众网络科技有限公司 | Mechanical filter of enzymatic hydrolysis pool for crab shell |
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| CN105418802A (en) * | 2015-12-29 | 2016-03-23 | 广西钦州市绿源天然食品加工有限公司 | Method for extracting chitin from shrimp heads and shrimp shells by utilization of organic acids and combined with acidic proteases |
| CN109053930A (en) * | 2018-09-06 | 2018-12-21 | 黄河三角洲京博化工研究院有限公司 | A kind of technique preparing chitin and coproduction organic calcium fertilizer |
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| CN101289518B (en) * | 2008-06-06 | 2010-07-07 | 石勇 | Method for preparing chitin and process for preparing chitosan by using chitin |
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| CN103755834B (en) * | 2014-01-26 | 2016-05-11 | 扬州日兴生物科技股份有限公司 | A kind of method of preparing active peptide powder and chitin from shrimp crab accessory substance |
| CN103931735A (en) * | 2014-04-23 | 2014-07-23 | 昆山市富众网络科技有限公司 | Mechanical filter of enzymatic hydrolysis pool for crab shell |
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| CN104480228A (en) * | 2014-11-25 | 2015-04-01 | 荣成宏业海洋科技有限公司 | Method for preparing glucosamine by utilizing shrimp and crab shells |
| CN105418802A (en) * | 2015-12-29 | 2016-03-23 | 广西钦州市绿源天然食品加工有限公司 | Method for extracting chitin from shrimp heads and shrimp shells by utilization of organic acids and combined with acidic proteases |
| CN109924358A (en) * | 2017-12-15 | 2019-06-25 | 姜宏鹏 | A kind of feed of bacon hogs and preparation method thereof |
| CN109134703A (en) * | 2018-08-01 | 2019-01-04 | 农业部规划设计研究院 | A kind of method that shrimp and crab shells waste cleans comprehensive utilization |
| CN109053930A (en) * | 2018-09-06 | 2018-12-21 | 黄河三角洲京博化工研究院有限公司 | A kind of technique preparing chitin and coproduction organic calcium fertilizer |
| CN109647792A (en) * | 2018-12-27 | 2019-04-19 | 温州科技职业学院 | A kind of method of the lower shrimp shell desalination of ultrasound |
| CN110590628A (en) * | 2019-09-20 | 2019-12-20 | 林大昌 | Method for extracting natural astaxanthin from fresh shrimps and/or crab waste |
| CN113527540A (en) * | 2021-08-13 | 2021-10-22 | 上海应用技术大学 | Production method for extracting chitosan oligosaccharide from shrimp shells |
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