CN102277300A - Magnetic separation method of chlorella - Google Patents
Magnetic separation method of chlorella Download PDFInfo
- Publication number
- CN102277300A CN102277300A CN2011102252747A CN201110225274A CN102277300A CN 102277300 A CN102277300 A CN 102277300A CN 2011102252747 A CN2011102252747 A CN 2011102252747A CN 201110225274 A CN201110225274 A CN 201110225274A CN 102277300 A CN102277300 A CN 102277300A
- Authority
- CN
- China
- Prior art keywords
- chlorella
- magnetic
- medium
- nano particle
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a magnetic separation method of chlorella and a recycling and regenerating method of a magnetic medium. The method comprises the following steps: (1) dispersing Fe3O4 nano-particles to form a stable suspension; (2) adding the suspension into a chlorella culture solution, stirring, and preparing a polymer of chlorella and magnetic medium in a magnetic separation mode; (3) cleaning the polymer, performing a reaction by adding hydrochloric acid, and performing microfiltration, cleaning and filtrate collection after the reaction is completed; and (4) regulating the pH value of the filtrate to be between 0.8 and 1.5 by using ammonia water, and preparing Fe3O4 nano-particles by taking the regulated filtrate as a raw material so as to realize regeneration and recycling of the magnetic medium. The medium used in the magnetic separation method provided by the invention has simple synthesizing steps and is easily amplified; the method of dissolving hydrochloric acid and recrystallizing ammonia water is adopted to realize regeneration and recycling of the Fe3O4 nano-particles, the chlorella components cannot be destroyed, and no pollution is generated; and the magnetic medium recycling process is simple and effective, and can be applied to industrial separation of the chlorella, so that the cost can be lowered.
Description
Technical field
The present invention relates to a kind of magnetic medium recovery method that is used for the chlorella magnetic resolution, it belongs to little algae separation field.
Background technology
Chlorella is an eukaryote in unicell green alga, and cell contains abundant chlorophyll.Chlorella contains rich in protein, VITAMIN, mineral substance, foodstuff fibre, nucleic acid and chlorophyll etc., and particularly it contains compelling biologically active substance glycoprotein, polysaccharide body and up to 13% materials such as nucleic acid.
Chlorella has and strengthens human immunity, prevents virus multiplication, inhibition cancer cell propagation, suppresses blood sugar and rise, and reduces serum cholesterol content, gets rid of toxin, the functions such as damage of repairing rapidly body.For example, on TaiWan, China medical association magazine, delivered biochemical section of Taibei medical college research department and done the report of experiment, and confirmed that chlorella has the effect of the lowering blood glucose factor to diabetes in 1977 with Siberian chipmunk, and after blood sugar reduces, can't therefore continue to reduce and be hypoglycemia.On November 10th, 1978, Japanese The Daily Yomiuri publishes an article, and report studies medicine the professor research group chlorella that experiment showed, for many years greatly according to nearly Ji good blood pressure lowering effect.1979, wild this tortoise male professor of a specified duration of Kyushu University delivered laboratory report, confirmed that chlorella can make the T cell activation in the immunocyte in the organism, effectively brought back to life immunologic function, prolonged cancer patient's life.1988, the formal legislation of Japanese government's Health and human services department was classified chlorella as with curative effect function food.On October 28th, 1997, China Times were reported, Taibei hospital of medical college is that Lin Songzhou professor's the chlorella that experimental results show that can prevent the pneumonocyte fibrosis, prevention lung cancer; CGF has synergitic sterilization effect, and antibiotic dosage and the side effect that is brought thereof can minimize.
Based on the above-mentioned vital role of chlorella, chlorella is widely used at the aspects such as production of protective foods, natural product carotenoid, aquaculture bait, livestock feed additive.For example, chlorella is the healthy food of generally acknowledging in the world, the maximum kind of output in the little algae industry in the whole world, and continuous ten years sales volumes the first in Japanese health products, 2000 tons of whole world annual productions, main grown place is south east asia.In Japan, chlorella has been applied to clinical, and malnutrition, hypertension, diabetes, atherosclerosis and hypercholesterolemia and tumour etc. that wound, constipation, oligoleukocythemia, hypoferric anemia, juvenile's partial eclipse cause are carried out assisting therapy.
In recent years, rapid emergence along with the algae bio technology, chlorella is becoming a kind of good model animals aspect the researchs such as " space phycology ", photosynthesis mechanism, transmembrane transport mechanism, be the good host that foreign gene transforms and expresses, become the producer of high added value biomedical product.
Because the extensive use of chlorella, so the demand to chlorella is bigger on the market, cultivates extensive the amplification and industrial applications but the separation of little algae and collection have restricted little algae.The separation of present little algae and the method for collection mainly comprise: centrifugal, filtration, flocculation, air supporting.
