CN106509706A - Method for removing prometryn and heavy metal in porphyra - Google Patents

Method for removing prometryn and heavy metal in porphyra Download PDF

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Publication number
CN106509706A
CN106509706A CN201610965431.0A CN201610965431A CN106509706A CN 106509706 A CN106509706 A CN 106509706A CN 201610965431 A CN201610965431 A CN 201610965431A CN 106509706 A CN106509706 A CN 106509706A
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China
Prior art keywords
seaweed
prometryn
heavy metal
porphyra
enzymolysis
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CN201610965431.0A
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Chinese (zh)
Inventor
林洪
周青
付晓婷
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Ocean University of China
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Ocean University of China
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Priority to CN201610965431.0A priority Critical patent/CN106509706A/en
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Abstract

The invention belongs to the field of agricultural chemistry, and particularly relates to a method for removing prometryn and heavy metal in porphyra. The method comprises the specific steps that fresh porphyra is subjected to enzymolysis through one or more complex enzymes of cellulase, pectinase and papain, so that the prometryn and the heavy metal on the fresh porphyra can be removed. The method disclosed by the invention is combined with a conventional common-used porphyra processing technology, and only a simple removal technology link needs to be added, the prometryn and the heavy metal in the porphyra can be removed quickly and efficiently, the operation is simple, the cost is saved, pollution is not caused, besides, the removal effects are good, and influence on algae bodies is small. The method disclosed by the invention is safe, pollution-free, healthy and environmental-friendly, the quality of the porphyra is greatly improved, the economic benefits are increased, and the high-value utilization of porphyra industry is promoted.

