CN104591360B - A kind of algicide making frond flocculation also rapid subsidence and algae-removing method thereof - Google Patents
A kind of algicide making frond flocculation also rapid subsidence and algae-removing method thereof Download PDFInfo
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- CN104591360B CN104591360B CN201510025863.9A CN201510025863A CN104591360B CN 104591360 B CN104591360 B CN 104591360B CN 201510025863 A CN201510025863 A CN 201510025863A CN 104591360 B CN104591360 B CN 104591360B
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Abstract
The present invention relates to a kind of algicide and apply this algicide to carry out the method except algae.A kind of make frond flocculation the algicide of rapid subsidence, containing chitosan 3.75～30 parts, the fly ash autoclaved brick powder 200 of 80～160 mesh～1000 parts；The described chitosan HCl solution that 1～5 parts by volume concentration are 0.4%～2% is dissolved, is subsequently adding fly ash autoclaved brick powder, makes described algicide.A kind of algae-removing method making frond flocculation also rapid subsidence, first puts in algae pollution water body by a certain amount of potassium permanganate, pre-oxidizes 0～50 minute；Again by adding fly ash autoclaved brick powder after chitosan diluted hydrochloric acid dissolution, make algicide；Then a certain amount of algicide is added in the water body of algae pollution, stands, after making frond flocculation, be deposited to the bottom.The present invention makes frond flocculation the algicide of rapid subsidence and algae-removing method thereof, safe and reliable, except algae thoroughly, speed fast, algicide consumption is little and without stirring, it is possible to safely and effectively controls algal bloom, keeps the water surface clean.
Description
Technical field
The invention belongs to field of environment protection, be specifically related to a kind of safe algicide making frond flocculation also rapid subsidence, and apply this algicide to carry out the method except algae.
Background technology
Air ambient/water environment is all heavily polluted at present.Some areas blue-green alga bloom frequently breaks out, water body DO not only can be caused drastically to decline, water quality corrupt, and frustule decline or rupture the Microcystin discharged and also health is constituted serious threat.Therefore, control and improvement and the safe drinking water of water environment are significant by the algae of removing in water body.
Currently employed algae removal technology mainly has air supporting, microfiltration, contact filtration, adds the several ways such as oxidant.The most commonly used method for pre-oxidizing is prechlorination technique.Although prechlorination can strengthen the efficiency except algae, but chlorine generates the multiple harmful side products such as haloform with the Organic substance effect of higher concentration in water in chlorination process, and the use of this technique is limited by more and more national.Though and abroad some developed countries use ozone oxidation good except algae effect, but investment is too big, operating cost is high, it is difficult to use in developing country.Potassium permanganate is a kind of strong oxidizer, utilizes its pre-oxidation algae pollution water body can remove micro quantity organic pollutant in water, enhanced coagulation, it is used in water process, has and invest the advantages such as little, efficient, easy to use.
Chitosan is modified by Hu Yinghui etc. with the filtrate being filtrated to get after flyash acid activation, a kind of novel flocculant of preparation, with this flocculant, peace park, Shanghai City, crane park, Lu Xun Park, the landscape water body in river, Zhangwu road are carried out treatment research, and use Potassium Permanganate Preoxidation, strengthen flocculating effect, except algae efficiency is up to more than 90% (being published in water technology, 2010,36 (70): 50-52).Need before this modification of chitosan flocculant concentration with the potassium permanganate of 1mg/L, polluted-water to be pre-oxidized 1 hour, and also need 250r.min after adding flocculant-1Quickly stir 3min, 30r.min-1Low rate mixing 10min, latter quiet heavy 1 hour.Operation complexity, in-convenience in use, affect its practical value.
Summary of the invention
The present invention is directed to prior art not enough, it is proposed that a kind of can make frond rapid subsidence with chitosan, fly ash autoclaved brick powder for what raw material made and effectively remove the algicide of algae；
Simultaneously, it is proposed that this algicide of a kind of application carries out, effectively except the method for algae, around pre-oxidation, coagulation and three processes of sedimentation, utilizing this algicide quickly except algae, can making frond rapid subsidence.
The technical solution adopted in the present invention:
A kind of making frond flocculation the algicide of rapid subsidence, containing chitosan, fly ash autoclaved brick powder, described algicide, with weight portion content meter, containing chitosan 3.75～30 parts, the fly ash autoclaved brick powder 200 of 80～160 mesh～1000 parts；Chitosan every weight portion unit is in terms of g, and the described chitosan HCl solution that 1～5 parts by volume concentration are 0.4%～2%, in terms of L, is dissolved, is subsequently adding fly ash autoclaved brick powder, makes described algicide by hydrochloric acid parts by volume unit.
