CN104480016B - Self assembly magnetic modified flocculant for separating microalgae and its preparation method and application - Google Patents

Self assembly magnetic modified flocculant for separating microalgae and its preparation method and application Download PDF

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CN104480016B
CN104480016B CN201410741186.6A CN201410741186A CN104480016B CN 104480016 B CN104480016 B CN 104480016B CN 201410741186 A CN201410741186 A CN 201410741186A CN 104480016 B CN104480016 B CN 104480016B
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梁文艳
赵远
刘丽君
孙小丽
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Beijing Forestry University
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Abstract

The present invention relates to Chemical Engineering separation field, and in particular to self assembly magnetic modified flocculant for separating microalgae and its preparation method and application.The flocculant is amine-methylated tannin powder:Magnetic particle:Water is with 0.2mg:0.01g:1ml‑10mg:0.5g:1ml ratios are mixed to prepare.The Fe that the present invention uses3O4Magnetic particle is nanoscale magnetic particle, and it is more easy to be assembled with amine-methylated tannin, and the magnetizing mediums after assembling has flocculating property of 5 10 times more than traditional flocculant, but cost is the 1/10 of conventional flocculant.

Description

Self assembly magnetic modified flocculant for separating microalgae and its preparation method and application
Technical field
The present invention relates to Chemical Engineering separation field, and in particular to for separate microalgae self assembly magnetic modified flocculant and Its preparation method and application.
Background technology
In recent years, the increasingly depleted of fossil energy and environmental pollution is increasingly serious, searching is cleaned reproducible new energy Source turns into focus.Microalgae contains the nutriments such as abundant protein, unrighted acid, pigment, while has oil content again High, the advantages that growth cycle is short, biological yield is high, it is expected to the production of biodiesel raw material as a kind of great potential.But due to Microalgae individual is small (2-30 μm), and causing it to harvest, link cost is too high, and popularization and application are restricted.
Conventional microalgae recovery method has centrifugation, filtering, sedimentation, air supporting etc., but because microalgae individual is small, concentration is low, enters Before row harvesting, typically flocculation pretreatment is carried out to microalgae, it is gathered into larger flocculation in the presence of the medicament that flocculates Body, improve harvest efficiency.Conventional flocculant includes traditional inorganic salt class (aluminium salt, molysite), polymerization macromolecule class (polyaluminium Aluminium, PAFS, PAFC), biological species (clay, shell, chitosan etc.), but metallic salt flocculant can band Carry out the metal ion pollution of biomass, biological species flocculant such as chitosan, bacteria agent etc. is expensive.Therefore, it is a kind of efficiently, Inexpensively, degradable natural flocculating agent, there will be good application prospect.
Tannin is the phenols secondary metabolite in plant, the rich reserves in nature, is primarily present in plant It is the secondary product of forestry for being only second to cellulose, lignin, hemicellulose in skin, root, leaf and pulp.Because vegatable tannin contains greatly The phenolic hydroxyl structure of amount, micelle surface are negatively charged for largely having significant scattered work in the colloid of negative charge in water With, it is contemplated that the nucleophilicity of vegatable tannin benzene cyclic structure, it is electrically charged on the strong nucleophilic site of cyclic structure to introduce other After group-amine methyl group, flocculation property can be greatly improved.Because tannin derives from natural products, easily dropped by biology Solution, will not cause secondary pollution to environment, be a kind of new environmentally friendly material.
Magnetic material has the characteristics of easily separated, simple to operate, in recent years, the side of microalgae separation is carried out using magnetic material Method has been reported.Chinese Academy of Sciences's process Guo Chen, Hu Yiru et al. once invent " a kind of method of magnetic separator microalgae ", but The trim that this method uses is diallyldimethylammonium chloride polymer or polyethyleneimine, is finally re-dissolved in cation Recombinated in polyacrylamide, form magnetic flocculation agent, this can bring the noxious pollutants such as acrylamide to the biomass of harvest Residual.Liu and li etc. (Liu D., Li F.T., Zhang B.R.Water Sci.Technol.2009,59,1085) is used Chitosan-modified magnetic polymer has been successfully separated the blue-green algae of algal tufa in fresh water, but its Magneto separate is situated between as Magneto separate medium The synthesis of matter is complex, and magnetizing mediums is influenceed to reuse by ionic strength, plus the expensive cost of chitosan, pole Big adds cost, and large-scale application is very difficult.
