CN105236539B - A kind of efficient modification clay for eliminating red tide - Google Patents
A kind of efficient modification clay for eliminating red tide Download PDFInfo
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- CN105236539B CN105236539B CN201510712215.0A CN201510712215A CN105236539B CN 105236539 B CN105236539 B CN 105236539B CN 201510712215 A CN201510712215 A CN 201510712215A CN 105236539 B CN105236539 B CN 105236539B
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- red tide
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- inorganic aluminate
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Abstract
Present invention design belongs to hydro-ecological safety field and prevents and reduces natural disasters strategy, is further related to control and the improvement field of offshore waters red tide, specifically a kind of efficient modification clay for eliminating red tide.Modified clay is the compound of inorganic aluminate, clay mineral and oxidant, wherein counting in parts by weight, inorganic aluminate：Clay mineral：Oxidant=1:1‑500:0‑50.The modification clay and sea water mixing are sprayed at red tide water surface according to a certain concentration, can achieve the effect that quickly to eliminate a large amount of red tide planktons in water body at uniform suspension when use.The modification clay can overcome the problems, such as common PAC modifications clay, and when administering red tide, application conditions are harsh, are difficult to efficiently a wide range of application.
Description
Technical field
Present invention design belongs to hydro-ecological safety field and prevents and reduces natural disasters strategy, is further related to offshore waters red tide
Control and the field of improvement, specifically a kind of efficient modification clay for eliminating red tide.
Background technology
Red tide (Red tide) refers to the planktonic microalgae, protozoan in seawater or bacterium under certain environmental conditions
Deng sudden proliferation and aggregation in a short time, caused by water ecosystem seriously destroy, the disastrous life of water colour variation
State abnormal phenomenon.
The frequency and intensity of China coastal seas breakout of red tide are continuously increased in recent years, have seriously affected Offshore Ecology safety.
It is right especially in some culture zones, nursery garden and some landscapes or functional waters effectively to mitigate the harm of Disaster And Prevention Measures of Red Tides
The method that red tide can fast and effeciently be eliminated has active demand.
Currently, the method for red-tide control mainly has chemical method, Physical, bioanalysis.Although can theoretically administer
There are many method of red tide, but meet the considerably less of the requirements such as non-secondary pollution, at low cost, therefore these methods are confined to mostly
In laboratory research.Can be in breakout of red tide scene large-scale application, and the just less of ideal effect is obtained, therefore red tide control
It is still an international headache.
Administering harmful algal bloom using clay is proved to be a kind of effective method, it is also possible to currently the only to be able on a large scale
The method of application, it is favored because at low cost, source is wide, efficient, pollution is small.The cardinal principle of this method effect is
Using the flocculation of clay particle and harmful algal bloom biology by harmful algal bloom biology from water body surface settlement to bottom.Last century
The seventies, Japan have carried out the work place study that clay method administers red tide of sea, and this method is at low cost, pollution-free, causes state
Attention on border.The last century 90's, South Korea also utilized loess to administer harmful algal bloom, achieved good effect.But clay is former
Soil is very low to the removal efficiency of algal tufa biology, is the major defect of this method greatly with soil amount.It can only be by increasing in practical application
Clay dosage improves removal efficiency, is easy to there is a situation where that the mud quantity of slag is excessive.For the defect, in last century the nineties
State Institute Of Oceanology Yu Zhiming researcher proposes the clay table that removal efficiency is improved using clay surface modification technology
Face is modified theoretical (Yu et al.1994a, 1994b, 1995).Under this theoretical direction, the PAC prepared is modified clay (Yu Zhi
It is bright etc., 1994c), substantially increase the efficiency of removal algal tufa biology.But find under study for action, the PAC prepared using seawater is changed
Property slurry except algae efficiency be less than deionized water prepare slurry.When administering harmful algal bloom in the seawater, removal
Efficiency still has larger room for promotion.It is always to grind to improve efficiency of the modified clay technology in removing seawater harmful algal bloom
The emphasis studied carefully.
