CN104211227A - Method for removing algal toxin in water body by using nano-iron material - Google Patents
Method for removing algal toxin in water body by using nano-iron material Download PDFInfo
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- CN104211227A CN104211227A CN201410471425.0A CN201410471425A CN104211227A CN 104211227 A CN104211227 A CN 104211227A CN 201410471425 A CN201410471425 A CN 201410471425A CN 104211227 A CN104211227 A CN 104211227A
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Abstract
The invention discloses a method for removing algal toxin in a water body by using a nano-iron material. The method comprises the following steps: S1, adjusting the pH value of an algae liquid to neutral or acidic; S2, adding a coagulant into the algae liquid to coagulate algae; S3, adding a coagulant aid nano ferroferric oxide into the algae liquid; and S4, after stirring the algae liquid, precipitating to remove algal toxin in the algae liquid. The removal amount of the algal toxin in the coagulating sedimentation process is represented by means of detecting the content of the algal toxin in the supernatant liquid. The algal toxin in the water body can be effectively removed by using the nano-iron material as the coagulant aid by means of the small size effect and surface effect as well as the charged property of the nano-iron material under different conditions. The method is low in cost and simple and feasible.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of nano ferriferrous oxide removes Algae toxins in water body method as coagulant aids.
Background technology
Along with socioeconomic development, a large amount of nitrogen phosphorus substances flows in natural water, has caused the eutrophication process of nature major part water body
[1].According to the investigation of United Nations Environment Programme (UNEP), nowadays has the eutrophication problem that the natural water of 30%-40% suffers in various degree at least
[2].Body eutrophication can cause increasing crazily of algae, wherein remarkable with the growth of microcystic aeruginosa.But the growth of microcystic aeruginosa not only can cause water quality to cancerate, also can release microcapsule Algae toxins.Algae toxins is very large to the harm of organism, Rogers have studied to the Algae toxins of the injected in mice 8 μ g/kg ~ 128 μ g/kg of pregnancy, the anamorphosis of the young can be caused at low concentrations, under high density Algae toxins condition (>32 μ g/kg), directly can bring out the death of parent
[3].
also the Algae toxins all containing high density in the internal organ of fish in eutrophication water, liver and muscle is reported, even if the wawter bloom phenomenon of water body disappears, these Algae toxins still can be accumulated in fish body, and the highest 42 times of can reach normality (0.04 μ g/kg) of concentration, the mankind also just directly absorb Algae toxins once these fishes edible
[4].Nowadays the method processing high density algae water the most frequently used is exactly preoxidation+chemical coagulation process process, the reagent dioxide peroxide that general preoxidation is used
[5], ozone
[6], and potassium permanganate
[7]although these oxidising agents can destroy frustule in certain degree, the effect of enhanced coagulation, while destruction frustule, Algae toxins in born of the same parents also can be made to be released in water body, thus increase the amount of Algae toxins in the rear water body of process
[8].Even the coagulating agent of routine is polymerize aluminum chloride (PACl) such as, ferric sulfate, aluminum chloride etc. also can increase the amount of Algae toxins in the rear water body of process in coagulation process
[9,10].
In view of the deficiencies in the prior art, those skilled in the art are devoted to develop a kind of novel method removing Algae toxins content in water body.
Reference:
[1]Lawton,L.and?P.J.Robertson,Physico-chemical?treatment?methods?for?the?removal?of?microcystins(cyanobacterial?hepatotoxins)from?potable?waters.Chemical?Society?Reviews,1999.28(4):p.217-224.
[2] Xu Chuan, Shu Weiqun, Pollution of Microcystin situation, detects and toxic effect. foreign medical science: hygiology fascicle, 2005.32 (1): p.56-60.
[3]Rogers,E.,et?al.,The?cyanobacterial?toxin,cylindrospermopsin,induces?fetal?toxicity?in?the?mouse?after?exposure?late?in?gestation.Toxicon,2007.49(6):p.855-864.
[4]Magalhaes,V.d.,et?al.,Microcystins(cyanobacteria?hepatotoxins)bioaccumulation?in?fish?and?crustaceans?from?Sepetiba?Bay(Brasil,RJ).Toxicon,2003.42(3):p.289-295.