In addition, Fe3O4Magnetic particle is irregular graininess, and some flocculants can not carry out self assembly with it, will can not have Flocculation group-iron hydroxide micelle and the magnetic particle of effect fit together, and form effective magnetic modified flocculant.For example, with Polymeric ferric aluminum and magnetic compounding collect the microcystic aeruginosa in fresh water, and algae cell density is 1-2 × 109When, collection rate only has 70%, and higher is required to magnetic field intensity, it is time-consuming longer to collect process.In addition, also poly-ferric chloride, cation poly- third Acrylamide etc., collects microalgae cell after they are mixed with magnetic particle, effect is not also notable.
Amine-methylated tannin and magnetic particle on the premise of self assembly, by externally-applied magnetic field, are utilized the restructuring by the present invention Magnetizing mediums carries out magnetic capture to the microalgae in high density algae solution.Compared with traditional microalgae isolation technics, this method uses Novel ring Border friendly material, disengaging time is short, and effect is good, and is remained in supernatant almost without flocculant, and cost is flocculated less than tradition The 1/10 of agent, energy consumption reduce by more than 50%.
The content of the invention
It is an object of the invention to provide a kind of self assembly magnetic modified flocculant for being used to separate microalgae.
Another object of the present invention, which is to provide, prepares the above-mentioned method for being used to separate the self assembly magnetic modified flocculant of microalgae.
Another object of the present invention is to provide the method using self assembly magnetic modified flocculant separation microalgae.
The invention provides the environment protection type magnetic flocculant that a kind of amine-methylated tannin and magnetic particle are self-assembled into, biography is overcome System flocculant the problem of bringing heavy metal ion to pollute the biomass of harvest, high ionic strength is avoided in supernatant to culture The influence that base recycles, and the microalgae of harvest can be made to carry out second incubation, doubled yield, improve yield rate.According to the present invention Be used for separate microalgae self assembly magnetic modified flocculant be magnetic be modified amine-methylated tannin, first, claim falling for certain mass Leaf pine tannin, it is dissolved in the water of 20 times of its quality, filters and remove insoluble matter, then according to volume ratio (tannin:Petroleum ether=3: 1) ratio adds petroleum ether extraction, and layer solution is removed after concussion and adds three times volume ethanol, is evaporated after logical under 70 DEG C of water-baths Appropriate nitrogen, 10% (v/v) acetum is added, according to mass ratio (tannin:Dimethylamine:Formaldehyde=1:1:2) ratio adds Enter dimethylamine and formaldehyde, reaction product is freeze-dried after reacting 3h, obtains amine-methylated tannin powder；Then, by above-mentioned system The amine-methylated tannin powder obtained is made into (amine-methylated tannin powder with magnetic particle:Magnetic particle:Water)=(0.2mg:0.01g: 1ml-10mg:0.5g:Magnetizing mediums 1ml), added after standing mixing 1min in high density algae solution so that amine-methylated tannin Final concentration is in 20mg/L-1000mg/L, and magnetic particle final concentration is between 0.5mg/mL-50mg/mL.
According to the self assembly magnetic modified flocculant for being used to separate microalgae of the present invention, its improvement is, with common plant list Rather (final concentration 60-1000mg/L) flocculation separation high density algae solution, either 30s or 3h, all only 5%-10% separation Rate；Fe3O4Magnetic particle (final concentration 10-50mg/mL) separates algae solution, and separation rate also only has 30%-40%, even if by vegatable tannin (final concentration 60-1000mg/L) and Fe3O4Magnetic particle (final concentration 10-50mg/mL) carries out mixing and added, and separation rate still only has 40%-45%.But amine-methylated tannin (final concentration 20-500mg/L) and magnetic particle (final concentration 2-20mg/mL) are carried out After being self-assembled into magnetizing mediums, separation rate can bring up to 90% in 30s, and reach 95% in 3min, and the algae solution handled is not Need to remove by centrifugation the exocytosis material of high concentration, greatly reduce processing cost.
