CN1164504C - Method for treatment of sea red tides and fresh water bloom - Google Patents
Method for treatment of sea red tides and fresh water bloom Download PDFInfo
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- CN1164504C CN1164504C CNB011345284A CN01134528A CN1164504C CN 1164504 C CN1164504 C CN 1164504C CN B011345284 A CNB011345284 A CN B011345284A CN 01134528 A CN01134528 A CN 01134528A CN 1164504 C CN1164504 C CN 1164504C
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- magnesium silicate
- magnesio
- hydrated
- algae
- clay
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Abstract
The present invention relates to a method for the treatment of sea red tides and fresh water bloom, and in the method for the treatment of sea red tides and fresh water bloom, clay soil is used as an algae cell flocculating agent for the treatment, the effective component of the flocculating agent is hydrated magnesio-silicate salts comprising (Si6O15) or (Si4O10) structural units in ideal crystal cells, and the chemical formula of the hydrated magnesio-silicate salts is Mg8(H2O)4(Si6O15)2(OH)4.8H2O. The hydrated magnesio-silicate salts are in a granular, reticular and fibrous or scaly structure, the granular, reticular and fibrous or scaly structure is formed by the staggered arrangement of laminated structure unit layers and structural unit layers (Si6O15) along a b shaft direction, each laminated structure unit layer is formed by sandwiching a magnesium-oxygen octahedron layer in the middle of an upper silicon-oxygen tetrahedron layer and a lower silicon-oxygen tetrahedron layer, and each silicon-oxygen tetrahedron layer has six silicon-oxygen tetrahedrons. The chemical formula of the hydrated magnesio-silicate salts can be also Mg3[Si4O10](OH)2. The hydrated magnesio-silicate salts have convenient preparation or extraction and low cost. When the hydrated magnesio-silicate salts are used as the flocculating agent, algae flocculation removal efficiency which is much higher than the algae flocculation removal efficiency of the flocculating agents of the disclosed clay soil, the commodity polymerization iron and the commodity polymerization aluminum can be achieved.
Description
Technical field
The present invention relates to a kind of method of administering red tide of sea and fresh water bloom.Specifically, be that employing effective constituent is that structure cell includes (Si
6O
15) or (Si
4O
10) flocculation agent of moisture magnesium silicate of structural unit method that red tide of sea and fresh water bloom are handled.
Background technology
The outburst of harmful algae in natural sea-water, lake and the river (be commonly called as in seawater be red tide, be commonly called as in the fresh water be wawter bloom) has become global problem of environmental pollution.It not only makes water quality severe exacerbation, oxygen deprivation, causes a large amount of fish kills, and the algae toxin can enter food chain and causes human diseases even death.Up to the present, still not having technology in the world can be safely, effectively, economical, synthetically administer this class big scale natural disaster (Anderson, D.M., 1997 Turning back theharmful red tide, Nature, 388,513-514.).It comprehensively is four big classes that disclosed in the past technology can be concluded: chemistry is killed method, biological restraint method, air supporting collecting method, and flocculation sedimentation.Chemistry is killed method because of the pollution of chemical algicide to environment itself, is forbidden by multinational ENVIRONMENTAL LAW.Biological process comprises with microorganism or virus kills frustule.This method is difficult to extensively, uses on a large scale because of selectivity limits, prepares and the reasons such as cycle length, cost height that come into force.A kind of virus often only has the single-minded activity of killing to a kind algae.Owing to cause that the algae kind of red tide or wawter bloom is various, also because the outburst of red tide and wawter bloom has suddenly, be difficult to go out to have in a large number at a certain algal species cultivation in a short time the virus of the single-minded property killed simultaneously.In addition, because algae can produce resistance and immunity to infecting of virus, same virus is difficult to certain algae is continued the performance killing action.The air supporting collecting method is a kind of way with container mechanical harvest algae, is difficult to be applied to the removing (consuming time, consumption money) that the big area natural water body pollutes.Flocculation sedimentation comprises and uses chemical floc and with clay sedimentation algae.Chemical floc (such as composite polymeric aluminium, iron etc.) is owing to have certain toxicity to the biology in the natural water, has been acknowledged as to be used for natural aquatic system.Up to the present, to be known as most promising method be clay method to international scientific circle.
Disclosed now about in the method for clay, useful mineral acid (sulfuric acid) is handled the method (JP57131119) of clay (if you would take off soil), the method of useful hydrogen peroxide treatment clay (JP03255008), have tensio-active agent and clay blended method (JP09154466), have me to propose in recent years unsaturated fatty acids and clay blended method (US6071859).Used in the past clay is mainly kaolin or polynite.These methods can pollute and cost too high (as unsaturated fatty acids) can't big area uses on the spot natural water water quality except the loading chemical substance, defective on the major technique is that flocculation efficiency is low, not only can't thoroughly remove the harmful algae in the water, and because the excessive negative effect that causes the bed mud alluvial of consumption.Seek efficient, safe, cheap alga flocculating agent is the direction of this technical field always.The inventor had once proposed with a kind of based on ferric oxide, was the patented technology (UK GB2337749) of assisting with clay and other title complexs.But it is the frustule in the flocculating settling water body not only, but and the algae toxin of accelerate decomposition solubilised state, but aspect the algae flocculation efficiency, be not greatly improved yet.