Centrifugal separation adopts centrifuge to separate and obtains little algae.Typical centrifugal separation is shown in CN102051332A, it discloses a kind of collection method of oil-containing micro-algae, it comprises the steps: chitosan-Lewis acid flocculation agent is joined in the oil-containing micro-algae nutrient solution, make that Lewis acid concentration is 3-9mg/L in the micro algae culturing liquid, chitosan concentration is 2-30mg/L; Rotating speed with 200-500rpm stirs micro algae culturing liquid 1-5min fast, and the rotating speed with 20-70rpm stirs 20-40min at a slow speed again, afterwards micro algae culturing liquid is staticly settled 15-60min; With the centrifuge dehydration under the condition of rotating speed 3000～5000rpm of little algae flco, the total dehydration rate of resulting algae mud can reach more than 98%.But because centrifuging must adopt centrifugation apparatus, generally be that whizzer carries out, required equipment costs an arm and a leg, and fixed capital (whizzer) investment is big and energy consumption is higher.
CN 101693878A discloses the filter method of a kind of little algae, and it is discharged and collect moisture by siphon after with the moisture filter in little algae liquid, and to realize separating of little algae and moisture, its equipment therefor comprises: little algae cultivation pool is used for cultivating and collecting little algae; Micro-strainer places little algae cultivation pool, is equipped with in the micro-strainer to be used for filtering the moisture of little algae and little algae of damming by the microfiltration membrane of moisture; Siphon pipe, the one end is a Y-tube, wherein one lead to the water outlet that connects micro-strainer, the self-priming that is used for water, prevent cutout, another leads to water receiving and divides collecting tank, the moisture in little algae cultivation pool is flowed in the mode of flowing automatically by siphon pipe be positioned at the moisture collecting tank, and threeway connects gas/liquid recoil inlet; On the siphon pipe of connection moisture collecting tank and gas/liquid recoil ingress is respectively installed a magnetic valve respectively, and this magnetic valve is used for the control recoil, realizes that little algae is concentrated and collects operate continuously.But because the diameter of little algae is generally littler, for example the chlorella diameter only has 3～8 microns, therefore adopts the efficient of filter method low, and film stops up easily, and operation easier is big.
CN 101095459A discloses a kind of method of utilizing flocculence to concentrate marine microalgae, it adds the aqueous solutions of organic acids of chitosan in micro algae culturing liquid, the concentration that makes chitosan in the micro algae culturing liquid is 0.3～8.0 mg/litre, the pH value of regulating micro algae culturing liquid then is 4.5～8.5, make little algae flocculation, and adopt static layering or air-float method to collect throw out.Generally speaking, the employing flucculation process separates and collects little algae and need to use various Magnetic Isolation media, and Magnetic Isolation medium and little algae separation difficulty cause the pollution of target product easily.
Dissolved air flotation needs the auxiliary of Magnetic Isolation medium or surfactant usually when using in little algae, therefore exist the problem same with flucculation process.
For chlorella, although itself and microalgae are seemingly, because chlorella is take food and medicine production as purpose, so its separation is not allow to adopt to have flocculation or the pneumatically supported separation method that pollutes character.Simultaneously, because chlorella cells 1-5 μ m only, its particle diameter is too small, and filtration method is inapplicable equally.At present, the means of centrifugation are mainly adopted in the separation of chlorella in the suitability for industrialized production, and as little algae centrifuging, the centrifugation of chlorella needs centrifugation apparatus equally, cause its cost higher thus.
Because magneticsubstance has the separation of being easy to, lock out operation characteristic of simple, in recent years, adopted magneticsubstance to carry out the existing report of the isolating method of little algae.(Gao Z.W. such as Gao and Peng, Peng X.J., Zhang H.M., Luan Z.K., Fan B.Desalination, 2009,247,337) mixture of employing montmorillonite and copper ferriferous oxide, separating from water of success is harmful to little algae microcystic aeruginosa (Microcystis aeruginosa), its magnetic resolution medium can be reused, but the synthetic comparatively loaded down with trivial details and large usage quantity of this magnetic composite; (Liu D. such as Liu and Li, Li F.T., Zhang B.R.Water Sci.Technol.2009,59,1085) adopt chitosan-modified magnetic polymer as the magnetic resolution medium, successfully remove the algal tufa in the fresh water, but its magnetic resolution medium is synthetic comparatively complicated, the magnetic resolution medium can't be reused, and is subjected to ionic strength affect bigger.