Tannin used in the present invention is plant natural extract, is novel environmental friendly material.It is with magnetic particle from group After dress in the presence of additional low-intensity magnetic field, it can realize that (cell density is >=1 × 10 to high density algae solution in 3min9Individual/L) in The magnetic capture of frustule is collected, and separation rate can reach more than 95%.
The present invention is mainly achieved through the following technical solutions：
The magnetizing mediums separation microalgae of self assembly is provided, at ambient temperature by amine-methylated tannin and magnetic particle self assembly Directly it is added in high density algae solution and is thoroughly mixed afterwards, the micro- magnetic flco wrapped up by magnetic particle is formed, so as to additional Quick separating is carried out under conditions of low magnetic field intensity.
Separated microalgae include chlorella, chlorella vulgaris, braunii ball algae, protein pellet algae, chlorella ellipsoidea, It is Nannochloropsis oculata, scenedesmus obliquus, Scenedesmus quadricauda, tapering grid algae, rhombus algae, buttress shaft algae, Isochrysis galbana, the hidden dinoflagellates of Kou Shi, salt algae, brown Refer to algae, four algaes, schizochytrium limacinum, a variety of Trentepohlias of microcystic aeruginosa.Preferably ball algae, grid algae, microcystic aeruginosa.
It may comprise steps of according to the method for the self assembly magnetizing mediums of present invention separation microalgae：
1) the amine-methylated modification of tannin：Claim the larch tannin of certain mass, be dissolved in the water of 20 times of its quality, filter Insoluble matter is removed, then (tannin by volume:Petroleum ether=3:1) ratio adds petroleum ether extraction, and it is molten to remove layer after concussion Liquid adds three times volume ethanol, is evaporated after leading to appropriate nitrogen under 70 DEG C of water-baths, adds 10% (v/v) acetum, according to Mass ratio (tannin:Dimethylamine:Formaldehyde=1:1:2) ratio adds dimethylamine and formaldehyde, freezes reaction product after reacting 3h Dry, obtain amine-methylated tannin powder.
2) amine-methylated tannin powder made from step 1) and magnetic particle are made into (amine-methylated tannin powder:Magnetic particle: Water)=(0.2mg:0.01g:1ml-10mg:0.5g:Magnetizing mediums 1ml), algae listed by such scheme is added after standing mixing 1min Kind high density algae solution in so that amine-methylated tannin final concentration is in 20mg/L-1000mg/L, and magnetic particle final concentration is in 0.5mg/ Between mL-50mg/mL.
It is as described above, only when amine-methylated tannin powder and magnetic particle mass ratio are 1:10-1:Change in the range of 200 When, the magnetic flocculation agent after assembling just has preferable flocculating effect, amine-methylated tannin powder and Fe3O4Any material of magnetic particle Excessive or deficiency, can all cause effective flocculation group " amine methyl-iron hydroxide " that magnetic flocculation agent surface is formed to lose flocculation Effect.Amine-methylated tannin dosage is too low, is not enough to be formed enough flocculation groups and goes to separate high density algae solution；Dosage mistake Height, the effective group that can be formed assembling occur to dissociate again.Fe3O4Magnetic particle concentration is too low, and the magnetic flocculation agent being self-assembly of is not Can rapid subsidence under the action of a magnetic force, and excessive concentration, the surface weight of the positively charged magnetic flocculation agent in original surface can be made It is new negatively charged, electronegativity is shown, and it is mutually exclusive with itself negatively charged frustule, reduce flocculating effect.
3) pH to 4.2-7.1 of algae solution is adjusted；PH value is too low, and the frustule wall that can make to separate and collect, which ruptures, to lose activity； PH value is too high, and amine-methylated tannin surface can be made to form-NH4Group dissociates, and loses flocculation.
4) in the algae solution obtained by step 3), the magnetizing mediums that step 2) assembling obtains is added, is formed after being sufficiently stirred micro- Algae magnetic flocculation body.
5) microalgae magnetic flocculation body under applied field strengths >=500G field strength to step 4) carries out Magneto separate, in removal Clear liquid, collect the microalgae that separation obtains.When magnetic field intensity is too low, during less than 500G, microalgae magnetic can be prevented to coagulate body from by magnetic field The effect rapid subsidence of power, as long as so magnetic field intensity can meet requirement of the magnetic flocculation to magnetic field more than 500G.