Summary of the invention
The purpose of this invention is to provide a kind of method of administering red tide of sea and fresh water bloom, the moisture magnesium silicate that adopts a class to have particular chemical composition and structure in this treatment process comes the harmful algae in the efficient flocculating removal natural water.This moisture magnesium silicate preparation or extraction are convenient, with low cost, can reach the algae flocculation more much higher than polymerization iron, the aluminium flocculating agent of disclosed clay even commodity as flocculation agent and remove efficient.
Specifically, the method for improvement red tide of sea provided by the invention and fresh water bloom, it adopts the frustule flocculation agent to handle, and the resulting structure of this flocculation agent is that desirable structure cell contains (Si
6O
15) or (Si
4O
10) the moisture magnesium silicate of structural unit.
The structure that belongs to a kind of material of this class flocculation agent is by upper and lower two-layer each six silicon-oxy tetrahedron, and the octahedra laminate structure unit layer of forming of therebetween one deck magnesia is by structural unit layer (Si
6O
15) along the b direction of principal axis be staggered having of forming granular, netted, fibrous or lepidiod, with Mg
8(H
2O)
4(Si
6O
15)
2(OH)
48H
2O is the moisture magnesium silicate of effective ingredient.It has the high capability of anti-salt dispersiveness, and forming irregular fibre network in water also can be to Fe
3+Special propertys such as characteristic absorption are arranged.Theoretical surface is long-pending can to reach 900m
2/ g.Because above-mentioned chemical constitution and structure that this material had, it can produce the algae flocculation efficiency far above other clays in seawater and fresh water.
The another kind of material that belongs to this class flocculation agent can be used chemical formula Mg
3[Si
4O
10] (OH)
2Express.
The characteristics of above-mentioned these frustule flocculation agents are to mix with other clay minerals or metal oxide (as ferric oxide) when above-mentioned moisture magnesium silicate, and when the amount that contains above-mentioned effective constituent in the mixture surpassed 20% mark (w/w), then the frustule flocculation ability of this mixture also can significantly be urged to improve.
The moisture magnesium silicate of the invention described above mainly is present in sepiolite or the talcum mineral reserve at occurring in nature.
In addition, in the frustule flocculation agent of the invention described above, can add in ferric oxide, Z 250, kaolin, light shale, potter's clay, Attapulgite, silicon mud, illite clay, red bauxite, mica, clinoptilolite, montmorillonite, PAC, light skeletal float stone, white clay, zeolite, float stone, stranding pin stone, volcanic cinder, diatomite, the china clay one or more on the effective ingredient basis of flocculation agent, addition is not more than 80% of flocculation agent weight.
The method of improvement red tide of sea provided by the invention and fresh water bloom can be used the frustule flocculation agent of the invention described above.Its consumption is decided by the situation of processed seawater and fresh water, but preferably is no less than 0.05g/l.Usually administering in red tide of sea and the fresh water bloom, when the consumption that uses flocculation agent of the present invention during as 0.1-0.28g/l, its frustule clearance can reach 88-98%.
Flocculation agent with said structure of the present invention can utilize the preparation of conventional synthetic method or extracts from mineral.At occurring in nature, this material mainly is present in sepiolite and the talcum.This active substance is separated, extracted to available settling process from contain sepiolite or steatitic mineral.Through Fe
3+This material after the modification can possess higher frustule flocculation efficiency.This material is to human body and water surrounding totally nontoxic, harmless.
For example, when the microcystic aeruginosa cell concn be 4.8*10
6During cell/ml, add the sepiolite powder (100 order) that 0.2g/l extracts by the inventive method, the frustule concentration after 8 hours in the water body has reduced by 97.2%.Make comparisons with present commercial sewage treatment flocculating agent polymeric aluminum (PAC), under the same conditions, if add the PAC of 0.2g/l, then the frustule concentration in the water body has only reduced by 38.1% after 8 hours.Under the same conditions, if add the kaolin (armorphous) of 0.2g/l, then the frustule concentration in the water body has only reduced by 21.8% after 8 hours.If add the illite of 0.2g/l, then the frustule concentration in the water body has only reduced by 34.6% after 8 hours.If add the montmorillonite of 0.4g/l, then the frustule concentration in the water body has only reduced by 34.7% after 8 hours.This shows that sepiolite has the raising of essence than disclosed technology to the flocculation efficiency of microcystic aeruginosa.
