CN104211226B - A kind of method utilizing nano-iron material to remove Measures of Algae in Water Body - Google Patents
A kind of method utilizing nano-iron material to remove Measures of Algae in Water Body Download PDFInfo
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- CN104211226B CN104211226B CN201410471423.1A CN201410471423A CN104211226B CN 104211226 B CN104211226 B CN 104211226B CN 201410471423 A CN201410471423 A CN 201410471423A CN 104211226 B CN104211226 B CN 104211226B
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Abstract
The invention discloses a kind of method utilizing nano-iron material to remove Measures of Algae in Water Body, comprise the following steps: (1) carries out preoxidation to algae liquid; (2) regulate the pH value of algae liquid to alkalescence; (3) in algae liquid, nano ferriferrous oxide and polyacrylamide is added; (4) algae liquid sedimentation after stirring, the algae in algae liquid is removed.Advantage algae kind microcystic aeruginosa when choosing algal bloom in blue-green algae and the advantage algae kind scenedesmus obliquus in green alga, as research object, develop at KMnO
4under the condition of preoxidation, with the use of nano ferriferrous oxide and polyacrylamide as the minimizing technology of coagulating agent to algae, when medicine dosage is relatively low, clearance and the subsidence rate of algae can be improved to a great extent.Without the need to using the coagulating agent containing aluminium, the continuation that can reduce aluminium salt in environment increases.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of under the condition of Potassium Permanganate Preoxidation, nano ferriferrous oxide and polyacrylamide conbined usage remove the method for algae in water.
Background technology
The development trend of China's lake eutrophication is very severe, and in 26 state's control emphasis lakes, Water phosphorus pollutes higher, and quite a few lake there occurs wawter bloom disaster
[1].Taihu Lake blue-green alga bloom event in 2007, causes drinking and domestic water critical shortage of Wuxi City 5,000,000 people
[2].Therefore, during algal bloom, the improvement of algae is the great water environmental problems that China faces.Preoxidation and coagulating sedimentation are two kinds and study more algae-removing method.Preoxidation is generally potassium permanganate
[3], ozone, dioxide peroxide etc.
[4]strong oxidizer, coagulating sedimentation generally uses polymerize aluminum chloride (PACl)
[5], Tai-Ace S 150 (AS), chitosan etc. as coagulating agent, with polyacrylamide (PAM), Poly Dimethyl Diallyl Ammonium Chloride (PDM) etc. as coagulant aids with the use of the object reached except algae
[6].Also be common treatment process by preoxidation and coagulating sedimentation coupling, as KMnO
4add PACl and PAM after preoxidation and carry out alga removalby coagulation
[7].
Although aluminium salt is widely used as coagulating agent
[8], but in fact, aluminium has certain eco-toxicity, and in tap water, the increase of Residual Aluminum Content produces adverse influence to function of human body
[9-10], cause serious consequence; Meanwhile, a large amount of aluminium salt remains also has certain toxicity to the ecosystem
[11].Nano material received because of it in recent years paid close attention to widely owing to having small-size effect and large specific surface area, and nanometer Fe
3o
4as magnetic nanoparticle, in water treatment, be often used as the heavy metal in adsorbent and recovery waste water and organism
[12-13].
In view of the deficiencies in the prior art, those skilled in the art are devoted to develop a kind of substitute containing aluminium coagulating agent, and remove the novel method of Measures of Algae in Water Body with it.
Reference:
[1] Huang Huihui, Li Xiang, Du Chunlan. China's lake eutrophication research conditions general introduction [J]. theoretic discussion, 2011 (8): 259-260.
[2] Qin Baiqiang, Wang little Dong, Tang Xiangming, etc. tap water crisis-reasons and solutions [J] that Taihu Lake eutrophication and blue-green alga bloom cause. Advances in Earth Science, 2007,22 (9): 896-906.
[3]ZhuJW,ZhangZ,LiXM,XuXH,WangDH.ManganeseremovalfromtheQiantangRiversourcewaterbypre-oxidation:Acasestudy.JournalofZhejiangUniversityScienceA,2009,10(3)；450-457.