The magnetizing mediums that amine-methylated tannin used in the present invention is self-assembled into magnetic particle, operating method very simple.Tool Body, directly at room temperature, by Fe3O4Magnetic particle is stirred with amine-methylated tannin, distilled water, and amine-methylated tannin will Automatically magnetic particle surface is coated on, is assembled into the magnetic particle of flocculating function, self assembly thing can be now with the current, and normal temperature preserves.Its Described in Fe3O4Magnetic particle commercially available can also be obtained with now with the current.
Above-mentioned steps 3) described in algae solution pH adjust to 4.2-7.1, such as：4.2、4.5、5、5.5、6.0、6.5、7.1.For Different microalgae, there is preferable separating effect within the range.It is used regulation algae solution pH value the preferred NaOH solution of reagent and HCl solution, concentration range 0.1mol/L-1mol/L.
Above-mentioned steps 3) described in magnetizing mediums dosage be about 0.25%-10% (v/v), such as 0.25% (v/v), 0.50% (v/v), 1.50% (v/v), 2.0% (v/v), 3.0% (v/v), 4.0% (v/v), 5.0% (v/v), 8.0% (v/v), 10.0% (v/v).
Magnetizing mediums is added in high density algae solution by methods described, mixing time 30s-1min, for example, 30s, 40s, 50s, 1min, preferably 40s-1min.Speed of agitator is 50-200rpm, for example, 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, preferably 80-100rpm.
In step 5), the Magneto separate is carried out on NdFeB permanent magnets, and magnetic field intensity is >=500G, as 500G, 800G, 1000G, 1500G, 2000G, 2500G, 3000G, 5000G, preferably 1000-3000G.
The Magneto separate time is 0.5-3min, further excellent such as 30s, 1min, 1.5min, 2min, 2.5min, 3min Elect 0.5-1.5min as.
The magnetism separate method advantage of the present invention can be summarized as follows：
1) this magnetism separate method main object is the higher microalgae stoste of grease yield, before separation algae solution need not move through from The heart, dilution etc. pre-process, and cell density is high, for 10-100 times of conventional flocculation algae cell density.
2) raw material tannin of the present invention is the secondary metabolites in plant, can be dropped within natural environment middle or short term Solution, half-life period is about 3-5 days, will not bring secondary pollution to environment, is novel environmental friendly material.
3) tannin is compared compared with other biological flocculant, cheap, and amine-methylated modification is simple to operate, and cost is relatively low, Laboratory is easy to control, workable.
4) Fe that the present invention uses3O4Magnetic particle is nanoscale magnetic particle, and more easy, group is assembled with amine-methylated tannin Magnetizing mediums after dress has flocculating property of 5-10 times more than traditional flocculant, but cost is the 1/10 of conventional flocculant.
5) magnetic flocculation method provided by the invention, magnetic flocculation medium consumption is few, and cost is low, and disengaging time is short, and separation is set It is standby to require relatively low, it is expected to industrialize large-scale promotion use.
6) Fe used in the present invention3O4Magnetic particle easily reclaims, and can Reusability, only need to simply wash after use permanent magnet Container either side is placed in, supernatant room temperature is outwelled and dries, the recovery to magnetic particle can be realized, and reaches returning for 89%-95% Yield.
Embodiment
Embodiment 1:The amine-methylated tannin of 50mg/L and 10mg/mL Fe3O4Magnetic particle separates braunii ball algae (Botryococcus braunii)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:200, the two is added to cell density as 1.56 × 10 after uniformly mixing 1min10Individual/L braunii ball algae algae In liquid, algae solution pH value is adjusted to 5.86, the amine-methylated final concentration of 50mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle.It hurry up Standing sedimentation on 2000G magnetic field is placed in after speed stirring 1min, supernatant algae cell density is calculated after 0.5min and is separated Rate is 94.6%.
Embodiment 2:The amine-methylated tannin of 100mg/L and 8mg/mL Fe3O4Magnetic particle separates Scenedesmus quadricauda (Scenedesmus quadricauda)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:80, the two is added to cell density as 2.11 × 10 after uniformly mixing 1min10In individual/L Scenedesmus quadricauda algae solution, Algae solution pH value is adjusted to 5.69, and amine-methylated tannin final concentration of 100mg/L, Fe3O4The final concentration of 8mg/mL of magnetic particle.Quickly Standing sedimentation on 3000G magnetic field is placed in after stirring 1min, supernatant algae cell density is calculated after 0.5min and obtains separation rate For 95.2%.
