CN100581380C - Method for obtaining free amino acid by the hydrolyzation of water bloom blue algae - Google Patents
Method for obtaining free amino acid by the hydrolyzation of water bloom blue algae Download PDFInfo
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- CN100581380C CN100581380C CN200710025549A CN200710025549A CN100581380C CN 100581380 C CN100581380 C CN 100581380C CN 200710025549 A CN200710025549 A CN 200710025549A CN 200710025549 A CN200710025549 A CN 200710025549A CN 100581380 C CN100581380 C CN 100581380C
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Abstract
The present invention relates to a method capable of hydrolyzing algae bloom cyanophyte to obtain free amino acid. Said method includes the following steps: placing dehydrated algae bloom cyanophyte whose water content is 75-97% into a reaction still, adding concentrated sulfuric acid or concentrated hydrochloric acid whose added quantity is 15-30% of dehydrated cyanophyte volume, making reaction for 5-8hr, then adding catalyst which can be zinc salt and/or copper salt, continuously making reaction for 2-5hr so as to obtain acid cyanophyte solution, controlling temperature of reaction still at 100-120 deg.C, cooling, acid cyanophyte solution to normal temperature, then regulating its pH value to 6-7 by using alkaline neutralizing agent, evacuating and filtering so as to obtain water preparation containing rich amino acid, making said water preparation containing rich amino acid undergo the process of spray-drying or freeze-drying or vacuum drying treatment so as to obtain powder preparation containing rich amino acid.
Description
Technical field
The present invention relates to the method that a kind of bloom blue algae hydrolysis obtains free amino acid, especially a kind of bloom blue algae hydrolysis obtains the method for amino acid fertilizer and amino acid feed additive product, belongs to the category that bloom blue algae resource deep development utilizes.
Background technology
Be subjected to the influence of discharging of industrial wastewater and sanitary sewage and widespread pollution from the overuse of fertilizers and pesticides in rural area, the eutrophication of water body increases the weight of day by day, it is more and more frequent that a notable feature of body eutrophication is that blue-green alga bloom breaks out, bloom blue algae breaks out and rots, not only caused the severe contamination of drinking water and dangerous, and still make water body lose functions such as original ecology, amusement, sightseeing, and then initiation ecocatas-trophe, therefore, bloom blue algae is in time collected salvaging and disposed, be subjected to attention and people's common attention of governments at all levels and department.
At present, domestic and international research and utilization to algae mainly concentrates on spirulina, chlorella and Du Shi algae etc.; About causing blue-green algae, the green alga of body eutrophications such as lake, reservoir, administer more, but less for the research of its comprehensive utilization.Japan administers the lake of eutrophication and adopts blue, the green alga of directly removal, and with the measure of its recycling, with algae such as Microcystis aeruginosa as organic fertilizer, its fertilizer efficiency is better than general chemical fertilizer, nitrogen, phosphorus, potassium content all are higher than vegetalitas organic fertilizer such as soya-bean cake, Chinese milk vetch, and do not contain heavy metal to crop and human body harmful, can contaminated soil after the use.1992, the dehydration Microcystis aeruginosa of Japan was all realized fertilizerization, annual production 120-180t.After Microcystis aeruginosa was realized recycling, disposal cost had descended 30%.The Australia researcher extracts carrotene and has reached commercial size from the little algae in salt lake, and has applied for patent.
Because of containing abundant nutrition compositions such as vegetable protein, polysaccharide in the blue-green alga bloom, therefore, in recent years to the cultivation of blue-green algae with utilize the research and development focus that has become subjects such as biology, life health science, food engineering.The purposes of blue-green algae mainly contains: extract natural colouring matter, extract phycobniliprotein, extract polysaccharide, algae toxin study and utilization, biological nitrogen fixation and other aspects etc.
