CN102106493B

CN102106493B - Method for reclaiming fluoride in Antarctic krill and preparing low-fluorine krill meal

Info

Publication number: CN102106493B
Application number: CN2011100331725A
Authority: CN
Inventors: 马伟; 吴志敏; 程子洪; 吕腾飞; 王天罡
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2011-01-30
Filing date: 2011-01-30
Publication date: 2012-11-21
Anticipated expiration: 2031-01-30
Also published as: CN102106493A

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

Reclaim the method for fluoride and the low fluorine shrimp med of preparation in a kind of krill

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.It is thus clear that, 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; Realize reducing the content of fluorine through the oxidation of aluminium and 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, acid condition settle protein, 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 realizing above-mentioned purpose, the technical scheme that the present invention adopted is:

After krill cleaned the back and in pH value be the solution of 8-11, pull an oar, sieve, remove insoluble matters such as shrimp shell with the 60-120 purpose; At least use a kind of strong acid acid adjustment to pH＜3 to the homogenate that obtains, carry out reduction vaporization, reclaim through 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, gets into 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 like 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, in homogenate, add nonpoisonous organic solvents such as ethanol, 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 like 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 with 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 done further explain.

Instance 1:

Krill 10g is cleaned and is after 1: 10 (liquid is water) pulverized making beating by solid-to-liquid ratio, and 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%.

Instance 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

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 with 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 use the 5%-15%NaOH solution absorption.

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 ethanol; Or at slurrying stage adding ethanol.

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 claim 1, a kind of krill described in 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 with 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.