Embodiment 3:The amine-methylated tannin of 200mg/L and 10mg/mL Fe3O4Magnetic particle protein isolate chlorella (Chlorella pyrenoidosa)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:80, the two is added to cell density as 2.54 × 10 after uniformly mixing 1min10Individual/L protein pellet algae algae solution In, regulation algae solution pH value is 6.01, the amine-methylated final concentration of 200mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, Standing sedimentation in 2800G magnetic field is placed in after quick stirring 1min, supernatant algae cell density is calculated after 3min and is separated Rate is 96.0%.
Embodiment 4:The amine-methylated tannin of 150mg/L and 20mg/mL Fe3O4Magnetic particle separation Du Shi algaes (Dunaliella primolecta)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:134, the two is added to cell density as 2.01 × 10 after uniformly mixing 1min10In individual/L dunaliella liquid, It is 4.98 to adjust algae solution pH value, the amine-methylated final concentration of 150mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, quickly Standing sedimentation in 3800G magnetic field is placed in after stirring 1min, supernatant algae cell density is calculated after 1min and obtains separation rate is 95.4%.
Embodiment 5:The amine-methylated tannin of 300mg/L and 20mg/mL Fe3O4Magnetic particle separates scenedesmus obliquus (Scenedesmus obliqnus)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:67, the two is added to cell density as 3.15 × 10 after uniformly mixing 1min10In individual/L scenedesmus obliquus algae solution, It is 5.02 to adjust algae solution pH value, the amine-methylated final concentration of 300mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, quickly Standing sedimentation in 3800G magnetic field is placed in after stirring 1min, supernatant algae cell density is calculated after 1min and obtains separation rate is 94.4%.
Embodiment 6:The amine-methylated tannin of 300mg/L and 10mg/mL Fe3O4Magnetic particle separates chlorella vulgaris (Chlorella vulgaris)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:34, the two is added to cell density as 3.98 × 10 after uniformly mixing 1min10Individual/L chlorella vulgaris algae solution In, regulation algae solution pH value is 5.45, the amine-methylated final concentration of 300mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, Standing sedimentation in 3800G magnetic field is placed in after quick stirring 1min, supernatant algae cell density is calculated after 1min and is separated Rate is 96.1%.
Embodiment 7:The amine-methylated tannin of 500mg/L and 20mg/mL Fe3O4Magnetic particle separates Nannochloropsis oculata (Nannochloropsis sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:Cell density is added to as 1.01 × 10 after 1min is uniformly mixed both 4011In individual/L Nannochloropsis oculata algae solution, It is 6.09 to adjust algae solution pH value, the amine-methylated final concentration of 500mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, quickly Standing sedimentation in 4000G magnetic field is placed in after stirring 1min, supernatant algae cell density is calculated after 3min and obtains separation rate is 97.5%.
Embodiment 8:The amine-methylated tannin of 300mg/L and 5mg/mL Fe3O4Magnetic particle separates schizochytrium limacinum (Schizochytrium sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:60, the two is added to cell density as 1.01 × 10 after uniformly mixing 1min11In individual/L schizochytrium limacinum algae solution, It is 6.33 to adjust solution ph, the amine-methylated final concentration of 300mg/L of tannin, Fe3O4The final concentration of 50mg/mL of magnetic particle, quickly Standing sedimentation in 2000G magnetic field is placed in after stirring 1min, supernatant algae cell density is calculated after 3min and obtains separation rate is 95.2%.
Embodiment 9:The amine-methylated tannin of 200mg/L and 20mg/mL Fe3O4Magnetic particle separates Phaeodactylum tricornutum (Phaeodactylum tricornutum)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:100, the two is added to cell density as 1.78 × 10 after uniformly mixing 1min10Individual/L Phaeodactylum tricornutum algae solution In, regulation algae solution pH value is 5.69, the amine-methylated final concentration of 200mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, Standing sedimentation in 4000G magnetic field is placed in after quick stirring 1min, supernatant algae cell density is calculated after 1min and is separated Rate is 94.3%.