[4]PlummerJD,EdzwardJK.Effectsofchlorineandozoneonalgalcellpropertiesandremovalofalgaebycoagulation[J].WaterSRT-Aqua,2002,51(6):307-318.
[5]TakaaraT,SanoD,KonnoH,etal.Affinityisolationofalgalorganicmattersabletoformcomplexwithaluminumcoagulant[J].WaterSciTechnol:WaterSupply,2005.4(5/6):95-102.
[6]GhernaoutB,GhernaoutD,SaibaA.Algaeandcyanotoxinsremovalbycoagulation/flocculation:areview[J].DesalinWaterTreat,2010,(1/2/3):133-143.
[7] Zhang Long, Qiao Junlian, Lei Qing. Potassium Permanganate Preoxidation enhanced coagulation removes the research [J] of green alga. ACTA Scientiae Circumstantiae, 2013.33 (1): 73-78.
[8] Wang Min, Tong Fanghua. the progress [J] of aluminum salt. Jiangxi chemical industry, 2005, (2); 9-11.
[9]GauthierE,FortierI,CourchesneF,etal.AluminumformsindrinkingwaterandriskofA1zheimerdisease[J].EnvironRes,2000,84:234-246.
[10]Sanz-MedelA,SoldadoCabezueloAB,MilihR,etal.Thechemicalspeciationofaluminuminhumanserum[J].CoordinationChemReviews,2008,228:373-383.
[11] anticipatory remark is loyal, Qu Weidong, Wu Desheng. and the hydrolysis in aqueous of aluminium salt and polyreaction cause the impact [J] of Rat Development toxicity to aluminium. environment and health magazine, 2001,18 (3); 143-145.
[12]ShenYF,TangJ,NieZH,etal.PreparationandapplicationofmagneticFe3O4nanoparticlesforwastewaterpurification[J].SeparationandPurificationTechnology,2009,68:312-319.
[13]BadruddozaAZM,TayASH,TanPY,etal.Carboxymethyl-beta-cyclodextrinconjugatedmagneticnanoparticlesasnano-adsorbentsforremovalofcopperions:Synthesisandadsorptionstudies[J].JournalOfHazardousMaterials,2011,185(2-3),1177-1186.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of novel method removing Measures of Algae in Water Body, and without the need to using the coagulating agent containing aluminium in this method, the continuation that can reduce aluminium salt in environment increases.
In order to solve the problems of the technologies described above, the present invention nano ferriferrous oxide (Fe
3o
4) replace aluminium chlorohydroxide (PACl) as coagulating agent use, remove the algae in water.Advantage algae kind microcystic aeruginosa when choosing algal bloom in blue-green algae and the advantage algae kind scenedesmus obliquus in green alga, as subjects, develop at KMnO
4under the condition of preoxidation, with the use of nano ferriferrous oxide and polyacrylamide (PAM) as the minimizing technology of coagulating agent to algae.The present invention is achieved through the following technical solutions:
Utilize nano-iron material to remove a method for Measures of Algae in Water Body, comprise the following steps:
Step one, preoxidation is carried out to algae liquid;
The pH value of step 2, adjustment algae liquid is to alkalescence;
Step 3, in algae liquid, add nano ferriferrous oxide and polyacrylamide;
The sedimentation after stirring of step 4, algae liquid, the algae in algae liquid is removed.
Preferably, in step one, potassium permanganate is selected to carry out preoxidation to algae liquid.
Preferably, in step one, the time of preoxidation is 5 ~ 30min.
More preferably, in step one, the time of preoxidation is 15min.
Preferably, in step one, need when carrying out preoxidation constantly to stir, rotating speed 200r/min.
Preferably, in step 4, sedimentation is not for add magnetic field sedimentation, and the settling time is 60min.Before not adding magnetic field sedimentation, first stir 2min soon with the rotating speed of 200r/min, then stir 10min slowly with 100r/min.
Or in step 4, sedimentation is for adding magnetic field sedimentation, and the settling time is 10min.Before carrying out adding magnetic field sedimentation, stir 2min.
Preferably, algae is microcystic aeruginosa or scenedesmus obliquus.