[5]Ding,J.,et?al.,Release?and?removal?of?microcystins?from?microcystis?during?oxidative-,physical-,and?UV-based?disinfection.Journal?of?Environmental?Engineering,2009.136(1):p.2-11.
[6] Hou Cuirong, Jia Ruibao, chemical oxidation destroys release characteristics of microcystins research in frond and born of the same parents. Chinese water supply and drainage, 2006.22 (13): p.98-101.
[7]Ou,H.,et?al.,Immediate?and?long-term?impacts?of?potassium?permanganate?on?photosynthetic?activity,survival?and?microcystin-LR?release?risk?ofMicrocystis?aeruginosa.Journal?of?hazardous?materials,2012.219:p.267-275.
[8]Daly,R.I.,L.Ho,and?J.D.Brookes,Effect?of?chlorination?on?Microcystis?aeruginosa?cell?integrity?and?subsequent?microcystin?release?and?degradation.Environmental?science&technology,2007.41(12):p.4447-4453.
[9] Li Lei, et al., controls algae in Raw Drinking Water, water factory's treatment process of Algae toxins. Chinese water supply and drainage, 2008.6.
[10] Zhu Guangcan, Lv Xiwu, removes the water technology progress of Algae toxins. Chinese water supply and drainage, 2003.19 (8): p.36-39.
Summary of the invention
Technical problem to be solved by this invention removes synchronous in algae process the Algae toxins produced.
In order to solve the problems of the technologies described above, this invention exploits and utilize nano ferriferrous oxide to work in coordination with aluminium chlorohydroxide (PACl) alga removalby coagulation as coagulant aids, and having investigated different pH value, the amount of different coagulants and the Fe of different-grain diameter
3o
4to the removal effect of Algae toxins, remove for Algae toxins in the coagulation project application of water treatment and provide a kind of new idea and thinking.The present invention is achieved through the following technical solutions:
Utilize nano-iron material to remove a method for Algae toxins in water body, comprise the following steps:
The pH value of step one, adjustment algae liquid is to neutral or acid;
Step 2, in algae liquid, add coagulating agent coagulation is carried out to algae;
Step 3, in algae liquid, add coagulant aids nano ferriferrous oxide;
Step 4, algae liquid are through stirring postprecipitation, and the Algae toxins in algae liquid is removed.
Preferably, in step one, the pH value of algae liquid is adjusted to 7 or 5.
More preferably, in step one, regulate the pH value of algae liquid with the NaOH solution of 0.1mg/L and the HCl solution of 0.1mg/L.
Preferably, in step 2, coagulating agent is aluminium chlorohydroxide.
Preferably, the coagulating agent added and the mass ratio of nano ferriferrous oxide are 4:1.
Preferably, the concentration of nano ferriferrous oxide is 2.5mg/L ~ 12.5mg/L.
Preferably, the particle diameter of nano ferriferrous oxide is less than 100nm.
Preferably, the particle diameter of nano ferriferrous oxide is less than 20nm.
Preferably, stir and carry out in two steps, first stir 2min with 200r/min rotating speed, then stir 10min with 100r/min.
Preferably, algae liquid, through stirring postprecipitation, by detecting the content of Algae toxins in supernatant liquid, characterizes precipitation process of coagulation to the removal amount of Algae toxins.
The invention has the beneficial effects as follows, nano-iron material, as coagulant aids, utilize its small-size effect and surface effects, and it is with electrical properties at different conditions, can effectively eliminate Algae toxins in water body, with low cost, simple.
Accompanying drawing explanation
Fig. 1 is that different pH value is to nanometer Fe
3o
4remove the effectiveness comparison figure of Algae toxins.The residue Algae toxins amount of left coordinate refers to the concentration of Algae toxins in supernatant liquor after algae liquid coagulation, and what the clearance of right coordinate was corresponding is add nanometer Fe
3o
4and PACl with add separately PACl coagulation after water body remain comparing of Algae toxins.
Fig. 2 is that different coagulants concentration is to nanometer Fe
3o
4remove the effectiveness comparison figure of Algae toxins.The residue Algae toxins amount of left coordinate refers to the concentration of Algae toxins in supernatant liquor after algae liquid coagulation, and that the clearance of right coordinate is corresponding is plus nano Fe
3o
4and PACl with add separately PACl coagulation after water body remain comparing of Algae toxins.