This shows, adopt existing magneticsubstance to carry out the separated and collected of little algae, its material is synthetic complicated, and toward contact need modification or bag be aggregated thing with the frustule coupling, the higher means of calcination of energy consumption is adopted in the recycling of magneticsubstance, and be unfavorable for the comprehensive utilization of little algae, these have all greatly increased cost, the large-scale application difficulty is bigger, therefore, the selection of magnetic medium and recovery technology thereof are the decision magnetic separation techniques in one of little algae separates and can assembling sphere successful Application key issue.
Simultaneously, present magnetic material only is applicable to little algae, and for chlorella, because its size, characteristic etc. all are different from little algae, and therefore present magnetic material and be not suitable for chlorella.Therefore, selecting suitable magnetic medium and utilize this magnetic medium to separate and collect chlorella, is one of technical problem of facing of affiliated technical field.
Summary of the invention
At the deficiencies in the prior art, one of purpose of the present invention is to provide the recovery method of a kind of chlorella magnetic resolution method and this magnetic nanoparticle.
The invention provides a kind of magnetic separation method of chlorella, described method comprises: with Fe
3O
4Nano particle is the Magnetic Isolation medium, cultivates chlorella and finishes the rear described Fe of adding
3O
4Nano particle Magnetic Isolation medium carries out Magnetic Isolation and the collection of chlorella, and the chlorella cells of acquisition and the polymer of magnetic medium are after washing, preferably wash through deionized water, in the polymer of chlorella cells and magnetic medium, add hydrochloric acid, dissolve and carry out micro-filtration, obtain chlorella.
The present invention adopts Fe
3O
4Nano particle is the Magnetic Isolation medium, works as Fe
3O
4When nano particle contacts with chlorella, chlorella cells and magnetic medium polymerization (gathering) form polymer (aggregation) together, when adopting Magnetic Isolation, as shown in Figure 2, described polymer separates with clear liquid, obtain the polymer (aggregation) of chlorella cells and magnetic medium polymerization, after adding hydrochloric acid, Fe
3O
4Nano particle Magnetic Isolation medium is decomposed into FeCl
2And FeCl
3Enter solution, obtain chlorella through micro-filtration, thereby realized the separation of chlorella.
For the FeCl in the solution
2And FeCl
3, regulate the pH value by adding ammoniacal liquor, and then according to existing Fe
3O
4Nanometer grain preparation method is prepared into Fe with it
3O
4Nano particle, thus realized Fe
3O
4The regeneration of nano particle, the Fe of described regeneration
3O
4Nano particle and then continuation contact with the chlorella nutrient solution, thereby have realized Fe
3O
4Recycling of nano particle.
According to chlorella magnetic resolution method of the present invention, said method comprising the steps of:
(1) makes Fe
3O
4Nanoparticulate dispersed forms stable suspension, and it is for subsequent use to obtain the Magnetic Isolation medium.
Described Fe
3O
4Nano particle can prepare, and also is commercially available.Fe
3O
4The preparation of nano particle can be adopted the method for existing bibliographical information, such as the disclosed method of the people such as Peng (Peng Z.G., Hidajat K., Uddin M.S., J.Colloid Interface Sci., 2004,271,277).
Described Fe
3O
4The particle diameter of nano particle is nanoscale, described nano level typical case but limiting examples is the 6-80 nanometer, preferred 8-20 nanometer, more preferably 10-15 nanometer.
The suspension that described formation is stable can adopt the method for the supending that meets arbitrarily restrictive condition, and typical but non-limiting example such as ultrasonic dispersion are through the ultrasonic Fe that makes
3O
4Nanoparticulate dispersed forms stable suspension in deionized water.
(2) add the magnetic resolution medium that step (1) obtains at the chlorella nutrient solution, and it is mixed.
The consumption of described magnetic resolution medium is a significant quantity, and described significant quantity can be obtained according to actual conditions by the person of ordinary skill in the field, and the present invention is 0.02%w/v, more preferably 0.02-0.05%w/v at least preferably.
Described mixing can be adopted any known hybrid mode in this area, typical but non-limiting hybrid mode as, at room temperature stir, it is mixed.Described stirring can begin to stir after the magnetic resolution medium adds fully, also can stir while adding when the magnetic resolution medium adds.
Preferably, the method according to this invention is inserted described micro algae culturing liquid in the stirred reactor, and wherein mixing speed is 200-400rpm, and churning time is 1-3 minute.
(3) chlorella that obtains in the step (2) is carried out magnetic resolution, remove clear liquid, obtain the polymkeric substance of chlorella and magnetic medium.
Work as Fe
3O
4When nano particle contacts and mixes with microalgae cell, Fe
3O
4Nano particle and microalgae cell surface conjunction, thus polymer (aggregation) formed.
Described magnetic resolution adopts the existing magnetic resolution unit operation in this area, because magnetic resolution is a unit operation known in the art, the present invention gives unnecessary details no longer at this point.
