CN102249369B - Pumice-carried cyanobacteria scavenger capable of floating on water surface - Google Patents
Pumice-carried cyanobacteria scavenger capable of floating on water surface Download PDFInfo
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- CN102249369B CN102249369B CN2011101117199A CN201110111719A CN102249369B CN 102249369 B CN102249369 B CN 102249369B CN 2011101117199 A CN2011101117199 A CN 2011101117199A CN 201110111719 A CN201110111719 A CN 201110111719A CN 102249369 B CN102249369 B CN 102249369B
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Abstract
The invention relates to a pumice-carried cyanobacteria scavenger capable of floating on water surface and a preparation method thereof. The cyanobacteria scavenger is characterized in that: a TiO2-pillared montmorillonite photocatalyst is coated on an external surface of a pumice carrier, a drying treatment is adopted to obtain the cyanobacteria scavenger; the TiO2-pillared montmorillonite photocatalyst is prepared through adding a titanium pillared agent to suspension of sodium-based montmorillonite, wherein a mass percentage concentration of the suspension of the sodium-based montmorillonite is 2-3%; the titanium pillared agent is prepared through hydrolyzing TiCl4 under a strong acidic condition until the color of the solution is changed from yellowish green to colourlessness, wherein a ratio of the volume of the TiCl4 to the weight of the sodium-based montmorillonite is 0.8-1.2 mL/g, then a standing process, a aging process, a centrifugating process, a washing process and a drying process are adopted to obtain the titanium pillared agent. The pumice-carried cyanobacteria scavenger capable of floating on the water surface has characteristics of easy use, quick effect, low cost, easy recovery and utilization, no secondary pollution and strong adaptability, and can be widely applicable for various water areas suffered cyanobacteria pollution.
Description
Technical field
The present invention relates to the water pollution control field, be specifically related to a kind of agent for removing algae from aquatic system and preparation method thereof.
Background technology
Blue-green algae is an algae bio, cries blue-green algae again.In all algae bios, blue-green algae be the most simply, primary is a kind of.The phenomenon that extremely badly causes a large amount of breedings of blue-green algae to destroy the eubiosis owing to water resource environment is called " blue-green alga bloom ".Blue-green alga bloom can cause fishes and shrimps dead, causes water pollution, Human's production and life is caused seriously influence.In addition, the also health of harm humans seriously of cyanophycean toxin.All there is report to cause the incident that fish domestic animal and people's death by poisoning are died in states such as the U.S., Japan, Australia, Brazil because of the algae toxin.China's numerous water body in lake blue-green alga bloom occurrence frequency is high, and the algae bio amount is huge, and the product virulence is strong.Therefore, it is very urgent seeking a kind of long-acting, the economic and safe prevention and the method for control blue-green alga bloom.
According to the domestic and foreign literature report, existing blue-green algae improvement method is divided methods such as physics, chemistry and biology.
Chemical process is to utilize algicide to remove algae, and is simple, is prone to row; To the not influence of lake surface view, yet, zoobenthos and zooplankton there is adverse influence because it can cause secondary pollution; And consequent dead algae can produce secondary pollution as new source of pollution, is unfavorable for the use of tap water, can raise lakebed simultaneously; Aging, the paludification in acceleration lake, rather than a kind of suitable effective removal method.
Physical method is pulled blue-green algae or centrifugal out as through method for floating from water, it is treated both principal and secondary aspect of disease; Water quality and hydrobiont population are had no adverse effect, non-secondary pollution, and can carry the pollutent in the water outlet; But this method cost is high, is not suitable for large-area applications, need adhere to for a long time removing; In addition, the lake surface view there is certain influence.
Biological method can reduce the pollutent in the water significantly, and in the regular hour, keeps the cleaning of water body, to the not influence of lake surface view.But its time is long, and DeGrain can not fundamentally be removed the pollutent in the lake; Lake biotic population structure, species diversity are affected; Dead algae can produce secondary pollution as new source of pollution, and raises lakebed, aging, the paludification in acceleration lake.
