CN102106493A - Method for reclaiming fluoride in Antarctic krill and preparing low-fluorine krill meal - Google Patents
Method for reclaiming fluoride in Antarctic krill and preparing low-fluorine krill meal Download PDFInfo
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- CN102106493A CN102106493A CN2011100331725A CN201110033172A CN102106493A CN 102106493 A CN102106493 A CN 102106493A CN 2011100331725 A CN2011100331725 A CN 2011100331725A CN 201110033172 A CN201110033172 A CN 201110033172A CN 102106493 A CN102106493 A CN 102106493A
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- krill
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 43
- 239000011737 fluorine Substances 0.000 title claims abstract description 43
- 241000239366 Euphausiacea Species 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 235000012054 meals Nutrition 0.000 title claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract 3
- 230000001105 regulatory effect Effects 0.000 claims abstract 2
- 241000238557 Decapoda Species 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000009834 vaporization Methods 0.000 claims description 8
- 230000008016 vaporization Effects 0.000 claims description 8
- 238000010009 beating Methods 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 8
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 235000021393 food security Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000239370 Euphausia superba Species 0.000 description 1
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention belongs to the fields of resource reclamation and food safety, and relates to a method for reclaiming fluoride in Antarctic krill and preparing low-fluorine krill meal. The method comprises the following steps of: cleaning the Antarctic krill, crushing and pulping, performing filtration to remove solid impurities so as to obtain Antarctic krill homogenate, regulating the acidity by using strong acid, and performing reduced pressure evaporation; and performing conventional distillation and purification on the obtained condensate, reclaiming fluorocarboxylic acid, and absorbing non-condensable gas by using alkali solution. The method can prepare the low-fluorine krill meal, the fluorine content of the krill meal is less than 2mg/kg, and the yield of the krill meal is over 90 percent. The flow is simple, harmful chemical reagents are not added, the process is environmentally-friendly, and the low-fluorine krill meal reaching the pollution-free food standard can be prepared and can be used as a raw material for various foods, health-care products and medicaments.
Description
Technical field
The invention belongs to resource and reclaim and the food security field, relate to the method that reclaims fluoride and the low fluorine shrimp med of preparation in a kind of krill.
Background technology
Krill is a kind of shell-fish zooplankter that lives in Nanjing University's midocean, and is individual little, but reserves are but very surprising, about 4~600,000,000 tons.Krill is the food of high protein.Measure according to the biologist, contain protein 17.56% in the krill meat, fat 2.11%, and contain the necessary whole amino acid of human body.Fluorine content scope in each whole krill is 1102~1432 μ g/g, average out to 1232 μ g/g; Content scope in crust is 3828~4278 μ g/g, average out to 4028 μ g/g; Excursion in cephalothorax and tail, foot is 2338~3028 μ g/g, average out to 2724 μ g/g and 2828 μ g/g; The content scope is 178~285 μ g/g in the muscle, average out to 226 μ g/g.As seen, in the krill fluorinated volume not only be higher than far away fluorinated volume in the harmless food (≤2mg/kg), simultaneously owing to fish for the cost height, so the recovery of fluorine and resource have great importance.
At present, the resource research of the fluorine of krill is few; Mainly concentrate on the defluorinate research of krill, external publication only has UK2240786, document utilization be the content that a kind of enrichment method of electrolysis reduces fluorine, the main aluminium electrode that adopts, oxidation by aluminium also realizes reducing the content of fluorine to the enrichment process of fluorine, the result shows and handles after 120 minutes, fluorine-containingly can reach 15ppm, and still be higher than the requirement of GB2762-2005 food contaminant fluorine limit standard: fish (fresh water) should and have potential aluminum pollution problem less than 2.0mg/kg.The preparation method of a domestic patent CN101690538A low-fluorine Euphausia superba protein base materials, utilize alkaline soluble protein, precipitating proteins under the acid condition, the method for protein being carried out the pickling defluorinate, the moisture that makes product is 82%~87%, and does not relate to fluorine recovery problem.And fluorocarboxylic acid salt wherein is a kind of important chemical and medicine intermediate raw material.
Summary of the invention
The invention provides the method that reclaims fluoride and the low fluorine shrimp med of preparation in a kind of krill.
For achieving the above object, the technical solution adopted in the present invention is:
It is in the solution of 8-11 after the making beating in pH value that krill is cleaned the back, uses the 60-120 purpose to sieve, and removes insoluble matters such as shrimp shell; At least use a kind of strong acid acid adjustment to pH<3 to the homogenate that obtains, carry out reduction vaporization, reclaim by the organic solvent and the fluorine of condensation to volatilization; For preventing that the pollution of not coagulating gas from utilizing the aqueous slkali of 5%-15% to absorb gas.For containing the acid condensate liquid that organic solvent closes fluorine, utilize conventional distillation technology that condensate liquid is purified and reclaim organic solvent, and obtain the recovery of the form realization fluorine of fluorocarboxylic acid; Obtain the shrimp med that contains albumen, amino acid and shrimp sauce mixture of low fluorine content through repeatedly circulating, can utilize correlation technique to reclaim the product of albumen, polypeptide and shrimp sauce.