(4) with the chlorella of acquisition in the step (3) and the polymkeric substance of magnetic medium, wash and remove clear liquid.
Described washing is as the criterion with chlorella and the magnetic medium polymer that obtains free from admixture or meet pre-provisioning request, and the present invention preferably adopts the deionized water washing, further preferred the employing with the deionized water washing of 2-6 times of volume at least 2 times, preferred 3-6 time, more preferably 3 times.
The described clear liquid of removing preferably adopts magnetic resolution to remove clear liquid.
(5) in the polymer that step (4) obtains, add hydrochloric acid reaction, so that chlorella separates, obtain chlorella by micro-filtration then.
Described adding hydrochloric acid preferably adds the hydrochloric acid of 2-5mL/g polymer so that chlorella separates, and concentration of hydrochloric acid is 6-9mol/L.
The chlorella cells that described micro-filtration obtains can further wash and remove Cl
-And Fe
2+And Fe
3+Deionized water washing is preferably adopted in described washing, more preferably through deionized water rinsing at least 2 times, and preferred 3-6 time, more preferably 3 times.
Preferably, the method according to this invention, in step (5), the microfiltration membrane aperture that micro-filtration adopts is 0.1-1 μ m.
Owing in the filtrate that the filtrate of micro-filtration and washing produce, contain Cl
-And Fe
2+And Fe
3+, therefore one of purpose of the present invention also comprises Fe
3O
4The method that recycles of nano particle (magnetic medium).Described method is included in above-mentioned steps (5) and carries out afterwards:
(6) step (5) is obtained filtrate pH and be adjusted to 0.5-1.5, take filtrate as raw material, prepare Fe
3O
4Nano particle, the described Fe for preparing
3O
4The step (1) of returning nano particle continues to use.
Described pH regulator preferably adopts ammoniacal liquor.
Described Fe
3O
4The preparation method of nano particle, it is the known technology of affiliated technical field, the present invention is not described in detail, and typical but non-limiting preparation method is such as, the people such as Peng (Peng Z.G., Hidajat K., Uddin M.S., J.Colloid Interface Sci., 2004,271,277) Fe that adopts
3O
4The preparation method of nano particle.
For magnetic separation method of chlorella, wherein, step (5) is added hydrochloric acid with Fe according to of the present invention
3O
4The nano particle dissolving, the reaction time is 20-60s, preferred 40s; The described reaction time should strictly be controlled, and the inventor finds, if too short then magnetic medium of reaction time can not dissolve fully; The long FeCl that then can cause dissolving rear formation of reaction time
2Oxidation, the destroyed intracellular organic matter that causes of microalgae cell is secreted outward, is unfavorable for the Fe of subsequent step
3O
4Regeneration and the follow-up deep processing of chlorella.
Therefore, preferably,, may further comprise the steps according to chlorella magnetic resolution method of the present invention:
(1) Fe
3O
4Nano particle is scattered in the deionized water it through ultrasonic, forms stable suspension, namely obtains the Magnetic Isolation medium, and it is for subsequent use to put into then the refrigerator and cooled Tibetan, and the concentration of suspension is 2-5% (w/v);
(2) will cultivate the chlorella nutrient solution that obtains inserts in the stirred reactor at ambient temperature, under the rotating speed of 200-400rpm, add the magnetic resolution medium that step (1) obtains, chlorella in the nutrient solution is separated, the consumption of magnetic resolution medium is 0.02-0.05% (w/v), and churning time is 1-3 minute;
(3) magnetic is removed supernatant liquor after separating, and collects the chlorella cells of separation acquisition and the polymer of magnetic medium, washs at least 3 times with the deionized water of 4-6 times of volume, and each washing is rear removes supernatant liquor by the magnetic separation.
(4) the hydrochloric acid reaction 20-60s of adding 2-5mL/g polymkeric substance in through the polymkeric substance after the washing, concentration of hydrochloric acid is 6-9mol/L, and reaction finishes the back micro-filtration and removes chlorella cells, and chlorella cells is through deionized water rinsing at least 3 times and micro-filtration, collect all filtrates, its main component is FeCl
3, FeCl
2And HCl.
(5) with ammoniacal liquor the filtrate pH of step (4) is adjusted to pH 0.8-1.5, take filtrate as raw material, adopts method (Peng Z.G., the Hidajat K. of existing bibliographical information, Uddin M.S., J.Colloid Interface Sci., 2004,271,277), again prepare Fe
3O
4Nano particle is scattered in the deionized water it through ultrasonic, namely obtains the Magnetic Isolation medium, realizes that the regeneration of magnetic medium is reclaimed, and continues on for separation and the collection of little algae.