The means of the bacterial control of new development because also unresolved at present it safety and operational issue and drop.Other biological method is as filtering-feed fish control and algae competition, is not very effective or to the green tide of large-scale outburst safety inadequately.
Use commerce and in natural water, remove marine alga with flocculation agent (like Poly aluminum Chloride (PAC) and poly-ferric chloride); It exists the aluminium in safety-problems such as the Poly aluminum Chloride (PAC) can cause cerebral nervous system damage etc.; And the flocculation agent consumption is very big, and cost is high, and this has also limited its use.
Though many methods that blue-green algae is administered are arranged at present, and each method has relative merits separately, can not be used widely.The research of blue-green algae at present and administer the serious present situation that relative blue-green algae pollutes and also be nowhere near is so all carrying out improvement or the research of all kinds about blue-green algae in the worldwide.
Summary of the invention
It is the Cyanobacterial scavenger that can bubble through the water column of carrier and preparation method thereof with the float stone that technical problem to be solved by this invention is to provide a kind of.It is high that it removes blue-green algae efficient, instant effect, non-secondary pollution.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of is the Cyanobacterial scavenger that carrier can be bubbled through the water column with the float stone, it is characterized in that: it is at float stone carrier outside surface parcel TiO
2The pillared montmorillonite photocatalyst obtains through the oven dry processing then;
Described TiO
2The pillared montmorillonite photocatalyst is in mass percent concentration is the suspension-s of na-montmorillonite of 2～3 %, to add the titanium column-supporting agent, and described titanium column-supporting agent is TiCl
4Under strong acidic condition, being hydrolyzed is become colorless by yellow-green colour to solution obtains said TiCl
4Volume and the ratio of na-montmorillonite weight be 0.8～1.2mL/g, leave standstill agingly then, obtain through centrifugal, washing, oven dry.
A kind of is the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier with the float stone, it is characterized in that: may further comprise the steps:
(1) TiO
2The preparation of pillared montmorillonite photocatalyst:
(1.1) take by weighing na-montmorillonite and add in the zero(ppm) water, stir it is uniformly dispersed, obtain mass percent concentration and be the suspension-s of 2%～3% na-montmorillonite;
(1.2) under the condition of 60～80 ℃ of water-baths, in the suspension-s of the na-montmorillonite that step (1.1) obtains, drip the titanium column-supporting agent, described titanium column-supporting agent is TiCl
4Under strong acidic condition, being hydrolyzed is become colorless by yellow-green colour to solution obtains said TiCl
4Volume and the ratio of na-montmorillonite weight be 0.8～1.2 mL/g, still continue to stir after dropwising it is fully reacted, obtain pillared liquid;
(1.3) the pillared liquid chamber that step (1.2) is obtained is gentle and quiet puts aging, centrifugal, washing, oven dry below 100 ℃ is ground and promptly got TiO
2The pillared montmorillonite photocatalyst;
The preparation of the Cyanobacterial scavenger that (2) can bubble through the water column:
Get pumice in lumps, organic binder bond is evenly coated on the surface, again the TiO of step (1) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
Press such scheme, the titanium column-supporting agent in the said step (1.2) is with TiCl
4Is that 1:1～1:10 mixes with the strong acid solution of 4～8 mol/L according to volume ratio, adds water then and is hydrolyzed to be become colorless by yellow-green colour to solution and obtains.
Press such scheme, the drop rate in the said step (1.2) is 2～4 ml/min.
Press such scheme, the block particle diameter of pumice in lumps≤5 cm described in the step (2).