Fig. 3 is the Fe of different size under different coagulants concentration conditions
3o
4to the effectiveness comparison figure that Algae toxins is removed.The residue Algae toxins amount of left coordinate refers to the concentration of Algae toxins in supernatant liquor after algae liquid coagulation, and what the clearance of right coordinate was corresponding is add Fe
3o
4and PACl with add separately PACl coagulation after water body remain comparing of Algae toxins.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The elementary operation of experiment, based on coagulating sedimentation, is carried out coagulation for coagulating agent to algae with aluminium chlorohydroxide (PACl), is added coagulant aids nano ferriferrous oxide (Fe simultaneously
3o
4) precipitate.Test concrete operations be add in the beaker of 100mL 50mL OD value about 0.25, frustule concentration is 10
6the algae liquid of individual/mL, then add PACl solution, by nanometer Fe
3o
4add according to mass ratio 1:4 ratio with PACl.Coagulation process first stirs 2min soon with the rotating speed of 200r/min, then stirs 10min slowly with 100r/min, and precipitation 60min, gets the mensuration that supernatant liquor carries out Algae toxins after precipitation terminates.The mensuration of Algae toxins utilizes Microcystin quick detection kit (ENVIROLOGIX, USA), got supernatant liquor is repeatedly mixed with the reagent in test kit, reacts, finally use microplate reader (VARIOSKAN FLASH, Thermo, USA) be that spectrophotometric value is measured at 450nm place at wavelength, and calculate clearance.Often organize test and establish three Duplicate Samples, average.
Embodiment 1: nanometer Fe under different pH condition
3o
4algae toxins is removed as coagulant aids
The pH value of former algae liquid is close to 11, and the pH value regulating algae liquid with the NaOH solution of 0.1mg/L and the HCl of 0.1mg/L, is adjusted to 11,9,7 and 5 respectively by the pH value of algae liquid.After pH value regulates, add separately the PACl that PACl group adds 30mg/L and carry out coagulation experiment.Add nanometer Fe
3o
4group, adds the nanometer Fe of PACl and 7.5mg/L of 30mg/L
3o
4(add mass ratio PACl:Fe
3o
4=4:1) carry out coagulation test.
Utilizing nanometer Fe
3o
4remove in Algae toxins process as coagulant aids, pH value has a significant effect for removal effect.As shown in Figure 1, when adding separately PACl, no matter algae liquid is acid, alkaline or neutral, and the residue Algae toxins content after coagulation in water body is all high than Algae toxins content in former algae liquid.In PACI and nanometer Fe
3o
4when jointly adding, under the condition of pH=7 and pH=5, PACl and nanometer Fe
3o
4acting in conjunction has certain clearance to Algae toxins, when pH=5, clearance close to 40%, but along with the increase of pH value, under the condition of especially pH > 7, nanometer Fe
3o
4ineffective as the removal of coagulant aids to Algae toxins.
To nanometer Fe
3o
4sign known, under the condition of pH≤7, nanometer Fe
3o
4surface is positively charged; Under the condition of pH > 7, nanometer Fe
3o
4surface is electronegative.The surface of corresponding Algae toxins is all electronegative, therefore, under the condition of pH≤7, and nanometer Fe
3o
4may be adsorbed by electrostatic attraction effect the removal of Algae toxins.Under the condition of pH > 7, nanometer Fe
3o
4be all negatively charged with the surface of Algae toxins, the two can not interact because of electrostatic interaction, therefore nanometer Fe
3o
4algae toxins can not be removed with this understanding.As can be seen here, nanometer Fe
3o
4remove Algae toxins as coagulant aids and only under neutrality and acidic conditions, just there is positive effect.
Embodiment 2: different concns nanometer Fe
3o
4algae toxins is removed as coagulant aids
The pH value of former algae liquid is adjusted to neutrality, adds separately PACl group adds 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L PACl respectively to neutral algae liquid.For PACl and nanometer Fe
3o
4group, respectively to adding PACl and 2.5mg/L of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, the nanometer Fe of 5mg/L, 7.5mg/L, 10mg/L, 12.5mg/L in algae liquid
3o
4, then carry out coagulation stirring test.