Killing red tide plankton by strong oxidation has had many reports, such as it is proposed that special using oxygen radical
Profit CN 1594136A, CN1810672A, CN102107944A and CN103058349A), sulphuric acid free radical (patent No. CN
101172692A), this method can not only kill frustule, and with oxygen content in raising water body and then improve in water body
The effect of rate of contaminant degradation.But it is found in putting into practice, the oxidizer dose needed when eliminating red tide plankton by killing approach
It is higher, moreover, the broken of frustule, some substances in cell, as algae toxin, intracellular dissolve can be caused by killing frustule usually
Organic matter etc. can be released from cell, be likely to result in secondary pollution.And when flocculation sedimentation eliminates red tide plankton,
The locomitivity of frustule can reduce the efficiency of modified clay removal algal tufa biology, but can if the locomitivity for reducing frustule
The efficiency of enough modified clay removal algal tufa biologies of enhancing.Therefore now it is badly in need of a kind of effective methods.
Invention content
The purpose of the present invention is administer to provide a kind of efficient modification clay for eliminating red tide for red tide of sea.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of efficient modification clay for eliminating red tide, modified clay are the compounding of inorganic aluminate, clay mineral and oxidant
Object, wherein counting in parts by weight, inorganic aluminate：Clay mineral：Oxidant=1:1-500:0-50.
The efficient elimination red tide is modified clay, wherein inorganic aluminate be aluminum sulfate, aluminum sulfate hydrate, aluminium chloride,
The mixing of one or more of aluminum chloride hydrate.
The efficient elimination red tide is modified clay, and wherein oxidant is potassium peroxymonosulfate or monopersulfate
Potassium.
The efficient elimination red tide is modified clay, is in proportion uniformly to mix inorganic aluminate with oxidant, after mixing
Powder clay mineral mixing, stockyard again is added, after curing 1-3h, is ground to the powder that granularity is less than 200 mesh.
The efficient elimination red tide is modified clay, when use will modified clay and sea water mixing at uniform suspension,
The water surface for breaking out red tide is sprayed onto to a concentration of 0.01-20g/L, after 1-4 hours natural subsidences, can effectively be gone
Except red tide plankton.
The present invention is had the advantage that：
The present invention is based on free aluminium ions can have with fast hydrolyzing in clay particle surface formation in meta-alkalescence seawater
The hydroxyl aluminium compound of absorption-flocculation ability is realized to improve the binding ability of clay particle and frustule and improves clay wadding
The ability of solidifying-removal red tide frustule；In addition, when adding appropriate strong oxidizer in the aluminum salt modified clay that dissociates, the addition
Agent is dissolved in the locomitivity that can effectively reduce red tide frustule after water by strong oxidation, and further synergy is modified clay wadding
The ability of solidifying removal red tide plankton.
Compared with the modified clay of conventional polymeric aluminium chloride (PAC), the present invention is modified clay in red tide water using aluminium ion
In-situ hydrolysis effect occurs in body can more effectively promote the combination of clay and frustule, reduce the use of aluminium class modifying agent
Amount.Significant complementary synergistic effect is shown between the new modified clay each component of the present invention, and it is modified viscous to overcome tradition
Soil application needs the limitation of salt-free water (such as deionized water), the elimination especially suitable for red tide in seawater when preceding pre-dispersed.
Description of the drawings
Fig. 1 is that three kinds of aluminium compound Modified soil suspension provided in an embodiment of the present invention eats gold goal removing algae efficiency to suppression
Figure.
Fig. 2 is that three kinds of aluminium compound Modified soil suspension provided in an embodiment of the present invention removes algae efficiency chart to chlorella,
Wherein, clay concentration 0.4g/L.
Fig. 3 is that three kinds of aluminium compound Modified soil suspension provided in an embodiment of the present invention removes algae efficiency to Heterosigma akashiwo
Figure.
Fig. 4 is that three kinds of aluminium compound Modified soil suspension provided in an embodiment of the present invention removes algae efficiency to phaeocystis globosa
Figure.