The mineral porous material if you would take off stone, attapulgite, zeolite etc., and chemical property is stable, and is nontoxic, low price; The source is wide, and specific surface area is big, has the good adsorption performance; Blue-green algae in the adsorbable water body, but elimination efficiency is low, and the cyanophycean toxin of can not degrading; Titanium oxide has characteristics such as photocatalysis efficiency height, nontoxicity, chemicalstability are good with photocatalyst, has been widely used at present in various waste water, the waste gas photocatalysis treatment, but because TiO
2Particle diameter is little, runs off easily after the light-catalyzed reaction.It is that carrier makes TiO that the present invention adopts with mineral porous material na-montmorillonite
2The pillared montmorillonite photocatalyst, this photocatalyst aperture is even, adjustable, and specific surface area is big, can strengthen TiO simultaneously
2Photocatalysis efficiency, nontoxic, chemicalstability is good, but efficiently removing blue algae, the degraded cyanophycean toxin, then with this TiO
2Pillared montmorillonite photocatalyst parcel can obtain Cyanobacterial scavenger with the float stone carrier surface, and float stone is claimed pumice or foam again, surface irregularity, and hole is many, light weight, unit weight be less than 1 g/cm
3, can bubble through the water column.The Cyanobacterial scavenger that makes thus can be bubbled through the water column, and is easy to be recycled.While float stone surface irregularity, hole is many, and absorption property is good, also can promote the removing of this Cyanobacterial scavenger to blue-green algae.
Therefore the present invention can fully utilize the adsorption and the TiO of smectite
2The pillared montmorillonite photocatalyst is photocatalytic Degradation efficiently, and when rivers and lakes were polluted by blue-green alga bloom, effectively removed blue-green algae within a short period of time fast, and this Cyanobacterial scavenger itself can be bubbled through the water column simultaneously, and is easy to be recycled.
Beneficial effect of the present invention:
Provided by the invention is that the Cyanobacterial scavenger that can bubble through the water column of carrier is easy to use with the float stone, and it is high to remove blue-green algae efficient, and instant effect is easy to be recycled, non-secondary pollution, and adaptive faculty is strong, can be widely used in the various waters that polluted by blue-green algae.
Provided by the invention is that the advantages of nontoxic raw materials that adopts of the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier is harmless with the float stone, and the source is wide, and cost is low; Easy and simple to handle, controlled.
Embodiment
Below in conjunction with specific embodiment summary of the invention of the present invention is elaborated, but following examples do not limit the scope of the invention.
Embodiment 1
(1) take by weighing the 8.8g na-montmorillonite, add in the zero(ppm) water, stirred 3 hours, obtaining mass percent concentration is the smectite suspension-s of 2.5 %;
(2) under 70 ℃ water bath condition, the speed with 2 ml/min in the smectite suspension-s of step (1) preparation drips the titanium column-supporting agent, and described titanium column-supporting agent is with 8.8 mL TiCl
4Is that 1:10 mixes with the hydrochloric acid soln of 6 mol/L according to volume ratio, add then water be hydrolyzed to solution be colourless obtaining by yellow-green colour, still continue to stir after dropwising and it fully reacted in 3 hours, obtain pillared liquid;
(3) the pillared liquid chamber that step (2) is obtained is gentle and quiet put aging 12 h after, 4000 leave the heart 5 min, washs 3 times, 75 ℃ of oven dry grindings promptly get TiO
2The pillared montmorillonite photocatalyst;
(4) get the pumice in lumps of particle diameter≤5 cm, organic binder bond is evenly coated on the surface, again the TiO of step (3) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
Embodiment 2
(1) take by weighing the 8.8g na-montmorillonite, add in the zero(ppm) water, stirred 3 hours, obtaining mass percent concentration is the smectite suspension-s of 2.6 %;
(2) under 60 ℃ water bath condition, the speed with 4 ml/min in the smectite suspension-s of step (1) preparation is added dropwise to the titanium column-supporting agent, and described titanium column-supporting agent is 7.1 mLTiCl
