CN105236539A - Modified clay capable of eliminating red tide with high efficiency - Google Patents
Modified clay capable of eliminating red tide with high efficiency Download PDFInfo
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- CN105236539A CN105236539A CN201510712215.0A CN201510712215A CN105236539A CN 105236539 A CN105236539 A CN 105236539A CN 201510712215 A CN201510712215 A CN 201510712215A CN 105236539 A CN105236539 A CN 105236539A
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Abstract
The invention belongs to disaster prevention and mitigation strategies in the field of water ecological safety, and further relates to the fields of control and treatment of red tide in offshore water areas, and specifically to modified clay capable of eliminating the red tide with high efficiency. The modified clay is a compound material prepared from inorganic aluminum salt, clay mineral and an oxidant in a ratio of 500: 0-1: 1-50 by weight. When in use, the modified clay is uniformly mixed with seawater into a uniform suspension which is sprayed on the surface of the red tide water according to a certain concentration, so the effect of rapid elimination of a large number of red tide organisms in water is achieved. The modified clay can solve the problems of harsh application conditions and difficult highly-efficient large-scale application of common PAC modified clay in treatment of the red tide.
Description
Technical field
The present invention's design belongs to hydro-ecological safety field and to prevent and reduce natural disasters strategy, further relates to the Control and treatment field of offshore waters red tide, specifically a kind of modified clay of efficient elimination red tide.
Background technology
Red tide (Redtide) refers under certain environmental conditions, sudden propagation and the gatherings at short notice such as the planktonic microalgae in seawater, protozoon or bacterium, and the disastrous ecological unusual phenomenon of the water ecosystem havoc caused, water colour change.
The frequency of China coastal seas breakout of red tide and intensity constantly increase in recent years, have badly influenced Offshore Ecology safety.For effectively alleviating the harm of Disaster And Prevention Measures of Red Tides, particularly in some culture zones, nursery garden and some views or functional waters, to the method fast and effeciently can eliminating red tide, there is active demand.
At present, the method for red-tide control mainly contains chemical method, Physical, biological process.Although the method can administering red tide is theoretically a lot, meet non-secondary pollution, cost low etc. require considerably less, therefore these methods are confined in laboratory study mostly.In the on-the-spot large-scale application of breakout of red tide, and can obtain the just less of ideal effect, therefore red tide control is still an international headache.
Utilizing clay to administer harmful algal bloom and be proved to be a kind of effective means, also may be the method being uniquely able at present large-scale application, it because cost is low, source wide, efficiency is high, pollute little and favored.The cardinal principle of this method effect utilizes the throwing out of clay particle and harmful algal bloom biology by biological for harmful algal bloom from water body surface settlement to bottom.Last century the seventies, Japan has carried out clay method and has administered the work place study of red tide of sea, and the method cost is low, pollution-free, causes international attention.Eighties of last century Korea S's nineties also utilizes loess to administer harmful algal bloom, achieves good effect.But clay original soil is very low to the removal efficiency of algal tufa biology, be greatly the major defect of the method by soil amount.Removal efficiency can only be improved by increasing clay consumption when practical application, easily there is the situation that the mud quantity of slag is excessive.For this defect, last century, the nineties Institute of Oceanology of the Chinese Academy of Sciences Yu Zhiming researcher proposed the clay surface modification theory (Yuetal.1994a, 1994b, 1995) utilizing clay surface modification technology to improve removal efficiency.Under this theoretical direction, the PAC modified clay (Yu Zhiming etc., 1994c) prepared, substantially increases the efficiency removing algal tufa biology.But find under study for action, use the slurry that the PAC modified clay suspension of seawater preparation is prepared lower than deionized water except algae efficiency.When administering harmful algal bloom in the seawater, removal efficiency still has larger room for promotion.Improve modified clay technology and remove the emphasis that the efficiency in seawater harmful algal bloom is research always.