Description of drawings
Fig. 1 removes the result of algae for adopting sepiolite flocculation of the present invention.
Fig. 2 be different sepiolite content remove the algae efficiency ratio.
Fig. 3 is that the flocculation efficiency of sepiolite and other clay flocculating compares.
Fig. 4 removes the algae effect relatively for the modified meerschaum flocculation.
Embodiment
Give further detailed explanation below by embodiment to technology of the present invention.
Embodiment 1 sepiolite extracts preparation
With sepiolite raw ore drying, be crushed to certain particle size (70～180 order), be scattered in the distilled water, be mixed with the suspension that concentration is about 10h/L, stir and leave standstill 30min, supernatant liquor is taken out in siphon.With gained supernatant liquor centrifugation 10min under 12000rpm, collect the settling of gained, oven dry 12h ground 180 orders under 65 ℃, and through the X-diffraction analysis, the sepiolite purity of gained reaches more than 90%.
Embodiment 2 Fe
3+Modified meerschaum
Take by weighing the prepared 1.00g sepiolite (90%) of embodiment 1, be scattered in 50mL, the Fe of 1000mg/L
3+(use NH in the solution
4Fe (SO
4)
212H
2The O preparation), after normal temperature vibrates 5h down, centrifugation 10min under the 12000rpm, the sepiolite of collecting gained also places 65 ℃ of oven dry 12h down, grinds 180 orders and promptly gets modified meerschaum.
The embodiment of algae is removed in the flocculation of embodiment 3 sepiolites
The sepiolite that takes by weighing the made 0.1g of embodiment 1 is in the 800ml beaker, and adding 500ml fast, to have prepared concentration be 4.78*10
6The algae liquid of cell/ml (the NaCl solution preparation algae liquid with 0.5%) places to begin immediately on the six coagulation stirrers to stir, and picks up counting simultaneously.Mixing parametric is: 600rpm stirred 4 minutes down fast, changed 50rpm then over to and continued to stir 2 minutes down, stopped at last stirring, and left standstill.And by the time under liquid level about 3cm place sampling and measuring frustule concentration, and calculating frustule clearance.Result such as Fig. 1 (adding dose is 0.2g/l).As seen from Figure 1, the algae clearance surpasses 90% after handling 100 minutes, and the algae clearance surpasses 99% after 300 minutes, near going algae fully.
The comparison of embodiment 4 sepiolite flocculation efficiencies and other clays or flocculation agent
Press and embodiment 3 identical operations conditions, add dose by 0.7g/l and add different clays or flocculation agent, measured 10,30,90,240, the algae clearance in the time of 480 minutes.Below only compare after 8 hours, different flocculation agents are removed the effect (algae clearance) of algaes:
Sepiolite (embodiment 1 is made) (99.8%)＞talcum (97.6%)＞di-iron trioxide (96.5%)＞tri-iron tetroxide (95%)＞kaolin (crystal formation, 93%)＞light shale (92%)＞potter's clay (85.9%)＞concave convex rod (78.7%)＞silicon mud (73.8%)＞illitic soil (58.6%)＞red bauxite (46.2%)＞mica (46.1%)＞clinoptilolite (43.8%)＞montmorillonite (43.7%)＞PAC (37.8%)＞lightweight aggregate float stone (35.6%)＞white clay (34.1%)＞zeolite (30.5%)＞float stone-stranding pin stone (29.1%)＞scoria (27.2%)＞diatomite (24.3%)＞china clay (24.1%)＞high potassic feldspar (9%)＞quartz (4%).
Embodiment 5 different sepiolite content remove the algae efficiency ratio
Press and embodiment 3 identical operations conditions, add the flocculation agent (other is quartzite) (100 order) that dose adds different sepiolite content, the algae clearance when having measured 10,30,90,240,480 minutes by 0.4g/l.When sepiolite content is 50%, remove algae efficient in 8 hours and can reach 96% (frustule concentration: 4.78*106cell/ml is during dosage 0.4g/l), concrete outcome is seen Fig. 2.By embodiment 5 as can be known, can directly adopt sepiolite content to be used for removing algae as flocculation agent in the method for the invention greater than 20% scpiolitc.
Embodiment 6
Press embodiment 3 described methods, the flocculation efficiency of comparing embodiment 1 made other preferable clay flocculating agent, it the results are shown in Fig. 3.As seen from Figure 3, when dosage is reduced to 0.2g/l, descend significantly when the efficient of other best clay flocculating agent is all than 0.7g/l except that sepiolite, sepiolite still keeps 8 hours 97% alga-killing rate only.