4Is that 1:5 mixes with the sulphuric acid soln of 4 mol/L according to volume ratio, add then water be hydrolyzed to solution be colourless obtaining by yellow-green colour, still continue to stir after dropwising and it fully reacted in 3 hours, obtain pillared liquid;
(3) the pillared liquid chamber that step (2) is obtained is gentle and quiet put aging 12 h after, 4000 leave the heart 5 min, washs 3 times, 75 ℃ of oven dry grindings promptly get TiO
2The pillared montmorillonite photocatalyst;
(4) get the pumice in lumps of particle diameter≤5 cm, organic binder bond is evenly coated on the surface, again the TiO of step (3) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
Embodiment 3
(1) takes by weighing the 8.8g na-montmorillonite, add in the zero(ppm) water, stirred 3 hours, obtain mass percent concentration and be 2% smectite suspension-s;
(2) under 60 ℃ water bath condition, the speed with 3 ml/min in the smectite suspension-s of step (1) preparation is added dropwise to the titanium column-supporting agent, and described titanium column-supporting agent is 7.1 mL TiCl
4Is that 1:1 mixes with the hydrochloric acid soln of 8 mol/L according to volume ratio, add then water be hydrolyzed to solution be colourless obtaining by yellow-green colour, still continue to stir after dropwising and it fully reacted in 3 hours, obtain pillared liquid;
(3) the pillared liquid chamber that step (2) is obtained is gentle and quiet put aging 12 h after, 4000 leave the heart 5 min, washs 3 times, 75 ℃ of oven dry grindings promptly get TiO
2The pillared montmorillonite photocatalyst;
(4) get the pumice in lumps of particle diameter≤5 cm, organic binder bond is evenly coated on the surface, again the TiO of step (3) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
Embodiment 4
(1) take by weighing the 8.8g na-montmorillonite, add in the zero(ppm) water, stirring is uniformly dispersed it, and obtaining mass percent concentration is the smectite suspension-s of 3 %;
(2) under 80 ℃ water bath condition, in the smectite suspension-s of step (1) preparation, drip the titanium column-supporting agent, described titanium column-supporting agent is 10.5mL TiCl
4Is that 1:1 mixes with the hydrochloric acid soln of 4mol/L according to volume ratio, add then water be hydrolyzed to solution be colourless obtaining by yellow-green colour, still continue to stir after institute dropwises it fully reacted, obtain pillared liquid;
(3) the pillared liquid chamber that step (2) is obtained is gentle and quiet put aging after, washing, oven dry below 100 ℃ is ground and is promptly got TiO
2The pillared montmorillonite photocatalyst;
(4) get pumice in lumps, organic binder bond is evenly coated on the surface, again the TiO of step (3) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
Get the solid algicide that obtains among the embodiment 1, join the lake water that 250 ml have a large amount of blue-green algaes, after stirring, static depositing.Detected result is following:
| Sample | Chlorophyll (mg/L) | Microcystis aeruginosa (individual/uL) | Turbidity (%) | Chlorophyll clearance (%) | Algae is counted clearance (%) |
| Former state | 0.82 | 1236 | 32.3 | 0.00 | 0.00 |
| Add the sample of algicide | 0.042 | 80 | 23 | 94.87 | 93.52 |
Last table can be seen explanation: clarify basically on the blue-green algae lake water upper strata with the Cyanobacterial scavenger of the embodiment of the invention 1 preparation was handled, and visual inspection does not have blue-green algae, and the chlorophyll clearance is just up to 94.87%, and algae number clearance has 93.52%, and turbidity has descended 9.3%.This shows that it is remarkable that the blue-green algae algicide of the present invention's preparation is removed the blue-green algae effect, instant effect.
Claims (5)
1. one kind is the Cyanobacterial scavenger that carrier can be bubbled through the water column with the float stone, it is characterized in that: it is at float stone carrier outside surface parcel TiO
2The pillared montmorillonite photocatalyst obtains through the oven dry processing then;
Described TiO
2The pillared montmorillonite photocatalyst is in mass percent concentration is the suspension-s of 2～3% na-montmorillonite, to add the titanium column-supporting agent, and described titanium column-supporting agent is TiCl
4Under strong acidic condition, being hydrolyzed is become colorless by yellow-green colour to solution obtains said TiCl
4Volume and the ratio of na-montmorillonite weight be 0.8～1.2mL/g, leave standstill agingly then, obtain through centrifugal, washing, oven dry.