Kill red tide plankton by strong oxidation and have a lot of reports, propose if any people and utilize oxyradical patent No. CN1594136A, CN1810672A, CN102107944A and CN103058349A), sulphuric acid free radical (patent No. CN101172692A), the method can not only kill frustule, and has the effect improving oxygen level in water body and then improve rate of contaminant degradation in water body.But find in practice; the oxidizer dose needed during by killing approach and eliminating red tide plankton is higher; and; kill the fragmentation that frustule usually can cause frustule; some materials in cell; as dissolved organic matter etc. in Algae toxins, born of the same parents can discharge from cell, secondary pollution may be caused.And when flocculation sedimentation eliminates red tide plankton, the motor capacity of frustule can reduce the efficiency that modified clay removes algal tufa biology, if but reduce the motor capacity of frustule, the efficiency of algal tufa biology can be removed by enhancing modified clay.Therefore a kind of effective methods are now badly in need of.
Summary of the invention
The object of the invention is to administer for red tide of sea the modified clay that a kind of efficient elimination red tide is provided.
For achieving the above object, the technical solution adopted in the present invention is:
A modified clay for efficient elimination red tide, modified clay is the compound of inorganic aluminate, clay mineral and oxygenant, wherein counts by weight, inorganic aluminate: clay mineral: oxygenant=1:1-500:0-50.
Described efficient elimination red tide modified clay, wherein inorganic aluminate is the mixing of one or more in Tai-Ace S 150, aluminum sulfate hydrate, aluminum chloride, aluminum chloride hydrate.
Described efficient elimination red tide modified clay, wherein oxygenant is potassium peroxymonosulfate or Potassium Monopersulfate.
Described efficient elimination red tide modified clay is in proportion by inorganic aluminate and oxygenant Homogeneous phase mixing, adds that powder clay mineral mixes again, stockyard after mixing, after slaking 1-3h, is ground to granularity and is less than 200 object powders.
Described efficient elimination red tide modified clay, by modified clay and sea water mixing uniformly suspension liquid during use, being sprayed onto water surface to the concentration breaking out red tide is 0.01-20g/L, after the natural subsidence of 1-4 hour, effectively can remove red tide plankton.
The present invention has advantage:
The present invention is based on free aluminum ion can fast hydrolyzing in meta-alkalescence seawater, the hydroxyl aluminum compound with absorption-flocculation ability is formed in clay particle surface, thus improve the binding ability of clay particle and frustule, realize the ability improving clay flocculating-removal red tide algae cell; In addition, when adding appropriate strong oxidizer in free aluminum salt modified clay, effectively can be reduced the motor capacity of red tide algae cell after this additive is water-soluble by strong oxidation, the ability of red tide plankton is removed in further synergy modified clay flocculation.
Compared with conventional polymeric aluminum chloride (PAC) modified clay, the present invention's adopt aluminum ion modified clay to occur in red tide water combination that in-situ hydrolysis effect more effectively can promote clay and frustule, reduces the consumption of aluminium class properties-correcting agent.Show significant complementary synergistic effect between each component of new modified clay of the present invention, overcome traditional modified clay use front pre-dispersed time need the restriction of salt-free water (as deionized water etc.), be specially adapted to the elimination of red tide in seawater.
Accompanying drawing explanation
Three kinds of aluminum compound Modified soil suspension that Fig. 1 provides for the embodiment of the present invention eat gold goal removing algae efficiency diagram to pressing down.
Three kinds of aluminum compound Modified soil suspension that Fig. 2 provides for the embodiment of the present invention to chlorella except algae efficiency diagram, wherein, clay concentration is 0.4g/L.
Three kinds of aluminum compound Modified soil suspension that Fig. 3 provides for the embodiment of the present invention remove algae efficiency diagram to Heterosigma akashiwo.
Three kinds of aluminum compound Modified soil suspension that Fig. 4 provides for the embodiment of the present invention to phaeocystis globosa except algae efficiency diagram.