Description

A kind of method of prometryn and heavy metal in removing seaweed
Technical field
The invention belongs to agrochemical field, more particularly, to a kind of method of prometryn and heavy metal in removing seaweed.
Background technology
Seaweed (Pyropia spp.) is one of important artificial cultivation marine alga of China, its nutritious, delicious flavour, slightly Protein content reaches the 30%-50% of its dry weight, rich in multivitamin, abundant dietary fiber and amino needed by human Acid, inorganic salts.The having good quality of China's laver product, moderate, color and luster and good in taste has very in market competition Big advantage, but the international trade that the pollution problems such as the residual, heavy metal of agriculture limit China's laver product is also occasionally there are, have impact on me The further development of state's seaweed industry.
Prometryn (Prometryn) is a kind of conventional triazine herbicide, and originally which is mainly used in aquaculture Remove the harmful algae in the breeding water bodies such as fish, shrimp, crab, sea cucumber.The Ministry of Agriculture of China issue in 2010《Veterinary drug tentative standard is given up Only catalogue》In aquatic products prometryn powder listed in abrogate scope.But as prometryn structure is special, stable chemical nature, Can occasionally there is prometryn in seaweed by the modes such as river, sedimentation are into environment and are present in crop, environment water and soil Detected.
Furthermore, with developing rapidly for China's industry, while bringing tremendous economic interests, also result in serious environment Pollution problem.In greater coasting area, due to a large amount of discharges of Industrial " three Waste ", offshore pollution, especially heavy metal pollution into For one of more serious problem.Heavy metal element in the stronger enrichment environment that the pollution of marine environment and algae have in itself Characteristic, these heavy metals can be constantly accumulated in human body, and incubation period is very long, produce larger harm to health, become shadow Ring the principal element of laver product quality safety.
At present, for the removing sulfuldioxide of the pollutant in seaweed, very understatement road both at home and abroad, Jiang Hao etc. utilize ultrasonic disruption The heavy metals such as technical finesse porphyra haitanensis, removing cadmium.But due to the intensity of ultrasonication it is too big, it is easy to cause laver cell break Split, affect laver product quality, and for the very fragile Porphyra yezoensis of frond, can heavy damage frond using ultrasonication Cell, therefore the applicability of the method is not strong.For the removing sulfuldioxide of prometryn in seaweed, temporarily do not carry in current research Arrive.
The content of the invention
In order to overcome deficiency of the prior art, the removal methods of prometryn and cadmium in the seaweed that the present invention is provided, definitely Say be biology enzyme removing seaweed in prometryn and heavy metal method.The present invention can be mutually tied with the conventional processing technology of seaweed Close, adopt simple removing sulfuldioxide, with biology enzyme as scavenger, quickly and efficiently remove the prometryn and a huge sum of money in seaweed simultaneously Category.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows:In a kind of removing seaweed prometryn and The method of heavy metal, comprises the following steps:
(1) new fresh laver
New fresh laver is taken, impurity removing is chosen, is cleaned up, it is standby;
(2) digest pre-treatment
Clean sea water is taken, its pH is adjusted to into 2.0~5.0, then by solid-liquid ratio 1:5~1:New fresh laver is added to cleaning by 20 In seawater, stir to seaweed solution and be well mixed;
(3) digest
Seaweed solution adds the enzyme that volume fraction is 0.2~0.8%, vibration to digest while stirring, and controlled enzymatic hydrolysis temperature is 10~40 DEG C, enzymolysis time is 5~40min;Wherein enzyme be cellulase, pectase, one or more in papain Complex enzyme.
In above-mentioned, cellulase in decomposition of cellulose from biocatalysis, by cellulose decomposition into oligosaccharides or monose, It is widely used in food service industry and environmental industry.Pectase is to decompose plant main component, and which is distributed widely in high plant In thing and microorganism.Papain utilizes enzymatic reaction, makes the protein of food macromolecular be hydrolyzed into small-molecular peptides or amino Acid, can effective transforming protein matter utilization, greatly improve food value, reduces cost, be conducive to human body digestion and Absorb.
(4) clean
The enzymolysis mixture that step (3) is obtained is filtered, and removes a small amount of residual enzyme liquid, the purple after being digested on seaweed Dish;Filtered fluid pH is adjusted to into neutrality simultaneously.
In the foregoing description, seawater is filtrated to get by the clean sea water through chitosan gel rubber.
Further, currently preferred is to comprise the following steps:
(1) new fresh laver
New fresh laver 10g is taken, impurity removing is chosen, is cleaned up, it is standby;
(2) digest pre-treatment
Clean sea water is taken, its pH is adjusted to into 4.0, then by solid-liquid ratio 1:10 are added to new fresh laver in clean sea water, stir Mix to seaweed solution and be well mixed;
(3) digest
Seaweed solution adds the complex enzyme that volume fraction is 0.5% while stirring, and vibration enzymolysis, controlled enzymatic hydrolysis temperature are 30 DEG C, enzymolysis time is 30min;Wherein complex enzyme is that mass ratio is 7:3 cellulase and pectase composition,;
(4) clean
The enzymolysis mixture that step (3) is obtained is filtered, and removes a small amount of residual enzyme liquid, the purple after being digested on seaweed Dish;Filtered fluid pH is adjusted to into neutrality simultaneously.
The features such as single-minded, efficient, controllable that biology enzyme in above-mentioned has, seaweed is being carried out to remove the place of pollutant During reason, the local flavor and nutrient content of seaweed will not be destroyed, and effect is good, low cost.The present invention is using external enzymolysis side Formula carries out deep processing to seaweed, by certain enzymolysis, the cellulose, polysaccharide on degraded laver cell wall, so as to tie Separate together in pollutants such as the heavy metals on cellulose and polysaccharide, removed by modes such as cleanings, while improving human body pair Seaweed functional component is digested and assimilated, and the nutrient content in effectively utilizes seaweed, the simple row of its method be scientific and reasonable.
The present invention removing process is carried out using biological enzyme, can remove in specific manner on laver cell wall with polysaccharide, fibre The pollutant of the combinations such as dimension element, by the species of research institute's enzyme, consumption, hydrolysis temperature and pH value, is not destroying so as to reach On the basis of frond, the pollutant that frond surface combines is removed, and the quality and nutrient content to seaweed is not damaged.
Processing technology conventional with existing seaweed of the invention combines, need to only add simple removing process link, can It is fast and efficiently to remove prometryn and heavy metal in seaweed simultaneously, simple to operate, cost-effective, pollution-free, and remove effect Really good, the impact to frond is little.The inventive method safety non-pollution, health environment-friendly substantially improve the quality of seaweed, increased Economic benefit, promotes the higher value application of seaweed industry.