Described fly ash autoclaved brick powder, is obtained by such a way:
First the coal ash autoclaved fragment of brick discarded on construction site is pulverized and sieved, obtain the powder of 80～160 mesh, then it is carried out pretreatment, the Organic substance contained by removal, obtain fly ash autoclaved brick powder；
Then with 20～the H of 40%2O2The fly ash autoclaved brick powder obtained is carried out；
Finally, repeatedly clean fly ash autoclaved brick powder with deionized water, outwell supernatant liquid filtering, in the oven for drying of 50～60 DEG C of temperature.
A kind of make frond flocculation the algae-removing method of rapid subsidence, make algicide with chitosan, fly ash autoclaved brick powder, and potassium permanganate combine and carry out except algae,
First a certain amount of potassium permanganate is put in algae pollution water body, pre-oxidize 0～50 minute；
Again by adding fly ash autoclaved brick powder after chitosan diluted hydrochloric acid dissolution, make algicide；
Then a certain amount of algicide is added in the water body of algae pollution, stands, after making frond flocculation, be deposited to the bottom.
Described algae-removing method, the mass/volume of potassium permanganate and algae pollution water body is than for 0.9g:1000L.
Described algicide is when purifying application during algae pollution water body: staying water with the volume ratio of the consumption of algicide is: 100:2.4～4.8.
Beneficial effects of the present invention:
1, the present invention uses chitosan, fly ash autoclaved brick powder are the most nontoxic, although employing dilute HCl in algicide to dissolve chitosan, but do not cause the change of water body significantly pH value in the range of above-mentioned dosage.Can be directly added into this algicide after adding potassium permanganate in the water body of algae pollution, and without stirring, within direct quiet heavy 1 hour, can easily facilitate use in water body in the wild so that frond flocculation sinks under water, the impact on environment is little, non-secondary pollution.
2, without stirring when algicide of the present invention uses, frond can be made to be settled down to the bottom in quiet heavy 1 hour after interpolation, it is adaptable to the Small-scale Landscape Water Bodies with cyanophyceae as sociales removes algae.The method is safe and reliable, and except algae is thorough, speed is fast, algicide consumption is little and without stirring, it is possible to making algae be deposited to the bottom, safely and effectively control algal bloom, keep the water surface clean, water body is as clear as crystal, does not affect water body attractive in appearance.
3, algicide of the present invention, uses fly ash autoclaved brick discarded on construction site to make fly ash autoclaved brick powder, it is achieved that twice laid, beneficially environmental protection and resources conservation.
Accompanying drawing explanation
Fig. 1 is the Potassium Permanganate Preoxidation time influence curve figure to alga-killing rate；
Fig. 2 is Potassium Permanganate Preoxidation and does not aoxidizes the lower algicide addition influence curve figure to alga-killing rate.
Detailed description of the invention
Below by detailed description of the invention, technical scheme is described in further detail.
The present invention makes frond flocculation the algicide of rapid subsidence, and containing chitosan, fly ash autoclaved brick powder, described algicide, with weight portion content meter, containing chitosan 3.75～30 parts, the fly ash autoclaved brick powder 200 of 80～160 mesh～1000 parts；Chitosan every weight portion unit is in terms of g, and the described chitosan HCl solution that 1～5 parts by volume concentration are 0.4%～2%, in terms of L, is dissolved, is subsequently adding fly ash autoclaved brick powder, makes described algicide by hydrochloric acid parts by volume unit.
Embodiment 1
The algicide making frond flocculation also rapid subsidence of the present embodiment, chitosan every weight portion unit is in terms of g, hydrochloric acid parts by volume unit is in terms of L, containing chitosan 3.75～10 parts, fly ash autoclaved brick powder 800～1000 parts, the described chitosan HCl solution that 1～3 parts by volume concentration are 1% is dissolved, is subsequently adding fly ash autoclaved brick powder.
Embodiment 2
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 3.75～10 parts, fly ash autoclaved brick powder 200～400 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 1～2 parts by volume concentration are 0.4% by chitosan.
Embodiment 3
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 3.75～10 parts, fly ash autoclaved brick powder 400～800 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 1～2 parts by volume concentration are 0.7% by chitosan.