Embodiment
Modified clay of the present invention is made up of potassium peroxymonosulfate, inorganic aluminium compound and clay.In its preparation process, first use inorganic aluminium compound and potassium peroxymonosulfate to carry out surface modification treatment to clay, grinding, mixes.The ratio of each component in modified clay, can according to red tide plankton kind, the abundance that will remove, the envrionment conditions of water body and the price adjustment of each component.If outburst marine site red tide cell density suitably can improve more greatly the ratio of inorganic aluminium compound and potassium peroxymonosulfate; If marine site has the peculiar smell such as stench, the ratio of potassium peroxymonosulfate suitably can be improved.During use, modified clay and fresh water or sea water mixing are formed suspension, is sprayed at breakout of red tide region according to certain concentration, can effective place to go red tide plankton after natural subsidence after a while.
Embodiment 1
Take inorganic aluminate as properties-correcting agent (inorganic aluminate is aluminum chloride, Tai-Ace S 150 or polymerize aluminum chloride), be made into the certain density aqueous solution, add powder clay mineral in proportion again, utilize alkali compound (as Pian Zhuan caustic potash flakes, caustic soda, soda ash, unslaked lime, white lime etc.) to adjust mixture ph to 4 ~ 6, after slaking is stable, obtain different types of modified clay suspension liquid.Wherein with aluminum concentration in modified clay suspension liquid for 2.85 × 10
-2mol/L obtain aluminum chloride modified soil, Tai-Ace S 150 Modified soil, polymerize aluminum chloride Modified soil removal press down food Chroococcus (cell density 1.2 × 10
7cells/ml) be example, in algae liquid, add above-mentioned dissimilar modified clay by sea water mixing respectively reach 0.10,0.20,0.25,0.30,0.40,0.50,0.75,1.0g/L, shakes up, observes in algae liquid the change pressing down food Chroococcus cell density after static 2.5 hours.Various modified clay composition when different working concentration except algae efficiency as shown in Figure 1, result shows, aluminum chloride modified soil or Tai-Ace S 150 Modified soil except algae efficiency higher (see Fig. 1).
Embodiment 2
As described in Example 1, measure the efficiency that above-mentioned dissimilar modified clay removes water body middle-high density chlorella, and compared with the unmodified clay of same concentrations.Chlorella cells density 1.12 × 10 used
8cells/ml, adding modified clay is 0.40g/L to concentration, shakes up, and after static 2.5 hours, observation is except algae efficiency.Different clay except algae efficiency as shown in Figure 2, result show aluminum chloride modified soil or Tai-Ace S 150 Modified soil except algae efficiency higher (see Fig. 2).
Embodiment 3
As described in Example 1, measure the efficiency that above-mentioned dissimilar modified clay removes water body middle-high density Heterosigma akashiwo, and compared with the unmodified clay of same concentrations.Heterosigma akashiwo cell density 7.2 × 10 used
4cells/ml, adding modified clay is 0.10,0.20,0.35,0.50,0.75,1.0,1.5,2.0,2.5g/L to concentration, shakes up, and after static 2.5 hours, observation is except algae efficiency.Except algae efficiency as shown in Figure 3, result show aluminum chloride modified soil or Tai-Ace S 150 Modified soil except algae efficiency higher (see Fig. 3).
Embodiment 4
As described in Example 1, measure the efficiency that above-mentioned dissimilar modified clay removes water body middle-high density phaeocystis globosa, and compared with the unmodified clay of same concentrations.Phaeocystis globosa cell density 2.3 × 10 used
6cells/ml, adding modified clay is 0.10,0.20,0.35,0.50,0.75,1.0,1.5,2.0,2.5g/L to concentration, shakes up, and after static 2.5 hours, observation is except algae efficiency.Except algae efficiency as shown in Figure 4, result show aluminum chloride modified soil or Tai-Ace S 150 Modified soil except algae efficiency higher (see Fig. 4).
Embodiment 5
Study the interaction between three components in this modified clay technology, only consider interaction between the two.The interactive orthogonal experiment of design Three factors-levels band.In design modified clay, the consumption of clay is 0.20,0.50,0.80g, and addition of aluminum sulfate is 0.05,0.10,0.30g, and oxygenant (potassium peroxymonosulfate or Potassium Monopersulfate) consumption is 0,0.025,0.075g.Prepare composite modified clay.Study it to phaeocystis globosa (cell density 2 × 10
6cells/ml) except algae efficiency.Found that, (1) clay, Tai-Ace S 150 and Potassium Monopersulfate are on the impact except algae efficiency all extremely significantly (p < 0.01), (2) there is significant interaction (p < 0.01) between Tai-Ace S 150 and potassium peroxymonosulfate, both Application of composite can significantly improve except algae efficiency.