2. according to claim 1 is the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier with the float stone, it is characterized in that: may further comprise the steps:
(1) TiO
2The preparation of pillared montmorillonite photocatalyst:
(1.1) take by weighing na-montmorillonite and add in the zero(ppm) water, stir it is uniformly dispersed, obtain mass percent concentration and be the suspension-s of 2%～3% na-montmorillonite;
(1.2) under the condition of 60～80 ℃ of water-baths, in the suspension-s of the na-montmorillonite that step (1.1) obtains, drip the titanium column-supporting agent, described titanium column-supporting agent is TiCl
4Under strong acidic condition, being hydrolyzed is become colorless by yellow-green colour to solution obtains said TiCl
4Volume and the ratio of na-montmorillonite weight be 0.8～1.2 mL/g, still continue to stir after dropwising it is fully reacted, obtain pillared liquid;
(1.3) the pillared liquid chamber that step (1.2) is obtained is gentle and quiet puts aging, centrifugal, washing, oven dry below 100 ℃ is ground and promptly got TiO
2The pillared montmorillonite photocatalyst;
The preparation of the Cyanobacterial scavenger that (2) can bubble through the water column:
Get pumice in lumps, organic binder bond is evenly coated on the surface, again the TiO of step (1) preparation
2The pillared montmorillonite photocatalyst evenly is bonded in the float stone surface, and baking and curing promptly obtains product.
3. according to claim 2 is the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier with the float stone, and it is characterized in that: the titanium column-supporting agent in the said step (1.2) is with TiCl
4Is that 1:1～1:10 mixes with the strong acid solution of 4～8 mol/L according to volume ratio, adds water then and is hydrolyzed to be become colorless by yellow-green colour to solution and obtains.
4. according to claim 2 is the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier with the float stone, and it is characterized in that: the drop rate in the said step (1.2) is 2～4 ml/min.
5. according to claim 2 is the preparation method of the Cyanobacterial scavenger that can bubble through the water column of carrier with the float stone, it is characterized in that: the block particle diameter≤5cm of pumice in lumps in the said step (2).
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| CN102249369B true CN102249369B (en) | 2012-07-25 |
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| CN103936122B (en) * | 2014-04-18 | 2015-12-02 | 芜湖凯奥尔环保科技有限公司 | A kind of deodorizing powdery blue algae treatment agent and preparation method thereof |
| CN105731586A (en) * | 2016-04-14 | 2016-07-06 | 福建省福永德环境科技有限公司 | Floating-state carefree ecological pumice with self-purification function and application method of floating-state carefree ecological pumice |
| CN106732466A (en) * | 2017-02-27 | 2017-05-31 | 安徽埃克利环境工程有限公司 | A kind of adsorption reaction type formaldehyde eliminating agent and preparation method thereof |
| CN111870547B (en) * | 2019-11-06 | 2022-08-05 | 成都理工大学 | Montmorillonite-loaded nano ZnO composite uvioresistant agent and preparation method thereof |
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| EP1201609A4 (en) * | 1999-05-06 | 2006-12-13 | Japan Science & Tech Agency | DEVICE FOR OXIDATIVE DESTRUCTION OF HARMFUL TRUTH SUBSIDIES |
| CN100562351C (en) * | 2007-06-22 | 2009-11-25 | 奇迪电器集团有限公司 | Filter medium for removing microcystin, preparation method thereof, and filter element made of the filter medium |
| CN201089730Y (en) * | 2007-08-10 | 2008-07-23 | 华中科技大学 | Ultraviolet photocatalysis algae-removing device |
| CN101734754B (en) * | 2009-12-25 | 2011-12-28 | 中国地质大学（武汉） | Cyanobacterial scavenger with rare earth complex loaded on mineral material and preparing method thereof |
| CN201620092U (en) * | 2009-12-29 | 2010-11-03 | 苏州德华生态环境科技有限公司 | Photocatalytic oxidation-biology floating bed device |
| CN101817570B (en) * | 2010-04-27 | 2012-11-28 | 上海交通大学 | Automatic curtain temperature control algae killing device for shallow water |
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