Publication number is the CN1563083 patent, discloses the method that a kind of bloom blue algae prepares phycocyanin, is raw material with bright algae, at first extracts coarse filtration liquid, after the bright algae dehydration, add buffer solution, mixing, freezing then, after freezing, taking-up is put under the room temperature melt and dissolved, and plate-frame filtering is used in freeze thawing 3-5 time; Next is a ultrafiltration purification, is 1000-20 ten thousand daltonian hollow fiber membrane ultrafiltration devices with molecular cut off, and the crude extract of process micro-filtration makes the less various materials of molecular weight, is eliminated through milipore filter; The 3rd is to leave standstill-clarification, and the part of the phycocyanin of process ultrafiltration purification is removed most of little molecule, concentrates simultaneously, and the phycocyanin part through concentrating is in the uniform temperature preservation; The 4th is the hydroxyapatite column chromatography purification.This invention advantage is the phycocyanin that can obtain higher degree, the value of the product height, although this method is improved traditional handicraft, production technology is more complicated still, and production cost is higher, lacks product market competitiveness.
There are some researches show,, can greatly improve crops quality, improve crop yield, strengthen the crop disease-resistant ability, and improve the chemical fertilizer utilization rate to be rich in high nitrogen liquid or the high nitrogen solid fertilizer that amino acid is feature.In agricultural production, during particularly efficient agricultural product such as organic food are produced, be rich in high nitrogen liquid of amino acid or high nitrogen solid fertilizer and use increasingly extensive.Research also shows, is rich in amino acid whose feed addictive, can balance Animal nutrition, improve the animal feed utilization rate, promote animal growth, thereby be rich in the amino acid product and be widely used as feed addictive.
According to surveying and determination, the bloom blue algae protein content is at 50-60%, and is suitable with fish meal protein matter content, is a kind of high-protein plant resource.But owing to contain the algae toxin, from water body, salvage unsuitable directly as fertilizer sources of the blue-green algae that comes out or feed and use, and extract the phycocyanin complex process that is used, the cost height, and other protein resource is wasted.Utilize blue-green algae to produce products of amino acid, technology is simple, and cost is low, and the algae toxin is almost all destroyed, and is a kind of new way of cyanophycin matter resources effective utilization.
Summary of the invention
The objective of the invention is to: lack at present bloom blue algae protein resource and effectively utilize method, serious waste of resources, and from polluted-water, salvage the blue-green algae that comes out and in a single day can not get timely disposal, can cause serious present situations such as secondary pollution.The invention provides the method that obtains free amino acid in a kind of bloom blue algae hydrolyzate.
The object of the present invention is achieved like this: a kind of bloom blue algae hydrolysis obtains the method for free amino acid, it is characterized in that:
A) water content that will salvage after dewatering places reactor for the 75-97% bloom blue algae;
B) add the concentrated sulfuric acid or concentrated hydrochloric acid by 15～30% of dehydration blue-green algae volume, react after 5～8 hours, add catalyst again, continue reaction 2～5 hours, obtain acid blue-green algae solution, described catalyst is zinc salt and/or mantoquita, and the catalyst addition of per kilogram blue-green algae is 20～120g, and the temperature of reactor is controlled at 100～120 ℃;
C) acid blue-green algae solution is cooled to normal temperature after, adopt an amount of antalkali that pH value is adjusted to 6～7, vacuumizing filtration forms the aqua be rich in free amino acid.
In an application of the invention: the aqua that will be rich in free amino acid is handled by dry, makes its water content be lower than 5%, forms the pulvis that is rich in free amino acid.
In an application of the invention: the described concentrated sulfuric acid or concentrated hydrochloric acid are meant the concentrated sulfuric acid or the hydrochloric acid that technical grade is above; Described antalkali is meant liquid ammonia or NaOH or carbonic hydroammonium or sodium carbonate or potassium hydroxide.
In an application of the invention: described dry the processing is meant employing spray-drying or freeze drying or the vacuum drying product drying that is rich in free amino acid with liquid state, and the pulvis of free amino acid is rich in formation.
The invention has the advantages that: adopt a kind of acid hydrolysis process, not only the hydrolysis of blue-green algae cell all protein can be formed free amino acid and be used, and almost eliminate whole algae toxin, subsequent product application safety.The technological process of present technique is short, and preparation condition is less demanding, and production cost is low.