The chlorella magnetic resolution method that is used for of the present invention, and the advantage of the efficient recycling method of magnetic medium is:
(1) the present invention adopts Fe
3O
4Nano particle is as Magnetic Isolation medium, Fe
3O
4The synthesis step of nano particle is simple, is easy to amplify;
(2) for the characteristics of chlorella cells, adopt the method for dissolving with hydrochloric acid and ammoniacal liquor recrystallization to realize Fe
3O
4The regeneration recovery of nano particle and separating of chlorella, whole technical process can not produce the chlorella component and destroy, and whole technology is pollution-free;
(3) Fe
3O
4Nano particle Recovery of magnetic medium technology is simply effective, can be applicable to the industrial separation of chlorella, is conducive to reduce production costs.
Description of drawings
Fig. 1 is Fe of the present invention
3O
4The suspension of nano particle.
Fig. 2 is Fe of the present invention
3O
4Nano granule suspension with permanent magnet effect 10s after phenomenon figure.
Embodiment
Embodiment one
Adopt the present invention to utilize magnetic separation method of chlorella, carry out the chlorella Magnetic Isolation, and reclaiming Fe
3O
4The nano particle magnetic medium, described method step is as follows:
(1) with Fe
3O
4Nanoparticulate dispersed forms stable suspension in deionized water, being mixed with concentration is the Magnetic Isolation medium of 3% (w/v), puts into then refrigerator and cooled and hides for subsequent use.
(2) will cultivate the chlorella nutrient solution that obtains and insert in the stirred reactor, and add the magnetic resolution medium under the rotating speed of 300rpm, the consumption of magnetic resolution medium is 0.04% (w/v), and churning time is 2 minutes.
(3) remove supernatant liquid after the magnetic resolution, collect the chlorella cells of separation acquisition and the polymkeric substance of magnetic medium, the rate of recovery of chlorella reaches 99.2%; With the polymkeric substance of chlorella cells and magnetic medium with 5 times to the deionized water wash of this polymer volume at least 3 times, and carry out magnetic and separate, remove clear liquid.
(4) the hydrochloric acid reaction 40s of adding 4mL/g polymer in the polymer of chlorella cells and magnetic medium, concentration of hydrochloric acid is 8mol/L, after finishing, reaction adopt the micro-filtrate membrane filtration of 0.45 μ m to remove chlorella cells, with deionized water rinsing chlorella cells at least 3 times and micro-filtration, obtain chlorella cells.
(5) collect all filtrates, with ammoniacal liquor filtrate pH is adjusted to pH 1.0, take filtrate as raw material, again prepare Fe
3O
4Nano particle.
(6) Fe of preparation
3O
4Nano particle returns step (1), through ultrasonic it is scattered in the deionized water, namely obtains the Magnetic Isolation medium.
Described method has realized the reclaiming of magnetic medium, and the collection that the magnetic medium of regeneration is continued on for chlorella with separate, can reach and regeneration before equal separating effect, the Recovery of magnetic medium rate reaches 96.1%.The Fe that obtains is reclaimed in regeneration
3O
4The paramagnetism of nano particle is shown in Fig. 1-2.
Embodiment two.
Adopt magnetic separation method of chlorella of the present invention and Recovery of magnetic medium method, carry out Fe in the chlorella Magnetic Isolation
3O
4The recovery of nano particle, its step is as follows:
(1) with Fe
3O
4Nanoparticulate dispersed forms stable suspension in deionized water, being mixed with concentration is the Magnetic Isolation medium of 2% (w/v), puts into then refrigerator and cooled and hides for subsequent use.
(2) will cultivate the chlorella nutrient solution that obtains and insert in the stirred reactor, and add the magnetic resolution medium under the rotating speed of 200rpm, the consumption of magnetic resolution medium is 0.02% (w/v), and churning time is 3 minutes.
(3) magnetic is removed supernatant liquid after separating, and collects the chlorella cells of separation acquisition and the polymkeric substance of magnetic medium, and the rate of recovery of chlorella reaches 99.5%; With the polymkeric substance of chlorella cells and magnetic medium with 4 times to the deionized water wash of this polymer volume 3 times, and carry out magnetic and separate, remove clear liquid.
(4) the hydrochloric acid reaction 20s of adding 2mL/g polymkeric substance in the polymkeric substance of chlorella cells and magnetic medium, concentration of hydrochloric acid is 9mol/L, reaction finishes the back and adopts the micro-filtrate membrane filtration of 0.1 μ m to remove frustule, with deionized water rinsing chlorella cells 3 times and micro-filtration, obtains chlorella.