Specific implementation mode
The present invention is modified clay and is made of potassium peroxymonosulfate, inorganic aluminium compound and clay.It prepared at it
Cheng Zhong uses inorganic aluminium compound and potassium peroxymonosulfate to carry out surface modification treatment to clay first, grinds, mixing
Uniformly.The ratio of each component in modified clay, can be according to red tide plankton type, the abundance to be removed, the environmental condition of water body
And the price adjustment of each component.If breaking out, marine site red tide cell density is larger can to properly increase inorganic aluminium compound and list
The ratio of ammonium persulfate-sodium bisulfate；If marine site has the peculiar smell such as stench, potassium peroxymonosulfate can be properly increased
Ratio.In use, modified clay is formed suspension with fresh water or sea water mixing, breakout of red tide is sprayed at according to certain concentration
Region, can effective place to go red tide plankton after natural subsidence after a period of time.
Embodiment 1
Using inorganic aluminate as modifying agent (inorganic aluminate is aluminium chloride, aluminum sulfate or aluminium polychloride), it is made into certain
The aqueous solution of concentration, then be proportionally added into powder clay mineral, using alkali compound (such as caustic potash, caustic soda, soda ash, quick lime,
White lime etc.) for adjustment mixture ph to 4~6, curing obtains different types of modified clay suspension after stablizing.Wherein to change
Property clay suspension in aluminum concentration be 2.85 × 10-2Aluminum chloride modified soil, aluminum sulfate Modified soil, polyaluminium obtained by mol/L
The removal suppression food Chroococcus (cell density 1.2 × 10 of aluminium Modified soil7Cells/ml for), sea water mixing is used respectively in algae solution
It adds above-mentioned different type modification clay and reaches 0.10,0.20,0.25,0.30,0.40,0.50,0.75,1.0g/L, shake up, is quiet
The variation of suppression food gold goal algae cell density in algae solution is only observed after 2.5 hours.Various modified clay compositions are different using dense
When spending except algae efficiency it is as shown in Figure 1, the results showed that, aluminum chloride modified soil or aluminum sulfate Modified soil except algae efficiency it is higher (ginseng
See Fig. 1).
Embodiment 2
As described in Example 1, the efficiency that above-mentioned different type is modified clay removal water body middle-high density chlorella is measured, and
Compared with the unmodified clay of same concentrations.Chlorella cells density 1.12 × 10 used8Cells/ml adds modified clay
It to a concentration of 0.40g/L, shakes up, after static 2.5 hours, observation removes algae efficiency.Different clays remove algae efficiency as shown in Fig. 2,
The result shows that aluminum chloride modified soil or aluminum sulfate Modified soil except algae efficiency it is higher (referring to Fig. 2).
Embodiment 3
As described in Example 1, the effect that above-mentioned different type is modified clay removal water body middle-high density Heterosigma akashiwo is measured
Rate, and compared with the unmodified clay of same concentrations.Heterosigma akashiwo cell density 7.2 × 10 used4Cells/ml, addition
Modified clay shakes up, static 2.5 hours to a concentration of 0.10,0.20,0.35,0.50,0.75,1.0,1.5,2.0,2.5g/L
Afterwards, observation removes algae efficiency.Except algae efficiency is as shown in Figure 3, the results showed that the algae that removes of aluminum chloride modified soil or aluminum sulfate Modified soil is imitated
Rate is higher (referring to Fig. 3).
Embodiment 4
As described in Example 1, the effect that above-mentioned different type is modified clay removal water body middle-high density phaeocystis globosa is measured
Rate, and compared with the unmodified clay of same concentrations.Phaeocystis globosa cell density 2.3 × 10 used6Cells/ml, addition
Modified clay shakes up, static 2.5 hours to a concentration of 0.10,0.20,0.35,0.50,0.75,1.0,1.5,2.0,2.5g/L
Afterwards, observation removes algae efficiency.Except algae efficiency is as shown in Figure 4, the results showed that the algae that removes of aluminum chloride modified soil or aluminum sulfate Modified soil is imitated
Rate is higher (referring to Fig. 4).