Krill is cleaned back pulverizing making beating pH be controlled at 8-11, the 60-120 order removes by filter the solids such as shell that do not have pulverizing, the homogenate acid adjustment that obtains makes pH<3, and can adding nonpoisonous organic solvents such as ethanol, to carry out reduction vaporization be vacuum 0.01Mpa-0.09Mpa, and temperature is 40 ℃-240 ℃.Fluorine in the homogenate can volatilize along with organic solvent, enters condensate recovery liquid after the condensation.Through repeatedly circulation, the fluorine content in the monitoring shrimp med until the fluorine index that reaches control (is below the 2mg/kg as the food security GB), stops circulation.
Adopt the mode of circulation acid adjustment to reclaim fluorine and the low fluorine shrimp med of preparation, the clearance of fluorine in the rate of recovery of assurance fluorine and shrimp, the solvent extractable matter.Be to strengthen defluorinate and cycle-index, add nonpoisonous organic solvents such as ethanol in homogenate, the not comminuted solids impurity that filtration is obtained also can carry out organic solvent extraction wherein albumen and grease are changed in the solution; According to the characteristic that adopts organic dispersing agent, controlled condition is carried out rectifying to condensate recovery liquid and is reclaimed organic solvent and reclaim fluorine with the form of fluorocarboxylic acid.Do not coagulate gas in reduction vaporization and the distillation process and use aqueous slkali,, absorb, guarantee non-secondary pollution as 5%-15%NaOH solution.
Can adopt the falling film heating evaporimeter for strengthening the efficient evaporimeter.The falling film evaporation apparatus removes and is used for krill homogenate, also can be used for treatment fluids such as enzymolysis liquid, extract.
For avoiding the external acid pollution of product, in the acid adjustment process, preferably adopt ionic membrane method to reduce the mode of pH.
The invention has the beneficial effects as follows that this method adopts acid adjustment, the method for reduction vaporization reclaims fluorine in the mode of fluorocarboxylic acid, and the low fluorine krill meal of circulation defluorinate and preparation fluorine-containingly is lower than 2mg/kg, and the shrimp med yield is greater than 90%.Flow process is simple, does not add harmful chemical reagent, and the technology environmental protection can prepare the low fluorine shrimp med that reaches harmless food standard, can be used as the raw material of various food, health products and medicine
Description of drawings
Accompanying drawing is a process chart of the present invention.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Example 1:
Krill 10g cleaned and is after 1: 10 (liquid is water) pulverizes making beating by solid-to-liquid ratio, slurry pH is that 9,100 orders remove by filter not that comminuted solids obtains homogenate, gets 100ml homogenate and regulates homogenate pH=1.8 with hydrochloric acid.With above-mentioned solution decompression distillation, the control temperature is 70 ℃-80 ℃, and vacuum is 0.08MPa-0.09MPa, does not coagulate gas and absorbs with 5%NaOH solution.Carry out acid adjustment, evaporation continued operation, circulating and obtaining non-volatile solid shrimp med after 24 hours is 4.20g, and fluorinated volume is 1.8mg/kg; The shrimp med yield is 91%.
Example 2:
The krill cleaning is extracted with ethanol, obtain getting 50ml behind the water, regulate homogenate pH<3 with hydrochloric acid again.With above-mentioned solution decompression distillation, the control temperature is 70 ℃-80 ℃, and vacuum is 0.08MPa-0.09MPa, does not coagulate gas and absorbs with 5%NaOH solution.Carry out acid adjustment, evaporation continued operation, circulate and obtain the solvent extractable matter 14.25g of non-volatile low fluorine after 24 hours; Fluorinated volume is 1.8mg/kg; The shrimp med yield is 90%.
Claims (7)
1. reclaim fluoride and prepare the method for hanging down the fluorine shrimp med in a krill, adopt acid adjustment, the method for reduction vaporization reclaims fluorine in the mode of fluorocarboxylic acid, and the fluorine krill meal is hanged down in circulation defluorinate and preparation; It is characterized in that: krill is cleaned, after pH is to pulverize making beating 60-120 order under the 8-11 condition and remove by filter not comminuted solids impurity, the krill homogenate that obtains, with the strong acid acid adjustment to pH<3, carry out reduction vaporization, temperature is controlled at 40 ℃-240 ℃, and vacuum is 0.01MPa-0.09MPa; The condensate liquid that obtains is carried out the conventional rectification purification reclaim fluorocarboxylic acid, coagulate gas and absorb with 5%-15%NaOH solution.
2. reclaim the method for fluoride and the low fluorine shrimp med of preparation in a kind of krill according to claim 1, it is characterized in that: after the acid adjustment of krill homogenate, add nonpoisonous organic solvent; Or at slurrying stage adding nonpoisonous organic solvent.