The specific embodiment
Embodiment 1
Fish for water content and be 90% bloom blue algae, the dehydration back obtains 100L dehydration blue-green algae, will place reactor, adding 20L concentration is 98% industrial sulfuric acid, be heated to 110 ℃, react after 8 hours, add 1Kg zinc sulfate+1Kg copper sulphate, continued to add thermal response 2 hours, temperature in the reactor is controlled at 110～120 ℃, be cooled to normal temperature after, being neutralized to pH with the potassium hydroxide (KOH) of 10mol/L is 6, vacuumizing filtration obtains the brown transparent amino acid whose aqua that is rich in.Be rich in amino acid whose kind and content referring to table 1.
Free amino acid testing result in the table 1 blue-green algae hydrolyzate
| The amino acid kind | Code name | Relative amount (%) |
| Asparatate | Asp | 11.61 |
| Threonine | Thr | 5.86 |
| Serine | Ser | 6.00 |
| Glutamic acid | Glu | 17.55 |
| Glycine | Gly | 5.20 |
| Alanine | Ala | 0.77 |
| Cystine | Cys | 1.47 |
| Valine | Val | 6.76 |
| Methionine | Met | 0.71 |
| Isoleucine | Ile | 6.00 |
| Leucine | Leu | 11.60 |
| Tyrosine | Tyr | 2.72 |
| Phenylalanine | Phe | 5.37 |
| Lysine | Lys | 6.40 |
| Histidine | His | 1.37 |
| Arginine | Arg | 6.80 |
| Proline | Pro | 3.80 |
| Amount to | 100.00 |
The detection of Microcystin in the blue-green algae hydrolyzate:
In advance respectively with 5ml methyl alcohol and the activation of 5ml water, C18 solid phase extraction column on the filtrate is used 10ml water, 10ml 35% methyl alcohol (containing 0.1% trifluoroacetic acid) washing respectively, 5ml80% methyl alcohol (containing 0.1% trifluoroacetic acid) wash-out with sample solution 5ml.Eluent nitrogen in 50 ℃ of water-baths purges near to be done, and separates with 1ml is water-soluble, crosses 0.45 μ m filter membrane, analyzes for HPLC.
The HPLC condition: HP1100 high performance liquid chromatograph (Agilent, the U.S.) is furnished with chem workstation, automatic sampler, column oven, UV-detector.Chromatographic column: ODS-3C18 (Hypersil, Japan, 250*4.6mm); Mobile phase A: 0.05M KH
2PO
4(pH H
3PO
4Transfer to 3.0), B:CH
3OH.Flow velocity: 1ml/min; Column temperature: 35 ℃; Sample size: 10 μ L.Gradient elution:
Qualitative, quantitative approach: it is qualitative to utilize retention time to carry out, and external standard method is carried out quantitatively.
Result: in the blue-green algae hydrolyzate, all do not detect algae toxin MC-RR and MC-LR (detection limit: 5ng/ml).
Embodiment 2
Fish for water content and be 80% bloom blue algae, the dehydration back obtains 50L dehydration blue-green algae, is placed in the reactor, add the 12.5L industrial hydrochloric acid, be heated to 120 ℃, react after 6 hours, add 5Kg zinc sulfate, continued to add thermal response 4 hours, temperature in the reactor is controlled at 100～120 ℃, be cooled to normal temperature after, being neutralized to pH with the NaOH (NaOH) of 10mol/L is 6.5, vacuumizing filtration obtains the brown transparent amino acid whose aqua that is rich in.Be rich in amino acid whose kind and content referring to table 2
Free amino acid testing result in the table 2 blue-green algae hydrolyzate
| The amino acid kind | Code name | Relative amount (%) |
| Asparatate | Asp | 10.17 |
| Threonine | Thr | 5.01 |
| Serine | Ser | 5.12 |
| Glutamic acid | Glu | 18.50 |
| Glycine | Gly | 4.37 |
| Alanine | Ala | 8.53 |
| Cystine | Cys | 1.52 |
| Valine | Val | 6.76 |
| Methionine | Met | 1.56 |
| Isoleucine | Ile | 5.93 |
| Leucine | Leu | 10.33 |
| Tyrosine | Tyr | 2.14 |
| Phenylalanine | Phe | 4.92 |
| Lysine | Lys | 5.43 |
| Histidine | His | 1.17 |
| Arginine | Arg | 5.50 |
| Proline | Pro | 3.05 |
| Amount to | 100.00 |
Adopt the detection method of the identical Microcystin of embodiment 1, do not detect algae toxin MC-RR and MC-LR equally.