The invention has the beneficial effects as follows, without the need to using the coagulating agent containing aluminium in this method, the continuation that can reduce aluminium salt in environment increases.At KMnO
4under the condition of preoxidation, nanometer Fe
3o
4with PAM as the coagulating agent effect of cooperatively interacting, when medicine dosage is relatively low, clearance and the subsidence rate of algae can be improved to a great extent.
Accompanying drawing explanation
Fig. 1 is KMnO
4nanometer Fe under pre-oxidizing conditions
3o
4with under PAM mating reaction to the effect diagram of microcystic aeruginosa;
Fig. 2 is KMnO
4nanometer Fe under pre-oxidizing conditions
3o
4with under PAM mating reaction to the effect diagram of scenedesmus obliquus;
Fig. 3 is KMnO
4preoxidation time is to the effect diagram of microcystic aeruginosa;
Fig. 4 is KMnO
4preoxidation time is to the effect diagram of scenedesmus obliquus;
Fig. 5 is the effect diagram of pH value to microcystic aeruginosa clearance;
Fig. 6 is the effect diagram of pH value to scenedesmus obliquus clearance.
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 embodiment based on coagulating sedimentation, namely to through KMnO
4nanometer Fe is added in the algae liquid system of preoxidation
3o
4with PAM as coagulating agent and coagulant aids, the algae in system is removed.Concrete operations are in the beaker of 100mL, add 50mL absorbance (order of magnitude is 10 about 0.25
6individual/mL) algae liquid, KMnO
4preoxidation churning time is 15min, rotating speed 200r/min; Agitation condition after dosing coagulant is, does not need the system adding magnetic field precipitation first to stir 2min soon with the rotating speed of 200r/min, then stirs 10min slowly with 100r/min, finally precipitate 60min during precipitation; Add after the system precipitated in magnetic field only stirs 2min soon and add magnetic field precipitation 10min.Determine its concentration in system 1/2 At The Height sampling and measuring absorbancy after precipitation, and calculate clearance.Selected KMnO
4concentration 1.5mg/L, Fe
3o
4concentration 50mg/L, PAM concentration 0.3mg/L are the primary condition of effect test.
Embodiment 1: nanometer Fe
3o
4the impact on algae is coordinated with PAM
Fig. 1 and Fig. 2 is to microcystic aeruginosa and scenedesmus obliquus removal effect figure respectively, known from Fig. 1 and Fig. 2, adds KMnO separately
4algae is oxidized and also has certain removal effect, but all 30% is not reached to the clearance of two kinds of algaes.
KMnO
4nanometer Fe is added after preoxidation
3o
4have a certain upgrade to the clearance of algae, not adding magnetic field sedimentation 60min to the clearance of scenedesmus obliquus is 40%, and the clearance of microcystic aeruginosa can reach 50%, and add the clearance of magnetic field sedimentation microcystic aeruginosa close to 65%, scenedesmus obliquus can reach 70%.
In order to improve the clearance of algae further, in system, add PAM to strengthen the coagulation effect of system.As depicted in figs. 1 and 2, although under the condition adding magnetic field sedimentation, in system, add nanometer Fe simultaneously
3o
4very less than what do not add that PAM improves to the clearance of algae with PAM, but under the condition not adding magnetic field sedimentation, add nanometer Fe simultaneously
3o
4can more than 60% be reached with the system algae clearance of PAM, exceed and only add nanometer Fe
3o
4system about 20%.For microcystic aeruginosa system, add nanometer Fe simultaneously
3o
4with the system of PAM under the condition not adding magnetic field sedimentation than only adding nanometer Fe
3o
4system exceed nearly 20%, and under adding the condition of magnetic field sedimentation, clearance can reach 90%, exceeds and only adds nanometer Fe
3o
4system 30%.
This shows, at KMnO
4under the condition of preoxidation, nanometer Fe
3o
4with PAM as the coagulating agent effect of cooperatively interacting, when medicine dosage is relatively low, clearance and the subsidence rate of algae can be improved to a great extent.