Embodiment 4
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 10～20 parts, fly ash autoclaved brick powder 400～800 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 1～2 parts by volume concentration are 1% by chitosan.
Embodiment 5
The algicide making frond flocculation also rapid subsidence of the present embodiment, containing chitosan 10～20 parts, fly ash autoclaved brick powder 800～1000 parts, add the fly ash autoclaved brick powder of 80～160 mesh with the HCl solution that 4～5 parts by volume concentration are 0.7% after being dissolved by described chitosan.Prepare described algicide.
Embodiment 6
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 10～20 parts, fly ash autoclaved brick powder 200～400 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 2～3 parts by volume concentration are 0.4% by chitosan.
Embodiment 7
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 20～30 parts, fly ash autoclaved brick powder 400～800 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 2～3 parts by volume concentration are 1% by chitosan.
Embodiment 8
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 20～30 parts, fly ash autoclaved brick powder 800～1000 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 4～5 parts by volume concentration are 1.5% by chitosan.
Embodiment 9
The present embodiment make frond flocculation the algicide of rapid subsidence, containing chitosan 20～30 parts, fly ash autoclaved brick powder 200～400 parts, the fly ash autoclaved brick powder of addition 80～160 mesh after being dissolved with the HCl that 1～2 parts by volume concentration are 2% by chitosan.
Fly ash autoclaved brick powder in foregoing embodiments, is obtained by such a way:
First the coal ash autoclaved fragment of brick discarded on construction site is pulverized and sieved, obtain the powder of 80～160 mesh, then it is carried out pretreatment, the Organic substance contained by removal, obtain fly ash autoclaved brick powder；
Then with 20～the H of 40%2O2The fly ash autoclaved brick powder obtained is carried out；
Finally, repeatedly clean fly ash autoclaved brick powder with deionized water, outwell supernatant liquid filtering, in the oven for drying of 50～60 DEG C of temperature.
During fly ash autoclaved brick powder is carried out, first fly ash autoclaved brick powder is put in thermostat water bath and heat, be then slowly added to H2O2, stirring while adding；When question response has heat release and gas to emerge completely and no longer, stop adding H2O2, continue heating in water bath half an hour.
Embodiment 10
Present embodiment discloses and apply aforementioned algicide to make frond flocculation the algae-removing method of rapid subsidence, combine with chitosan, fly ash autoclaved brick powder making algicide, and potassium permanganate and carry out except algae, make frond rapid subsidence and effectively except algae, the steps include:
First a certain amount of potassium permanganate is put in algae pollution water body, pre-oxidize 0～50 minute；
Again by adding fly ash autoclaved brick powder after chitosan diluted hydrochloric acid dissolution, make algicide；
Then a certain amount of algicide is added in the water body of algae pollution, stands, after making frond flocculation, be deposited to the bottom.
Described algae-removing method, the mass/volume of potassium permanganate and algae pollution water body is than for 0.9g:1000L.
Algicide application during purifying algae pollution water body: staying water with the volume ratio of the consumption of algicide is: 100:2.4～4.8.
Potassium permanganate has been widely used for during Drinking Water processes as oxidant, will not pollute water quality.Potassium permanganate has the strongest pre-oxidation effect to algae, can prevent algae flco under photosynthesis releasing oxygen and floating.
Chitosan and fly ash autoclaved brick powder flocculation make frond settle, but do not make frustule inactivate, the flco alive after precipitation under photosynthesis releasing oxygen so that frond floats again；Potassium permanganate makes it inactivate in the case of not destroying frustule, additionally, the hydrated manganese dioxide that Potassium Permanganate Preoxidation produces improves the settleability of frustule；Chitosan-coated is on fly ash autoclaved brick powder surface, macromolecular chain is wrapped in around fly ash autoclaved brick powder, the specific surface area making chitosan increases, add the chitosan contact with algae, and make fly ash autoclaved brick powder surface positively charged, both can condense electronegative frustule by the change of fly ash autoclaved brick powder surface electrical behavior again by the bonding bridging action flocculation frustule of chitosan, make the flocculation of modified fly ash autoclaved brick powder remove algae ability and be greatly improved.This flocculant is more existing has reported that flocculant substantially shortens the Potassium Permanganate Preoxidation time when application, and the shortest can be 0 minute, and without stirring, easily facilitates and applies in water body in the wild.
If table 1 below is that algicide removes algae Contrast on effect:
In table 1, chitosan dosage is 5mg, and the hydrochloric acid consumption of 0.7% is 5 mL, and 120 mesh fly ash autoclaved brick powder consumptions are 0.4 g, and experiment algae pollution water body is 25 mL.