Embodiment 10:The amine-methylated tannin of 200mg/L and 10mg/mL Fe3O4Magnetic particle separates four algaes (Tetraselmis sueica)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:50, the two is added to cell density as 2.01 × 10 after uniformly mixing 1min10In individual/L four algae algae solutions, adjust It is 5.89 to save algae solution pH value, the amine-methylated final concentration of 200mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, is quickly stirred Standing sedimentation in 3000G magnetic field is placed in after mixing 1min, 0.5min, which calculates supernatant algae cell density and obtains separation rate, is 93.9%.
Embodiment 11:The amine-methylated tannin of 400mg/L and 5mg/mL Fe3O4Magnetic particle separates the hidden dinoflagellate of bandit's formula (Crypthecodinium cohnii)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:25, the two is added to cell density as 3.34 × 10 after uniformly mixing 1min10Individual/L hidden dinoflagellate the algae solutions of Kou Shi In, regulation algae solution pH value is 6.89, the amine-methylated final concentration of 400mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, Standing sedimentation in 1800G magnetic field is placed in after quick stirring 1min, 0.5min calculates supernatant algae cell density and separated Rate is 96.9%.
Embodiment 12:The amine-methylated tannin of 150mg/L and 20mg/mL Fe3O4Magnetic particle separation rhombus algae (Nitzschia sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:133, the two is added to cell density as 2.11 × 10 after uniformly mixing 1min10In individual/L rhombus algae algae solution, It is 5.11 to adjust algae solution pH value, the amine-methylated final concentration of 150mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, quickly Standing sedimentation in 3500G magnetic field is placed in after stirring 1min, 1min, which calculates supernatant algae cell density and obtains separation rate, is 97.0%.
Embodiment 13:The amine-methylated tannin of 250mg/L and 10mg/mL Fe3O4Magnetic particle separates Isochrysis galbana (Isochrysis sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:40, the two is added to cell density as 3.5 × 10 after uniformly mixing 1min10In individual/L Isochrysis galbana algae solution, It is 5.74 to adjust algae solution pH value, the amine-methylated final concentration of 250mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, quickly Standing sedimentation in 2000G magnetic field is placed in after stirring 1min, 1min, which calculates supernatant algae cell density and obtains separation rate, is 95.3%.
Embodiment 14:The amine-methylated tannin of 500mg/L and 20mg/mL Fe3O4Magnetic particle separates buttress shaft algae (Cylindrotheca sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:40, the two is added to cell density as 5.89 × 10 after uniformly mixing 1min10In individual/L buttress shaft algae algae solution, adjust It is 6.21 to save algae solution pH value, the amine-methylated final concentration of 500mg/L of tannin, Fe3O4The final concentration of 20mg/mL of magnetic particle, is quickly stirred Standing sedimentation in 4000G magnetic field is placed in after mixing 1min, 1min, which calculates supernatant algae cell density and obtains separation rate, is 97.2%.
Embodiment 15:The amine-methylated tannin of 350mg/L and 5mg/mL Fe3O4Magnetic particle separation salt gives birth to single intestines algae (Monallanthus salina)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:15, the two is added to cell density as 5.89 × 10 after uniformly mixing 1min10Individual/L salt gives birth to single intestines algae algae solution In, regulation algae solution pH value is 6.17, the amine-methylated final concentration of 350mg/L of tannin, Fe3O4The final concentration of 5mg/mL of magnetic particle, soon Standing sedimentation in 2000G magnetic field is placed in after speed stirring 1min, 1min, which calculates supernatant algae cell density and obtains separation rate, is 98.1%.
Embodiment 16:The amine-methylated tannin of 100mg/L and 5mg/mL Fe3O4Magnetic particle separation chlorella (Chlorella sp.)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:50, the two is added to cell density as 1.12 × 10 after uniformly mixing 1min10In individual/L chlorella algae solution, adjust It is 5.34 to save algae solution pH value, the amine-methylated final concentration of 100mg/L of tannin, Fe3O4The final concentration of 5mg/mL of magnetic particle, is quickly stirred Standing sedimentation in 1800G magnetic field is placed in after mixing 1min, 10min, which calculates supernatant algae cell density and obtains separation rate, is 98.1%.