(5) collect all filtrates, with ammoniacal liquor filtrate pH is adjusted to pH 0.8, take filtrate as raw material, again prepare Fe
3O
4Nano particle is scattered in the deionized water it through ultrasonic, namely obtains the Magnetic Isolation medium, realizes that the regeneration of magnetic medium is reclaimed, and can be used for separation and the collection of little algae, and reaches and the front equal separating effect of regeneration, and the Recovery of magnetic medium rate reaches 95.8%.
Embodiment three
Adopt magnetic separation method of chlorella of the present invention and Recovery of magnetic medium method, carry out Fe in the chlorella Magnetic Isolation
3O
4The recovery of nano particle, its step is as follows:
(1) with Fe
3O
4Nanoparticulate dispersed forms stable suspension in deionized water, being mixed with concentration is the Magnetic Isolation medium of 5% (w/v), puts into then refrigerator and cooled and hides for subsequent use.
(2) will cultivate the chlorella nutrient solution that obtains and insert in the stirred reactor, and add the magnetic resolution medium under the rotating speed of 400rpm, the consumption of magnetic resolution medium is 0.05% (w/v), and churning time is 1 minute.
(3) magnetic is removed supernatant liquid after separating, and collects the microalgae cell of separation acquisition and the polymkeric substance of magnetic medium, and the rate of recovery of chlorella reaches 99.1%; With the polymkeric substance of chlorella cells and magnetic medium with 6 times to the deionized water wash of this polymer volume 3 times, and carry out magnetic and separate, remove clear liquid.
(4) the hydrochloric acid reaction 60s of adding 5mL/g polymkeric substance in the polymkeric substance of chlorella cells and magnetic medium, concentration of hydrochloric acid is 6mol/L, reaction finishes the back and adopts the micro-filtrate membrane filtration of 1 μ m to remove frustule, with deionized water rinsing chlorella cells 3 times and micro-filtration, obtains chlorella.
(5) collect all filtrates, with ammoniacal liquor filtrate pH is adjusted to pH 1.5, take filtrate as raw material, again prepare Fe
3O
4Nano particle is scattered in the deionized water it through ultrasonic, namely obtains the Magnetic Isolation medium, realizes that the regeneration of magnetic medium is reclaimed, and can be used for separation and the collection of little algae, and reaches and the front equal separating effect of regeneration, and the Recovery of magnetic medium rate reaches 95.5%.
Can find out that by embodiment 1-3 magnetic separation method of chlorella of the present invention can effectively be collected and separate chlorella, and has realized Fe
3O
4The reclaiming of nano particle magnetic medium has realized the recycling of magnetic medium in the Magnetic Isolation technology.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops on protection scope of the present invention and open range.
Claims (10)
1. magnetic separation method of chlorella, described method comprises: with Fe
3O
4Nano particle is the Magnetic Isolation medium, cultivates chlorella and finishes the rear described Fe of adding
3O
4Nano particle Magnetic Isolation medium carries out Magnetic Isolation and the collection of chlorella, and the chlorella cells of acquisition and the polymer of magnetic medium are after washing, preferably wash through deionized water, in the polymer of chlorella cells and magnetic medium, add hydrochloric acid, dissolve and carry out micro-filtration, obtain chlorella.
2. the method for claim 1 is characterized in that, the filtrate that micro-filtration obtains is prepared into Fe after regulating pH
3O
4Nano particle, described Fe
3O
4Nano particle continues to use as the Magnetic Isolation medium.
3. the method for claim 1 is characterized in that, described method comprises:
(1) makes Fe
3O
4Nanoparticulate dispersed forms stable suspension, obtains the Magnetic Isolation medium;
(2) add the magnetic resolution medium that step (1) obtains at the chlorella nutrient solution, and it is mixed;
(3) chlorella that obtains in the step (2) is carried out magnetic resolution, remove clear liquid, obtain the polymkeric substance of chlorella and magnetic medium;
(4) in the polymer that obtains, add hydrochloric acid reaction, so that chlorella separates, obtain chlorella by micro-filtration then.
4. method as claimed in claim 3 is characterized in that, described method is included in step (3) and and then carries out afterwards:
(3-1), wash and remove clear liquid with the chlorella of acquisition in the step (3) and the polymkeric substance of magnetic medium;
The deionized water washing is adopted in described washing, and preferred the employing with the deionized water of 2-6 times of volume washed 2 times at least, and preferred 3-6 time, more preferably 3 times;
The described clear liquid of removing preferably adopts magnetic resolution to remove clear liquid.
5. such as claim 3 or 4 described methods, it is characterized in that described Fe
3O
4The particle diameter of nano particle is the 6-80 nanometer, preferred 8-20 nanometer, more preferably 10-15 nanometer; The suspension that described formation is stable adopts ultrasonic dispersion, through the ultrasonic Fe that makes
3O
4Nanoparticulate dispersed forms stable suspension in deionized water.