As can be seen from Table 1 when without potassium permanganate oxidation, only adding 1 mL algicide, alga-killing rate is 88.40%；When increase 0.9mg/L Potassium Permanganate Preoxidation after add algicide again, alga-killing rate can increase to 97.84%, it can be seen that, Potassium Permanganate Preoxidation can increase algicide except algae effect.When in algicide without fly ash autoclaved brick powder, alga-killing rate is 28.06%；When not chitosan-containing in algicide, when only replacing algicide to remove algae with ultra-pure water and fly ash autoclaved brick powder, alga-killing rate is 24.93%, and result shows that algicide of the present invention is to make frond flocculate under the common effect of chitosan and fly ash autoclaved brick powder and be deposited to the bottom.
Fig. 1 is the Potassium Permanganate Preoxidation time influence curve figure to alga-killing rate.Algicide preoxidation time the most of the present invention short (0 minute can be as short as), without stirring after adding algicide, have efficiently, the advantage such as energy-saving and environmental protection, and frond rapid subsidence can be made to water-bed, be a kind of comparatively ideal algicide method of making algae settle.
It is respectively Potassium Permanganate Preoxidation shown in Fig. 2 and does not aoxidizes the lower algicide addition influence curve figure to alga-killing rate.As can be seen from Figure in the case of algicide addition is identical, using Potassium Permanganate Preoxidation, alga-killing rate can exceed 3～10 percentage points relatively.
Below in conjunction with the result of study of laboratory, the present invention is described in more detail:
Embodiment 11(experiment 1)
By 11mg chitosan 5mL
The hydrochloric acid solution of 1% constantly stirs with Glass rod and is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), add 1g
120 mesh fly ash autoclaved brick powder make algicide, take 1mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 50 minutes of 0.9mg/L, stand 1h, and algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 98.9%.
Embodiment 12(experiment 2)
5mg chitosan is added 5mL
The hydrochloric acid solution of 1% constantly stirs with Glass rod and is all dissolved in hydrochloric acid solution (can dissolve with ultrasound wave) to chitosan.Add 0.4g
120 mesh fly ash autoclaved brick powder, are stirred continuously to mix homogeneously with Glass rod.Adding 1mL algicide after adding the potassium permanganate of 0.9mg/L in the water body of 25 mL algae pollutions immediately, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 99.7%.
Embodiment 13(experiment 3)
By 11mg chitosan 5mL
The hydrochloric acid solution of 1% constantly stirs with Glass rod and is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), add 1g
160 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Taking 1mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 50 minutes of 0.9mg/L, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 99.3%.
Embodiment 14(experiment 4)
Add 5mg chitosan to 5mL
The hydrochloric acid solution of 0.4% constantly stirs with Glass rod to chitosan and all dissolve (can dissolve with ultrasound wave).Add 0.4g
120 mesh fly ash autoclaved brick powder, are stirred continuously to mix homogeneously with Glass rod.Adding 1mL algicide after adding the potassium permanganate of 0.9mg/L in the water body of 25 mL algae pollutions immediately, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 98.6%.
Embodiment 15(experiment 5)
Add 7mg chitosan to 5 mL
The hydrochloric acid solution of 2% constantly stirs with Glass rod and is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), add 0.6g
80 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Taking 1mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 50 minutes of 0.9mg/L, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 94.5%.
Embodiment 16(experiment 6)
Add 15mg chitosan to 5 mL
In the hydrochloric acid solution of 2%, constantly agitation is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), adds 0.6g
120 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Taking 1 mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 30 minutes of 0.9mg/L, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 98.5%.
Embodiment 17(experiment 7)
Add 20mg chitosan to 5mL
In the hydrochloric acid solution of 1%, constantly agitation is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), adds 1.0g
120 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Taking 1 mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 50 minutes of 0.9mg/L, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 94.7%.
Embodiment 18(experiment 8)
Add 25mg chitosan to 5mL
In the hydrochloric acid solution of 2%, constantly agitation is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), adds 0.4g
120 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Adding 1mL algicide after adding the potassium permanganate of 0.9mg/L in the water body of 25 mL algae pollutions immediately, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 99.3%.