Specific embodiment
In order to understand the present invention, the present invention is further illustrated with embodiment below, but is not limited to the present invention.
Embodiment 1
Embodiment 1:
The fresh seaweeds of 10g are taken in 500mL conical flasks, add 300mL water to clean up, remove silt in seaweed, Miscellaneous algae etc..
The pH of clean sea water is transferred to into 4.0, by solid-liquid ratio 1:10 are added to the seaweed after cleaning in seawater, and stirring makes seaweed Solution is well mixed.
Add cellulase and pectase that volume fraction is 0.5% in seaweed solution to after being well mixed while stirring (ratio of cellulase and pectase is 7 to the complex enzyme of composition:3), vibration enzymolysis, controlled enzymatic hydrolysis temperature is 30 DEG C, during enzymolysis Between be 30 minutes.
Seaweed after being filtrated to get enzymolysis, a small amount of enzyme liquid clean on removing seaweed with clean sea water, while by purple The pH of dish solution is cleaned to neutrality, and the seaweed handled well is processed for lower road.After can dry laver product, prometryn is carried out With the detection of heavy metal.
Embodiment 2
The fresh seaweeds of 10g are taken in 500mL conical flasks, add 300mL water to clean up, remove silt in seaweed, Miscellaneous algae etc..The pH of clean sea water is transferred to into 4.5, by solid-liquid ratio 1:10 are added to the seaweed after cleaning in seawater, and stirring makes seaweed Solution is well mixed.
Add cellulase and pectase that volume fraction is 0.5% in seaweed solution to after being well mixed while stirring (ratio of cellulase and pectase is 4 to the complex enzyme of composition:1), vibration enzymolysis, controlled enzymatic hydrolysis temperature is 35 DEG C, during enzymolysis Between be 25 minutes.
Seaweed after being filtrated to get enzymolysis, a small amount of enzyme liquid clean on removing seaweed with clean sea water, while by purple The pH of dish solution is cleaned to neutrality, and the seaweed handled well is processed for lower road.After laver product is dried, carry out prometryn and The detection of heavy metal.
Embodiment 3
The fresh seaweeds of 10g are taken in 500mL conical flasks, add 300mL water to clean up, remove silt in seaweed, Miscellaneous algae etc..The pH of clean sea water is transferred to into 5, by solid-liquid ratio 1:8 are added to the seaweed after cleaning in seawater, and stirring makes seaweed solution It is well mixed.
Add cellulase, pectase that volume fraction is 0.7% in seaweed solution to after being well mixed while stirring (ratio of cellulase, pectase and papain is 5 with the complex enzyme of papain composition:3:2), vibration enzymolysis, Controlled enzymatic hydrolysis temperature is 40 DEG C, and enzymolysis time is 15 minutes.Seaweed after being filtrated to get enzymolysis, is cleaned with clean sea water and is removed The a small amount of enzyme liquid gone on seaweed, while the pH of seaweed solution is cleaned to neutrality, the seaweed handled well is processed for lower road.Will After laver product drying, the detection of prometryn and heavy metal is carried out.
The seaweed that above three embodiment is obtained carries out the detection of prometryn and heavy metal, and concrete detection method is as follows:
(1) removal efficiency of heavy metal
Seaweed after new fresh laver and removing is respectively referred to into standard GB/T/T 5009.15-2003《Cadmium in foods Determine》With GB 500912-2010《The measure of Pb in food》In method digested, using graphite furnace atomic absorption spectrometry Method determines content of beary metal.Such as:The content of cadmium is respectively M1、M2
The calculating of the removal efficiency of cadmium:
In formula:
Removal efficiency %s of the A for cadmium;
M1For cadmium content (mg/kg) in new fresh laver;
M2Cadmium content (mg/kg) in seaweed after processing for removing.
The content of lead is respectively N1、N2
The calculating of the removal efficiency of lead:
In formula:
Removal efficiency %s of the B for lead;
N1For lead content (mg/kg) in new fresh laver;
N2Lead content (mg/kg) in seaweed after processing for removing.
(2) measure of prometryn
Respectively the seaweed that new fresh laver and removing are processed is dried at 40 DEG C, with reference to standard GB/T/T 18629-2002 《The measure of prometryn in food》In method, respectively to new fresh laver and removing after seaweed in prometryn content at Reason is determined, and the content for obtaining prometryn is respectively X1、X2
The calculating of prometryn removal efficiency:
In formula:
Removal efficiency %s of the C for prometryn;
X1For prometryn content (mg/kg) in new fresh laver;
X2Prometryn content (mg/kg) in seaweed after processing for removing.
(3) quality evaluation of seaweed
Total sugar content is determined
Respectively the seaweed that new fresh laver and removing are processed is dried at 40 DEG C, is 1 according to solid-liquid ratio:15 add water, in 80 DEG C heating extraction, extract and keep 2h, collect extract.Under the conditions of 4500r/min, centrifugation time 10min takes supernatant to extract Liquid, carries out rotary evaporation concentration, adds the 95% of 4 times of volumes ethanol, stand overnight in 4 DEG C in concentrating backward concentrate, from The heart takes precipitation.By sediment in baking oven low temperature drying, freeze-drying obtains seaweed Thick many candies sample.Then adopt anthrone-sulphur Acid system determines the content of total reducing sugar.
Protein determination
With reference to standard GB/T 5009.5-2010《The measure of Protein in Food》Before and after determining seaweed removing respectively Protein content changes.
(4) color difference measurement
Respectively the color and luster of seaweed before and after removing is measured with WSC-S types colour difference meter, by each monolithic seaweed positive and negative two L*, a*, b* value of face different parts is determined 10 times, calculates mean value.
After testing, after in embodiment 1, removing is processed, in seaweed, the removal efficiency of prometryn reaches 78.3%, the removing of cadmium and lead Rate respectively reaches 89.1% and 67.9%, and its content meets the limitation requirement to prometryn and heavy metal.
After in embodiment 2, removing is processed, the removal efficiency of prometryn reaches 75.1% in seaweed, the removal efficiency difference of cadmium and lead 86.9% and 60.2% is reached, its content meets the limitation requirement to prometryn and heavy metal.
3 removing of embodiment process after in seaweed the removal efficiency of prometryn reach 77.1%%, the removal efficiency difference of cadmium and lead 75.2% and 61.6% is reached, its content meets the limitation requirement to prometryn and heavy metal.
It can thus be seen that the content of the seaweed of this method removing, its prometryn and heavy metal is less than professional standard, significantly Improve the edible safety and the market competitiveness of seaweed.
The above, is only presently preferred embodiments of the present invention, not makees any pro forma restriction to the present invention, therefore It is every without departing from technical solution of the present invention content, any simply repaiied according to what the technical spirit of the present invention made to above example Change, equivalent variations and modification, still fall within the range of technical solution of the present invention.