6. as the described method of one of claim 3-5, it is characterized in that the consumption of described magnetic resolution medium is a significant quantity, preferably 0.02%w/v, more preferably 0.02-0.05%w/v at least;
Described mixing at room temperature stirring mixes it;
Described stirring can begin to stir after the magnetic resolution medium adds fully, also can stir while adding when the magnetic resolution medium adds;
Described stirring is, described micro algae culturing liquid is inserted in the stirred reactor, and wherein mixing speed is 200-400rpm, and churning time is 1-3 minute.
7. as the described method of one of claim 4-6, it is characterized in that described adding hydrochloric acid makes chlorella separate, and preferably adds the hydrochloric acid of 2-5mL/g polymkeric substance, concentration of hydrochloric acid is 6-9mol/L, and the reaction times is preferably 20-60s, more preferably 40s;
The chlorella cells that described micro-filtration obtains can further wash and remove Cl
-And Fe
2+And Fe
3+Deionized water wash is preferably adopted in described washing, more preferably through deionized water rinsing at least 2 times, and preferred 3-6 time, more preferably 3 times;
The microfiltration membrane aperture that described micro-filtration adopts is 0.1-1 μ m.
8. as the described method of one of claim 3-7, it is characterized in that, also comprise the steps:
(5) step (4) is obtained filtrate pH and be adjusted to 0.5-1.5, take filtrate as raw material, prepare Fe
3O
4Nano particle, the described Fe for preparing
3O
4The step (1) of can returning nano particle continues to use.
9. method as claimed in claim 8 is characterized in that described pH regulator preferably adopts ammoniacal liquor.
10. chlorella magnetic resolution method is characterized in that described method comprises:
(1) Fe
3O
4Nano particle is scattered in the deionized water it through ultrasonic, forms stable suspension, namely obtains the Magnetic Isolation medium, and the concentration of suspension is 2-5% (w/v);
(2) will cultivate the chlorella nutrient solution that obtains inserts in the stirred reactor at ambient temperature, under the rotating speed of 200-400rpm, add the magnetic resolution medium that step (1) obtains, chlorella in the nutrient solution is separated, the consumption of magnetic resolution medium is 0.02-0.05% (w/v), and churning time is 1-3 minute;
(3) magnetic is removed supernatant liquor after separating, and collects the chlorella cells of separation acquisition and the polymer of magnetic medium, washs at least 3 times with the deionized water of 4-6 times of volume, and each washing is rear removes supernatant liquor by the magnetic separation;
(4) hydrochloric acid of adding 2-5mL/g polymer in through the polymer after the washing, reaction 20-60s, concentration of hydrochloric acid is 6-9mol/L, micro-filtration was removed chlorella cells after reaction finished, chlorella cells obtains chlorella, and collects all filtrates through deionized water rinsing at least 3 times and micro-filtration;
(5) with ammoniacal liquor the filtrate pH of step (4) is adjusted to pH 0.8-1.5, take filtrate as raw material, preparation Fe
3O
4Nano particle, and with the Fe for preparing
3O
4Nano particle returns step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110225274 CN102277300B (en) | 2011-08-08 | 2011-08-08 | Magnetic separation method of chlorella |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110225274 CN102277300B (en) | 2011-08-08 | 2011-08-08 | Magnetic separation method of chlorella |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102277300A true CN102277300A (en) | 2011-12-14 |
| CN102277300B CN102277300B (en) | 2013-05-01 |
Family
ID=45103035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110225274 Expired - Fee Related CN102277300B (en) | 2011-08-08 | 2011-08-08 | Magnetic separation method of chlorella |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102277300B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586101A (en) * | 2012-01-16 | 2012-07-18 | 中国科学院过程工程研究所 | Industrial microalgae magnetic separation and collection device |
| CN103194394A (en) * | 2013-04-10 | 2013-07-10 | 中国科学院过程工程研究所 | Method for separating microalgae by taking polyethyleneimine modified Fe3O4 nanoparticles as flocculating agent |
| CN106179214A (en) * | 2016-07-28 | 2016-12-07 | 北京林业大学 | The functionalization graphene base magnetic nano material of efficient recovery of oil algae and preparation method |
| CN110684655A (en) * | 2019-10-18 | 2020-01-14 | 江苏大学 | Microalgae separation gradient magnetic stabilization fluidized bed device and microalgae harvesting method thereof |