Embodiment 2:KMnO
4preoxidation time is on the impact of algae
Fig. 3 and Fig. 4 is respectively KMnO
4preoxidation time is to the effect diagram of microcystic aeruginosa and scenedesmus obliquus clearance.As can be seen from Fig. 3 and Fig. 4, the impact of preoxidation time on two kinds of algae clearances demonstrates identical trend, and the increase of preoxidation time can improve the clearance of algae, but the amplitude improved reduces along with the increase of preoxidation time.KMnO
4preoxidation time is increased to 15min from 5min, and the clearance of microcystic aeruginosa increases about 30%, and the clearance of scenedesmus obliquus increases about 20%; But preoxidation time is increased to 30min from 15min, the clearance change of microcystic aeruginosa and scenedesmus obliquus is all very little.The preoxidation of 5min inhibits the activity of algae to a certain extent, has certain help to coagulating sedimentation.The preoxidation of 15min further suppress the activity of algae, improves the clearance of algae.And although the preoxidation of 30min further suppress the activity of algae, even make algae complete deactivation, from comprehensive algae clearance result and economic benefit, the preoxidation of 15min can meet the requirement of coagulating sedimentation for algae inactivation completely.
Embodiment 3:pH value is on the impact of algae clearance
Fig. 5 and Fig. 6 is the impact effect figure of pH value to algae clearance.Under the condition not adding magnetic field sedimentation, KMnO
4nanometer Fe under pre-oxidizing conditions
3o
4the removal effect removing microcystic aeruginosa and scenedesmus obliquus with PAM mating reaction shows identical trend: almost do not have clearance under acidic conditions, along with the increase clearance of pH value obviously increases, when pH value is 11, the clearance most significant digit 70% of microcystic aeruginosa, scenedesmus obliquus is 60%.Under the condition adding magnetic field, two kinds of algaes are also that clearance is less than 10% in acid condition, and under alkaline condition, the clearance of microcystic aeruginosa increases along with pH value and increases, it is 11 that the highest clearance 85% appears at pH value, the highest clearance 80% of scenedesmus obliquus appears at pH value and equals 9, and the clearance that pH value equals 10 and 11 reduces on the contrary gradually.Although KMnO
4preoxidation better effects if in acid condition, but PAM has better coagulation effect in the basic conditions.
Can reach a conclusion thus, pH value is for KMnO
4nanometer Fe is added after preoxidation
3o
4it is similar for coordinating except this method of algae acts on the impact that two kinds of different algal species produce with PAM: pH value is higher, and algae clearance is higher.
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 Measures of Algae in Water Body, it is characterized in that, comprise the following steps:
Step one, preoxidation is carried out to algae liquid;
The pH value of step 2, adjustment algae liquid is to alkalescence;
Step 3, in algae liquid, add nano ferriferrous oxide and polyacrylamide;
The sedimentation after stirring of step 4, algae liquid, the algae in algae liquid is removed, and wherein said sedimentation is not for add magnetic field sedimentation or to add magnetic field sedimentation.
2. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, it is characterized in that, in step one, selects potassium permanganate to carry out preoxidation to described algae liquid.
3. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, and it is characterized in that, in step one, the time of described preoxidation is 5 ~ 30min.
4. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 3, and it is characterized in that, in step one, the time of described preoxidation is 15min.
5. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, it is characterized in that, in step one, needs constantly to stir, rotating speed 200r/min when carrying out described preoxidation.
6. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, and it is characterized in that, in step 4, the described settling time not adding magnetic field sedimentation is 60min.
7. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 6, it is characterized in that, before not adding magnetic field sedimentation, first stirs 2min soon with the rotating speed of 200r/min, then stirs 10min slowly with 100r/min described in carrying out.
8. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, it is characterized in that, in step 4, described in add magnetic field sedimentation settling time be 10min.
9. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 8, it is characterized in that, before adding magnetic field sedimentation, stirs 2min described in carrying out.
10. a kind of nano-iron material that utilizes removes the method for Measures of Algae in Water Body as claimed in claim 1, and it is characterized in that, described algae is microcystic aeruginosa or scenedesmus obliquus.
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