Claims (5)
1. the efficient modified clay eliminating red tide, is characterized in that: modified clay is the compound of inorganic aluminate, clay mineral and oxygenant, wherein counts by weight, inorganic aluminate: clay mineral: oxygenant=1:1-500:0-50.
2. according to the modified clay of efficient elimination red tide according to claim 1, it is characterized in that: described inorganic aluminate is the mixing of one or more in Tai-Ace S 150, aluminum sulfate hydrate, aluminum chloride, aluminum chloride hydrate.
3. according to the modified clay of efficient elimination red tide according to claim 1, it is characterized in that: described oxygenant is potassium peroxymonosulfate or Potassium Monopersulfate.
4. according to the modified clay of efficient elimination red tide according to claim 1, it is characterized in that: described modified clay is in proportion by inorganic aluminate and oxygenant Homogeneous phase mixing, add after mixing that powder clay mineral mixes again, stockyard, after slaking 1-3h, be ground to granularity and be less than 200 object powders.
5. according to the modified clay of efficient elimination red tide according to claim 1, it is characterized in that: described modified clay and sea water mixing uniformly suspension liquid, being sprayed onto water surface to the concentration breaking out red tide is 0.01-20g/L, after the natural subsidence of 1-4 hour, effectively can remove red tide plankton.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186229A (en) * | 2016-08-12 | 2016-12-07 | 暨南大学 | Algicide and preparation method thereof, algae-removing 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 |
| CN107986412A (en) * | 2017-12-28 | 2018-05-04 | 中国科学院海洋研究所 | A kind of modification clay systems administered for breeding water body harmful algal bloom |
| CN108517307A (en) * | 2018-05-22 | 2018-09-11 | 清华大学深圳研究生院 | A kind of method that modified clay couples use inhibition algal grown with algal control bacterium |
| 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 |
| JP2019517908A (en) * | 2016-12-21 | 2019-06-27 | 中国科学院海洋研究所Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｏｃｅａｎｏｌｏｇｙ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Implementation Method to Optimize Use of Modified Clay Method to Remove Red Tide |
| 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 |
Citations (3)
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|---|---|---|---|---|
| CN1810672A (en) * | 2005-01-28 | 2006-08-02 | 中国科学院海洋研究所 | Modified white clay and its application in treating red tide and fresh water algalbloom |
| JP2009106898A (en) * | 2007-10-31 | 2009-05-21 | Kurita Water Ind Ltd | Method and apparatus for treating water |
| 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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2015
- 2015-10-28 CN CN201510712215.0A patent/CN105236539B/en active Active
Patent Citations (3)
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| CN1810672A (en) * | 2005-01-28 | 2006-08-02 | 中国科学院海洋研究所 | Modified white clay and its application in treating red tide and fresh water algalbloom |
| JP2009106898A (en) * | 2007-10-31 | 2009-05-21 | Kurita Water Ind Ltd | Method and apparatus for treating water |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186229A (en) * | 2016-08-12 | 2016-12-07 | 暨南大学 | Algicide and preparation method thereof, algae-removing method |
| JP2019517908A (en) * | 2016-12-21 | 2019-06-27 | 中国科学院海洋研究所Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｏｃｅａｎｏｌｏｇｙ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Implementation Method to Optimize Use of Modified Clay Method to Remove Red Tide |
| 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 |
| CN107986412A (en) * | 2017-12-28 | 2018-05-04 | 中国科学院海洋研究所 | A kind of modification clay systems administered for breeding water body harmful algal bloom |
| CN108517307A (en) * | 2018-05-22 | 2018-09-11 | 清华大学深圳研究生院 | A kind of method that modified clay couples use inhibition algal grown with algal control bacterium |
| 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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| CN105236539B (en) | 2018-07-20 |
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