Embodiment 3
The amino acid whose aqua that is rich in that will obtain according to the method for embodiment 1 adopts traditional spray-drying mode, makes its water content be lower than 5%, just can obtain to be rich in amino acid whose pulvis.
More than each embodiment be not to concrete restriction of the present invention, during enforcement, can select other antalkalis flexibly according to claim.
Claims (4)
1, a kind of bloom blue algae hydrolysis obtains the method for free amino acid, it is characterized in that:
A) will salvage dehydration back water content is that the bloom blue algae of 75-97% places reactor;
B) add the concentrated sulfuric acid or concentrated hydrochloric acid by 15～30% of dehydration blue-green algae volume, react after 5～8 hours, add catalyst again, continue reaction 2～5 hours, obtain acid blue-green algae hydrating solution, described catalyst is zinc salt and/or mantoquita, and the catalyst addition of per kilogram blue-green algae is 20～120g, and the temperature of reactor is controlled at 100～120 ℃;
C) acid blue-green algae hydrating solution is cooled to normal temperature after, adopt an amount of antalkali that the pH value is adjusted to 6～7, vacuumizing filtration forms the aqua be rich in free amino acid.
2, bloom blue algae hydrolysis according to claim 1 obtains the method for free amino acid, it is characterized in that: the aqua that will be rich in free amino acid is handled by dry, makes its water content be lower than 5%, forms the pulvis that is rich in free amino acid.
3, bloom blue algae hydrolysis according to claim 1 and 2 obtains the method for free amino acid, it is characterized in that: the described concentrated sulfuric acid or concentrated hydrochloric acid are meant the concentrated sulfuric acid or the hydrochloric acid that technical grade is above; Described antalkali is meant liquid ammonia or NaOH or carbonic hydroammonium or sodium carbonate or potassium hydroxide.
4, bloom blue algae hydrolysis according to claim 2 obtains the method for free amino acid, it is characterized in that: described dry the processing is meant that employing spray-drying or freeze drying or vacuum drying with the amino acid whose product drying of being rich in of liquid state, form the pulvis that is rich in free amino acid.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102511683B (en) * | 2011-12-16 | 2013-10-30 | 陈景河 | Preparation method of alga nutrient solution for prawn culture |
| CN102652533B (en) * | 2012-04-24 | 2014-03-26 | 江苏省农业科学院 | Toxin producing algae detoxification technology, product and application of product |
| CN104399315B (en) * | 2014-11-25 | 2016-01-20 | 湖南大学 | A kind of method of simultaneously blue-green algae being carried out to detoxification and dehydration |
| CN108882728B (en) * | 2016-04-07 | 2023-04-04 | 凯塞尔德国有限公司 | Phycocyanin for slow feeding of aquatic organisms |
| CN113563516A (en) * | 2020-04-29 | 2021-10-29 | 无锡蓝湾资源再生科技有限公司 | Blue algae resource utilization method |
| CN113735394A (en) * | 2021-09-18 | 2021-12-03 | 江苏省农业科学院 | Preparation method of blue algae mud amino acid, product and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207380A (en) * | 1997-08-04 | 1999-02-10 | 汤洁 | Method for preparing functional compound liquid fertilizer using marine living things |
| CN1229778A (en) * | 1998-03-20 | 1999-09-29 | 汤洁 | Method for prodn. of functional marine alga fertilizer |
| CN1259335C (en) * | 2004-03-27 | 2006-06-14 | 中国科学院水生生物研究所 | Method for preparing phycocyanin from blue algae in water bloom |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207380A (en) * | 1997-08-04 | 1999-02-10 | 汤洁 | Method for preparing functional compound liquid fertilizer using marine living things |
| CN1229778A (en) * | 1998-03-20 | 1999-09-29 | 汤洁 | Method for prodn. of functional marine alga fertilizer |
| CN1259335C (en) * | 2004-03-27 | 2006-06-14 | 中国科学院水生生物研究所 | Method for preparing phycocyanin from blue algae in water bloom |
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