Embodiment 17:The amine-methylated tannin of 200mg/L and 10mg/mL Fe3O4Magnetic particle separates chlorella ellipsoidea (Chlorella ellipsoidea)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:50, the two is added to cell density as 1.99 × 10 after uniformly mixing 1min10Individual/L chlorella ellipsoidea algae solution In, regulation algae solution pH value is 6.29, the amine-methylated final concentration of 200mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, Standing sedimentation in 3000G magnetic field is placed in after quick stirring 1min, 3min calculates supernatant algae cell density and obtains separation rate For 96.1%.
Embodiment 18:The amine-methylated tannin of 500mg/L and 10mg/mL Fe3O4Magnetic particle separates tapering grid algae (S.acuminatus)
Fe is added into the amine-methylated tannin aqueous solution3O4Magnetic particle, make amine-methylated tannin powder:Fe3O4Magnetic particle Mass ratio is 1:20, the two is added to cell density as 5.48 × 10 after uniformly mixing 1min10In individual/L tapering grid algae algae solution, It is 6.23 to adjust algae solution pH value, the amine-methylated final concentration of 500mg/L of tannin, Fe3O4The final concentration of 10mg/mL of magnetic particle, quickly Standing sedimentation in 3800G magnetic field is placed in after stirring 1min, 3min, which calculates supernatant algae cell density and obtains separation rate, is 97.8%.

Claims (8)

1. a kind of self assembly magnetic modified flocculant for being used to separate microalgae, it is characterised in that the flocculant is amine-methylated list Peaceful powder, Fe3O4Magnetic particle and water are obtained by mixing, wherein, amine-methylated tannin powder and Fe3O4The mass ratio of magnetic particle is 1: 200~1:15。
2. the self assembly magnetic modified flocculant according to claim 1 for being used to separate microalgae, it is characterised in that the amine first The preparation method of base tannin powder is as follows：Larch tannin solid dissolving in the water of 20 times of its quality, filter remove it is insoluble After thing, according to volume ratio tannin:Petroleum ether=3:1 ratio adds petroleum ether extraction, and acutely removing layer solution after concussion adds three Times volume ethanol, it is evaporated after leading to appropriate nitrogen under 70 DEG C of water-baths, adds 10% v/v acetum, compare tannin according to quality: Dimethylamine:Formaldehyde=1:1:2 ratio adds dimethylamine and formaldehyde, is freeze-dried reaction product after reacting 3h, obtains amine methyl Change tannin powder.
A kind of 3. method for preparing the self assembly magnetic modified flocculant for separating microalgae, it is characterised in that methods described includes Following steps：
1）Prepare amine-methylated tannin powder；
2）By amine-methylated tannin powder obtained above and Fe3O4Magnetic particle and water are made into self assembly magnetic modified flocculant, wherein Amine-methylated tannin powder and Fe3O4The mass ratio of magnetic particle is 1:200~1:15.
4. it is used for the application for separating the self assembly magnetic modified flocculant of microalgae described in claim 1, it is characterised in that by self assembly Magnetic modified flocculant is added in high density algae solution so that amine-methylated tannin final concentration in 0.05mg/mL-0.5mg/mL, Fe3O4Magnetic particle final concentration carries out magnetic point under applied field strengths >=500G between 5mg/mL-20mg/mL to frustule From.
5. application according to claim 4, it is characterised in that algae solution pH is 4.2-7.1.
6. application according to claim 4, it is characterised in that the dosage of self assembly magnetic modified flocculant is 0.25%-10% v/v。
7. application according to claim 4, it is characterised in that magnetic field intensity is >=500G.
8. application according to claim 4, it is characterised in that the microalgae is chlorella vulgaris（Chlorella vulgaris）, braunii ball algae, protein pellet algae（Chlorella pyrenoidosa）, chlorella ellipsoidea, Nannochloropsis oculata, Scenedesmus obliquus, Scenedesmus quadricauda, tapering grid algae, rhombus algae, buttress shaft algae, Isochrysis galbana, the hidden dinoflagellates of Kou Shi, salt algae, brown algae, four Algae, schizochytrium limacinum, microcystic aeruginosa.
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