Embodiment 5
The reciprocation between three components in the modification clay technology is studied, only considers reciprocation between the two.If
Count the interactive orthogonal experiment of Three factors-levels band.The dosage of clay is 0.20,0.50,0.80g in the modified clay of design,
Addition of aluminum sulfate is 0.05,0.10,0.30g, and oxidant (potassium peroxymonosulfate or Potassium Monopersulfate) dosage is 0,
0.025,0.075g.Prepare composite modified clay.It is studied to phaeocystis globosa (cell density 2 × 106Removing cells/ml)
Algae efficiency.As a result, it has been found that (1) clay, aluminum sulfate and Potassium Monopersulfate are to all extremely significantly (the p ＜ of the influence except algae efficiency
0.01), (2) between aluminum sulfate and potassium peroxymonosulfate there are significant reciprocation (p ＜ 0.01), the two it is compound
Using can significantly improve except algae efficiency.
Claims (2)
1. a kind of efficient modification clay for eliminating red tide, it is characterised in that：Modified clay is inorganic aluminate, clay mineral and oxidation
The compound of agent, wherein counting in parts by weight, inorganic aluminate：Clay mineral：Oxidant=1:1-500:0-50；
The inorganic aluminate is the mixed of one or more of aluminum sulfate, aluminum sulfate hydrate, aluminium chloride, aluminum chloride hydrate
It closes；The oxidant is potassium peroxymonosulfate or Potassium Monopersulfate；
Above-mentioned inorganic aluminate and potassium peroxymonosulfate carry out surface modification treatment to clay and are formed on its surface with suction
The hydroxyl aluminium compound of attached-flocculation ability is to get to modified clay；
The modified clay is in proportion uniformly to mix inorganic aluminate with oxidant, and powder clay mineral is added again after mixing
Mixing, stockyard, cure 1-3h after, be ground to granularity be less than 200 mesh powder.
2. the efficient modification clay for eliminating red tide described in accordance with the claim 1, it is characterised in that:The modified clay and seawater
It is mixed into uniform suspension, is sprayed onto the water surface for breaking out red tide to a concentration of 0.01-20 g/L, by 1-4 hours
After natural subsidence, red tide plankton can be effectively removed.
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| CN106186229A (en) * | 2016-08-12 | 2016-12-07 | 暨南大学 | Algicide and preparation method thereof, algae-removing method |
| CN106709603B (en) * | 2016-12-21 | 2020-10-16 | 中国科学院海洋研究所 | Implementation method for eliminating red tide by optimizing and utilizing modified clay method |
| CN107032465A (en) * | 2017-05-05 | 2017-08-11 | 中国科学院海洋研究所 | A kind of efficient modification clay composite material for removing microalgae red tide and preparation method thereof |
| CN107986412B (en) * | 2017-12-28 | 2020-11-03 | 中国科学院海洋研究所 | Modified clay system for controlling harmful algal blooms in aquaculture water |
| CN108517307B (en) * | 2018-05-22 | 2020-08-18 | 清华大学深圳研究生院 | Method for inhibiting algae growth by coupling modified clay and algae inhibiting bacteria |
| CN109553144A (en) * | 2019-01-21 | 2019-04-02 | 德州绿能水处理科技有限公司 | Natural biological algal control clarifying agent |
| CN111592006A (en) * | 2020-06-12 | 2020-08-28 | 上海交通大学 | Preparation method of modified clay and application method of modified clay for directionally recycling microalgae |
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| CN1325390C (en) * | 2005-01-28 | 2007-07-11 | 中国科学院海洋研究所 | Modified white clay and its application in treating red tide and fresh water algalbloom |
| JP5218731B2 (en) * | 2007-10-31 | 2013-06-26 | 栗田工業株式会社 | Water treatment method and water treatment apparatus |
| CN103224273A (en) * | 2013-04-23 | 2013-07-31 | 中国科学院海洋研究所 | Composite modified clay for eliminating seawater red tide |
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