Embodiment 19(experiment 9)
Add 20mg chitosan to 5 mL
In the hydrochloric acid solution of 1.5%, constantly agitation is all dissolved in hydrochloric acid solution to chitosan (can dissolve with ultrasound wave), adds 0.6g
120 mesh fly ash autoclaved brick powder, use ultrasound wave hydrotropy.Taking 1 mL algicide and add in the water body of the Potassium Permanganate Preoxidation 25 mL algae pollutions of 50 minutes of 0.9mg/L, stand 1h, algae is deposited to the bottom, and water body is limpid, detects its alga-killing rate and can reach 98.9%.
Claims (8)
1. making frond flocculation the algicide of rapid subsidence, containing chitosan, fly ash autoclaved brick powder, described algicide, with weight portion content meter, containing chitosan 3.75～30 parts, the fly ash autoclaved brick powder 200 of 80～160 mesh～1000 parts；It is characterized in that: described fly ash autoclaved brick powder, obtained by such a way:
First the coal ash autoclaved fragment of brick discarded on construction site is pulverized and sieved, obtain the powder of 80～160 mesh, then it is carried out pretreatment, the Organic substance contained by removal, obtain fly ash autoclaved brick powder；
Then with 20～the H of 40%2O2The fly ash autoclaved brick powder obtained is carried out；
Finally, repeatedly clean fly ash autoclaved brick powder with deionized water, outwell supernatant liquid filtering, in the oven for drying of 50～60 DEG C of temperature；
Chitosan every weight portion unit is in terms of g, and the described chitosan HCl solution that 1～5 parts by volume concentration are 0.4%～2%, in terms of L, is dissolved, is subsequently adding fly ash autoclaved brick powder, makes described algicide by hydrochloric acid parts by volume unit.
The algicide making frond flocculation also rapid subsidence the most according to claim 1, it is characterised in that: with the H of 30%2O2The fly ash autoclaved brick powder obtained is carried out: fly ash autoclaved brick powder is put in the thermostat water bath of 50 DEG C and heat, be then slowly added to the H of 30%2O2, stirring while adding；When question response has heat release and gas to emerge completely and no longer, stop adding H2O2, continue heating in water bath half an hour.
The algicide making frond flocculation also rapid subsidence the most according to claim 1 and 2, it is characterized in that: containing chitosan 3.75～30 parts, fly ash autoclaved brick powder 800～1000 parts, add the fly ash autoclaved brick powder of 80～160 mesh with HCl after being dissolved by chitosan.
The algicide making frond flocculation also rapid subsidence the most according to claim 1 and 2, it is characterized in that: containing chitosan 3.75～30 parts, fly ash autoclaved brick powder 200～400 parts, add the fly ash autoclaved brick powder of 80～160 mesh with HCl after being dissolved by chitosan.
The algicide making frond flocculation also rapid subsidence the most according to claim 1 and 2, it is characterized in that: containing chitosan 3.75～30 parts, fly ash autoclaved brick powder 400～800 parts, add the fly ash autoclaved brick powder of 80～160 mesh with HCl after being dissolved by chitosan.
The algicide making frond flocculation also rapid subsidence the most according to claim 1 and 2, it is characterized in that: containing chitosan 10～20 parts, fly ash autoclaved brick powder 400～800 parts, add the fly ash autoclaved brick powder of 80～160 mesh with HCl after being dissolved by chitosan.
7. make frond flocculation an algae-removing method for rapid subsidence, utilize the algicide described in claim 1 and potassium permanganate to combine and carry out except algae, it is characterised in that: first a certain amount of potassium permanganate is put in algae pollution water body, pre-oxidize 0～50 minute；The mass/volume of potassium permanganate and algae pollution water body is than for 0.9g:1000L；
Then a certain amount of algicide is added in the water body of algae pollution, stands, after making frond flocculation, be deposited to the bottom.
The algae-removing method making frond flocculation also rapid subsidence the most according to claim 7, it is characterised in that when described algicide is applied during purification algae pollution water body, staying water with the volume ratio of the consumption of algicide is: 100:2.4～4.8.
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| CN107176658B (en) * | 2017-06-07 | 2021-02-12 | 南华大学 | Preparation method and application of potassium permanganate modified shrimp shell capable of settling algae |
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| CN108862527A (en) * | 2017-05-11 | 2018-11-23 | 顺天大学校产学协力团 | Floatability green alga flocculating composition and the green alga minimizing technology for utilizing it |
| CN108862527B (en) * | 2017-05-11 | 2021-09-14 | 顺天大学校产学协力团 | Floating flocculation composition for green algae and method for removing green algae using same |
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