3. reclaim the method for fluoride and the low fluorine shrimp med of preparation in a kind of krill according to claim 1, it is characterized in that: the acid of regulating the pH use is a kind of strong acid, organic or inorganic acid; Or utilize the electrolysis with ion-exchange film acid adjustment.
4. according to the method that reclaims fluoride and the low fluorine shrimp med of preparation in a kind of krill described in the claim 1,2 or 3, it is characterized in that: the reduction vaporization process adopts falling film evaporator.
5. according to the method that reclaims fluoride and the low fluorine shrimp med of preparation in claim 1, the 2 or 3 described a kind of krills, it is characterized in that: the reduction vaporization condensate liquid, carry out rectification and purification and reclaim fluorine in the mode of fluorocarboxylic acid, and to not coagulating the absorption of gas employing aqueous slkali, the aqueous slkali that uses is the NaOH solution of 5%-15%.
6. according to the method that reclaims fluoride and the low fluorine shrimp med of preparation in claim 1, the 2 or 3 described a kind of krills, it is characterized in that: adopt endless form defluorinate, continued operation or intermittently operated.
7. reclaim the method for fluoride and the low fluorine shrimp med of preparation in a kind of krill according to claim 4, it is characterized in that: the falling film evaporation apparatus is used for krill homogenate, or is used for other treatment fluid.
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CN2011100331725A CN102106493B (en) | 2011-01-30 | 2011-01-30 | Method for reclaiming fluoride in Antarctic krill and preparing low-fluorine krill meal |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102258074A (en) * | 2011-09-01 | 2011-11-30 | 山东科芮尔生物制品有限公司 | Euphausia superba pancake and preparation method thereof |
CN102559825A (en) * | 2012-01-18 | 2012-07-11 | 辽宁省大连海洋渔业集团公司 | Method for preparing antarctic krill low-fluorine hydrolysis polypeptide |
CN103583931A (en) * | 2013-11-11 | 2014-02-19 | 山东师范大学 | Ultrasonic defluorination method for whole euphausia superba |
CN103837387A (en) * | 2014-03-03 | 2014-06-04 | 山东师范大学 | Method for displaying inorganic fluorine in situ in antarctic krill shell |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5210186A (en) * | 1988-11-18 | 1993-05-11 | Mikalsen Gunnar | Method for recovery and separation of chitin, proteins and astaxanthin and esters thereof |
CN101690538A (en) * | 2009-09-24 | 2010-04-07 | 中国海洋大学 | Method for preparing low-fluorine Euphausia superba protein base materials |
-
2011
- 2011-01-30 CN CN2011100331725A patent/CN102106493B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5210186A (en) * | 1988-11-18 | 1993-05-11 | Mikalsen Gunnar | Method for recovery and separation of chitin, proteins and astaxanthin and esters thereof |
CN101690538A (en) * | 2009-09-24 | 2010-04-07 | 中国海洋大学 | Method for preparing low-fluorine Euphausia superba protein base materials |
Non-Patent Citations (4)
Title |
---|
《Aquaculture》 20071231 Bunji Yoshitomi et al. 《Effect of total replacement of dietary fish meal by low fluoride krill (Euphausia superba) meal on growth performance of rainbow trout (Oncorhynchus mykiss) in fresh water》 219-225 1-7 第266卷, * |
《Marine Biology》 19981231 M.Sands et al. 《Fluoride in Antarctic marine crustaceans》 591-598 1-7 第132卷, * |
《有色冶炼》 20021231 张文恒等 《含氟废水的处理及氟化盐的回收利用》 32-33 1-7 , 第6期 * |
《海洋学报》 20000331 潘建明等 《南大洋磷虾富氟机制Ⅰ.氟的化学赋存形态研究》 58-64 1-7 第22卷, 第2期 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102258074A (en) * | 2011-09-01 | 2011-11-30 | 山东科芮尔生物制品有限公司 | Euphausia superba pancake and preparation method thereof |
CN102559825A (en) * | 2012-01-18 | 2012-07-11 | 辽宁省大连海洋渔业集团公司 | Method for preparing antarctic krill low-fluorine hydrolysis polypeptide |
CN103583931A (en) * | 2013-11-11 | 2014-02-19 | 山东师范大学 | Ultrasonic defluorination method for whole euphausia superba |
CN103583931B (en) * | 2013-11-11 | 2015-05-27 | 山东师范大学 | Ultrasonic defluorination method for whole euphausia superba |
CN103837387A (en) * | 2014-03-03 | 2014-06-04 | 山东师范大学 | Method for displaying inorganic fluorine in situ in antarctic krill shell |
CN103837387B (en) * | 2014-03-03 | 2016-05-11 | 山东师范大学 | A kind of method of krill shrimp shell inorganic fluorine home position manifestation |
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