Coagulant charging quantity is removed for microcystis aeruginosa toxin and is had a significant effect.As shown in Figure 2, when adding separately PACl, when the dosage of PACl rises to 20mg/L from 10mg/L, after coagulation, in supernatant liquor, Algae toxins content does not only reduce, and increases a part on the contrary.But after coagulation, the Algae toxins content of supernatant liquor reduces gradually when the dosage of coagulating agent continues to increase.This is because although coagulation effectively can remove the microcystic aeruginosa in algae liquid, lower to the clearance of Algae toxins; On the contrary, the rapid stirring process of coagulating agent and frustule effect and coagulation can destroy frustule itself, thus cause the release of Algae toxins in frustule, and although coagulating agent itself is unlikely to the destruction causing frustule, but frond glue can be caused to be disintegrated, frustule dehydration is out of shape, thus Algae toxins in release born of the same parents.But along with the continuation of PACl dosage increases, coagulation increases the clearance of Algae toxins, therefore when PACl amount is greater than 30mg/L, after coagulation, the content of supernatant liquor reduces along with the increase of coagulant charging quantity.In PACl and nanometer Fe
3o
4(PACl:Fe under the condition jointly added
3o
4=4:1), after coagulation, the Algae toxins content of supernatant liquor reduces along with the increase of coagulating agent always, this is because along with nanometer Fe
3o
4the increase of dosage, nanometer Fe
3o
4the surface site contacted with Algae toxins increases, and the ability of Adsorption is increased.In sum, along with adding of coagulating agent, residue Algae toxins entirety presents downward trend, but adding nanometer Fe
3o
4condition under, can more high efficiency removal Algae toxins.
Embodiment 3: different size nanometer Fe
3o
4algae toxins is removed as coagulant aids
In order to compare the Fe of different size
3o
4on the impact that Algae toxins is removed in coagulation process, by particle diameter 20nm, 100nm and micron-sized Fe
3o
4the Algae toxins in algae liquid is removed respectively as coagulant aids coagulation.As shown in Figure 3, at different coagulating agent and coagulant aids (PACl:Fe
3o
4=4:1) under dosage, Fe
3o
4size is less, and in algae liquid, the clearance of Algae toxins is higher.
The material of nano-scale itself has small-size effect and surface effects, and small-size effect and surface effects are all relevant with the size of nanoparticle.Work as nanometer Fe
3o
4small-sized time, the volume fraction shared by atom being positioned at surface is comparatively large, can produce very large surface energy.Along with Fe
3o
4the reduction of size, specific surface area can strengthen thereupon, and surface atom number and ratio also can increase.Therefore Fe in this research
3o
4particle diameter less, the specific surface area of particle is larger, Fe
3o
4the total area contacted with Algae toxins increases, and is conducive to the removal of Algae toxins in coagulation process.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. utilize nano-iron material to remove a method for Algae toxins in water body, it is characterized in that, comprise the following steps:
The pH value of step one, adjustment algae liquid is to neutral or acid;
Step 2, in algae liquid, add coagulating agent coagulation is carried out to algae;
Step 3, in algae liquid, add coagulant aids nano ferriferrous oxide;
Step 4, algae liquid are through stirring postprecipitation, and the Algae toxins in algae liquid is removed.
2. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, in step one, the pH value of algae liquid is adjusted to 7 or 5.
3. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, is characterized in that, in step one, regulate the pH value of algae liquid with the NaOH solution of 0.1mg/L and the HCl solution of 0.1mg/L.
4. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, in step 2, described coagulating agent is aluminium chlorohydroxide.
5. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, the described coagulating agent added and the mass ratio of described nano ferriferrous oxide are 4:1.
6. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, the concentration of described nano ferriferrous oxide is 2.5mg/L ~ 12.5mg/L.
7. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, the particle diameter of described nano ferriferrous oxide is less than 100nm.
8. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, the particle diameter of described nano ferriferrous oxide is less than 20nm.
9. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, described stirring is carried out in two steps, first stirs 2min with 200r/min rotating speed, then stirs 10min with 100r/min.
10. a kind of method utilizing nano-iron material to remove Algae toxins in water body as claimed in claim 1, it is characterized in that, algae liquid, through stirring postprecipitation, by detecting the content of Algae toxins in supernatant liquid, characterizes the removal amount of precipitation process of coagulation.
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Application publication date: 20141217 |