Claims (3)

1. it is a kind of removing seaweed in prometryn and heavy metal method, it is characterised in that:Comprise the following steps:
(1) new fresh laver
New fresh laver is taken, impurity removing is chosen, is cleaned up, it is standby;
(2) digest pre-treatment
Clean sea water is taken, its pH is adjusted to into 2.0~5.0, then by solid-liquid ratio 1:5~1:New fresh laver is added to clean sea water by 20 In, stir to seaweed solution and mix;
(3) digest
Seaweed solution adds the enzyme that volume fraction is 0.2~0.8% while stirring, vibration enzymolysis, and controlled enzymatic hydrolysis temperature is 10~ 40 DEG C, enzymolysis time is 5~40min;Wherein enzyme is cellulase, pectase, one or more in papain answer Synthase;
(4) clean
The enzymolysis mixture that step (3) is obtained is filtered, and removes a small amount of residual enzyme liquid, the seaweed after being digested on seaweed;Together When filtered fluid pH is adjusted to into neutrality.
2. it is according to claim 1 it is a kind of removing seaweed in prometryn and heavy metal method, it is characterised in that:It is described clear Clean seawater is the seawater that seawater is filtrated to get through chitosan gel rubber.
3. it is according to claim 1 it is a kind of removing seaweed in prometryn and heavy metal method, it is characterised in that:Including with Lower step:
(1) new fresh laver
New fresh laver 10g is taken, impurity removing is chosen, is cleaned up, it is standby;
(2) digest pre-treatment
Clean sea water is taken, its pH is adjusted to into 4.0, then by solid-liquid ratio 1:10 are added to new fresh laver in clean sea water, stir to Seaweed solution is well mixed;
(3) digest
Seaweed solution adds the complex enzyme that volume fraction is 0.5% while stirring, and vibration enzymolysis, controlled enzymatic hydrolysis temperature are 30 DEG C, Enzymolysis time is 30min;Wherein complex enzyme is that mass ratio is 7:3 cellulase and pectase composition,;
(4) clean
The enzymolysis mixture that step (3) is obtained is filtered, and removes a small amount of residual enzyme liquid, the seaweed after being digested on seaweed;Together When filtered fluid pH is adjusted to into neutrality.
CN201610965431.0A 2016-11-04 2016-11-04 Method for removing prometryn and heavy metal in porphyra Pending CN106509706A (en)

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CN113907165A (en) * 2021-10-11 2022-01-11 广西铂洋果业科技有限公司 Bamboo cane flavored syrup and preparation method thereof
CN114106969A (en) * 2020-08-31 2022-03-01 张勇云 Preparation method of brewed wine for reducing heavy metal content in brewed wine

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114106969A (en) * 2020-08-31 2022-03-01 张勇云 Preparation method of brewed wine for reducing heavy metal content in brewed wine
CN113907165A (en) * 2021-10-11 2022-01-11 广西铂洋果业科技有限公司 Bamboo cane flavored syrup and preparation method thereof

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Application publication date: 20170322