The flocculation of embodiment 7 modified meerschaums removes the algae effect
The modified meerschaum that takes by weighing a certain amount of embodiment 1 system sepiolite and embodiment 2 systems respectively is in two 800ml beakers, and adding 500ml fast, to have prepared concentration be 4.78*10
6The algae liquid of cell/ml (the NaCl solution preparation algae liquid with 0.5%) places to begin immediately on the six coagulation stirrers to stir, and picks up counting simultaneously.Mixing parametric is: 600rpm stirred 4 minutes down fast, changed 50rpm then over to and continued to stir 2 minutes down, stopped at last stirring, and left standstill.And by the time under liquid level about 3cm place sampling and measuring frustule concentration, and calculating frustule clearance.The result as shown in Figure 4.By Fig. 4 result as can be known, the sepiolite after the modification has better except that the algae effect.
Claims (5)
1. a class is administered the method for red tide of sea and fresh water bloom, is the method that adopts clay to handle as the frustule flocculation agent, and the effective constituent that it is characterized in that described flocculation agent is that structure cell contains (Si
6O
15) or (Si
4O
10) the moisture magnesium silicate of structural unit;
The chemical formulation of described moisture magnesium silicate is Mg
8(H
2O)
4(Si
6O
15)
2(OH)
48H
2O, it is by upper and lower two-layer each six silicon-oxy tetrahedron, the octahedra laminate structure unit layer of forming of therebetween one deck magnesia is by structural unit layer (Si
6O
15) granular, netted, the fibrous or lepidiod structure that has that is staggered and forms along the b direction of principal axis, perhaps
The structural table of described moisture magnesium silicate is shown Mg
3[Si
4O
10] (OH)
2And,
The content of described moisture magnesium silicate is more than 20% of flocculation agent weight.
2. method according to claim 1 is characterized in that described moisture magnesium silicate is sepiolite.
3. method according to claim 1 is characterized in that described moisture magnesium silicate is talcum.
4. method according to claim 1 is characterized in that described moisture magnesium silicate Fe3+ ion modification.
5. according to the method described in any in the claim 1 to 4, it is characterized in that on flocculation agent effective ingredient basis, adding in ferric oxide, Z 250, kaolin, light shale, potter's clay, Attapulgite, silicon mud, the Erie, in the red bauxite, mica, clinoptilolite, montmorillonite, PAC, light skeletal float stone, white clay, zeolite, float stone, stranding pin stone, volcanic cinder, diatomite, china clay one or more, addition is less than 80% of flocculation agent weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011345284A CN1164504C (en) | 2001-11-05 | 2001-11-05 | Method for treatment of sea red tides and fresh water bloom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011345284A CN1164504C (en) | 2001-11-05 | 2001-11-05 | Method for treatment of sea red tides and fresh water bloom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1417136A CN1417136A (en) | 2003-05-14 |
| CN1164504C true CN1164504C (en) | 2004-09-01 |
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ID=4672565
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011345284A Expired - Fee Related CN1164504C (en) | 2001-11-05 | 2001-11-05 | Method for treatment of sea red tides and fresh water bloom |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298220C (en) * | 2005-08-30 | 2007-02-07 | 姜哲 | Red tide inhibiting carbon powder and its prepn |
| CN1769198B (en) | 2005-09-05 | 2012-07-11 | 中国科学院生态环境研究中心 | Method for transferring water bloom to water-bed plant using clay agglomeration |
| CN101219828B (en) * | 2008-01-24 | 2010-06-23 | 云南大学 | Blue algae water bloom bioflocculation agent and production |
| CN101643261B (en) * | 2009-08-24 | 2011-06-29 | 暨南大学 | Algae-controlling laterite compound flocculant as well as preparation method and applications thereof |
| CN103691405B (en) * | 2013-12-20 | 2016-01-20 | 大连赛姆生物工程技术有限公司 | A kind of sepiolite water purification agent of fast purification marine culture water |
| CN104098190B (en) * | 2014-07-29 | 2016-08-17 | 中国水产科学研究院渔业机械仪器研究所 | A kind of method suppressing Cyanophyta microcystis kutz wawter bloom |
| CN105293651B (en) * | 2015-11-23 | 2018-08-21 | 天津大学 | A kind of algal control removes algae medicament |
| CN105668745A (en) * | 2016-04-07 | 2016-06-15 | 叶君芝 | Composite component for promoting sewage flocculation |
| CN105776474A (en) * | 2016-04-23 | 2016-07-20 | 陈斌 | Composition for promoting flocculation of sewage |
| CN105858786A (en) * | 2016-04-27 | 2016-08-17 | 陈书仁 | Sewage purifying agent |
| CN110642472A (en) * | 2019-10-24 | 2020-01-03 | 云南农业大学 | Mixed flocculant and method for treating cyanobacterial bloom by using same |
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2001
- 2001-11-05 CN CNB011345284A patent/CN1164504C/en not_active Expired - Fee Related
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