| CN114058513A (en) * | 2021-10-22 | 2022-02-18 | 江苏大学 | Method for culturing microalgae by using nanofluid and photo-biological reaction device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08332079A (en) * | 1995-06-09 | 1996-12-17 | Nippon Paper Ind Co Ltd | Culturing of chlorella |
| CN101892158A (en) * | 2009-05-18 | 2010-11-24 | 中国水产科学研究院东海水产研究所 | Method for preventing and treating protozoa in chlorella culture solution |
-
2011
- 2011-08-08 CN CN 201110225274 patent/CN102277300B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08332079A (en) * | 1995-06-09 | 1996-12-17 | Nippon Paper Ind Co Ltd | Culturing of chlorella |
| CN101892158A (en) * | 2009-05-18 | 2010-11-24 | 中国水产科学研究院东海水产研究所 | Method for preventing and treating protozoa in chlorella culture solution |
Non-Patent Citations (3)
| Title |
|---|
| DAN LIU，FENGTING LI AND BINGRU ZHANG: "Removal or algal blooms in freshwater using magnetic polymer", 《WATER SCIENCE AND TECHNOLOGY》 * |
| 王海英等,1: "小球藻营养成分积累的磁处理强化", 《海湖盐与化工》 * |
| 王海英等,1: "磁处理对小球藻超微结构的影响", 《激光生物学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586101A (en) * | 2012-01-16 | 2012-07-18 | 中国科学院过程工程研究所 | Industrial microalgae magnetic separation and collection device |
| CN102586101B (en) * | 2012-01-16 | 2013-07-31 | 中国科学院过程工程研究所 | Industrial microalgae magnetic separation and collection device |
| CN103194394A (en) * | 2013-04-10 | 2013-07-10 | 中国科学院过程工程研究所 | Method for separating microalgae by taking polyethyleneimine modified Fe3O4 nanoparticles as flocculating agent |
| CN106179214A (en) * | 2016-07-28 | 2016-12-07 | 北京林业大学 | The functionalization graphene base magnetic nano material of efficient recovery of oil algae and preparation method |
| CN106179214B (en) * | 2016-07-28 | 2019-01-25 | 北京林业大学 | The functionalization graphene base magnetic nano material and preparation method of efficient recovery of oil algae |
| CN110684655A (en) * | 2019-10-18 | 2020-01-14 | 江苏大学 | Microalgae separation gradient magnetic stabilization fluidized bed device and microalgae harvesting method thereof |
| CN110684655B (en) * | 2019-10-18 | 2023-03-17 | 江苏大学 | Microalgae separation gradient magnetic stabilization fluidized bed device and microalgae harvesting method thereof |
| CN114058513A (en) * | 2021-10-22 | 2022-02-18 | 江苏大学 | Method for culturing microalgae by using nanofluid and photo-biological reaction device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102277300B (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102277300B (en) | Magnetic separation method of chlorella | |
| CN108129547B (en) | Method for extracting extracellular polymeric substance of zoogloea | |
| CN109628316B (en) | Method for harvesting oil-producing microalgae in urban sewage culture system in large scale by using magnetic particles | |
| CN103493969B (en) | A kind of method of producing giant salamander polypeptide powder | |
| JPWO2020054755A1 (en) | Separation device and method of separating objects to be separated using it | |
| CN103740595A (en) | Method for producing chlorella concentrated solution | |
| CN103073652A (en) | Method for extracting polysaccharide of spirulina platensis | |
| CN104151424A (en) | Phycocyanin extraction method | |
| CN103479597A (en) | Preparation method and use of grape source active component nano-scale membrane type vesicle | |
| CN107487860B (en) | A kind of fish-farming with sewage microalgae device and preparation method thereof | |
| CN103333880A (en) | Method for harvesting microalgae with magnetic separator | |
| KR20060115793A (en) | Chitosan particle and process therefor | |
| CN1329103A (en) | Method for extracting protein, short peptide, nucleic acid, isoflavone, saponin and oligosaccharide by using high and low temperature soybean cake | |
| CN102321541B (en) | Botryococcus braunii magnetic separation method | |
| CN107987183B (en) | Method for extracting chitosan oligosaccharide from filamentous fungi | |
| TWI615467B (en) | Microalgae harvest module and method of harvesting microalgae | |
| CN103740594A (en) | Preparation method of chlorella cream | |
| CN211645261U (en) | Nicotinamide filter equipment that hydrolysises | |
| CN201525847U (en) | Immobilized enzyme carrier preparation facilities | |
| CN1699561A (en) | Process for preparing artemia hatching enzyme by using artemia hatching liquid | |
| CN1861781A (en) | Picking method of single cell algae | |
| CN207845533U (en) | A kind of chondroitin sulfate production line | |
| RU2488634C1 (en) | Method to produce dna from salmon roe | |
| CN101245326B (en) | Concentration method for virus or bacteria | |
| CN109371050B (en) | Preparation method of canine interferon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130501 Termination date: 20170808 |