Algae removing agent based on amphiphilic dendrimer and algae removing method thereof
Technical Field
The invention relates to the technical field of algae removal of water bodies, in particular to an algae removal agent based on amphiphilic dendrimers and an algae removal method thereof.
Background
In recent years, eutrophication of water and global warming accelerate the process of algal bloom, and bring great influence to ecological environment, human health and economic development. The current methods for controlling algal bloom can be mainly divided into a chemical algae control method, a biological algae control method and a physical algae control method. The physical algae removal method mainly utilizes algae removal machinery to remove algae from water, but the method has high cost and narrow application range, and is not convenient for large-scale use. Biological algae removal is mainly to introduce new organisms to control algae growth, however, the method has a long period, and the newly introduced organisms may damage ecological balance and food chain. Although chemical algaecides can be used for emergently coping with the outbreak of algal bloom, the traditional chemical algaecides bring secondary pollution to the environment.
The natural clay is utilized to flocculate and settle harmful algal bloom, which can be applied to the actual green algae removal method, but the low flocculation efficiency of the natural clay limits the application. Research has shown that the cationic modifier can improve the flocculation effect of clay, but the existing modifier still cannot meet the efficient algae removal effect, so that the design and exploration of novel flocculant and clay modifier have important significance.
Disclosure of Invention
The invention aims to provide an amphiphilic dendrimer-based algaecide which is simple and convenient to operate, high in flocculation efficiency and high in algaecide speed, so as to overcome the defects of the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: an algaecide based on amphiphilic dendrimers, the algaecide comprising a flocculant which is amphiphilic dendrimer C 18 -KK 2 。
Amphiphilic dendrimer C 18 -KK 2 Is a prior biomedical material which has been researched and prepared by some researchers, and the invention firstly proposes amphiphilic dendrimer C 18 -KK 2 Amphiphilic dendrimer C as flocculant in algaecides 18 -KK 2 Consists of two hydrophobic alkyl chains and a hydrophilic polylysine dendrite, and has the following structural general formula:
amphiphilic dendrimer C 18 -KK 2 The water-soluble algae has good solubility, has positive charges on the surface, and can be combined with algae cells efficiently through the electric neutralization, so that the algae cells are flocculated together and settled.
Preferably, the algae is microcystis aeruginosa which is a common algae species causing algal bloom.
Preferably, amphiphilic dendrimer C in algae liquid 18 -KK 2 The final concentration is 0.1-7 mug/mL.
Further, amphiphilic dendritic molecule C in algae liquid 18 -KK 2 The optimal final concentration is 6. Mu.g/mL.
Another object of the present invention is to provide a composite algaecide comprising a flocculant which is an amphiphilic dendrimer C and clay 18 -KK 2 。
Although amphiphilic dendrimer C 18 -KK 2 Has better flocculation capacity to algae cells, but is due to amphiphilic dendritic molecule C 18 -KK 2 The flocculated algae cells form loose floccule structures and are easy to float under the action of external force, so that the formed floccules are unstable. The clay is used as coagulant aid to obviously accelerate flocculation sedimentation, which is more beneficial to rapid clarification of water.
Preferably, the clay is sepiolite, which is prepared from amphiphilic dendrimer C 18 -KK 2 And the composite algicide composed of sepiolite can achieve good flocculation algicide effect.
Preferably, the amphiphilic dendrimer C in the composite algaecide 18 -KK 2 The final concentration of the sepiolite in the algae liquid is 0.1-6 mug/mL, and the final concentration of the sepiolite in the algae liquid is 40-320 mug/mL.
Preferably, the amphiphilic dendrimer C in the composite algaecide 18 -KK 2 The optimal final concentration in the algae solution is 4. Mu.g/mL.
Another object of the present invention is to provide an algae removal method of the above composite algae removal agent, wherein sepiolite is added into algae liquid, and then amphiphilic dendrimer C is added 18 -KK 2 And (5) fully and uniformly mixing. In the algae removal process, sepiolite with negative charges and algae cells are simultaneously attached to the amphiphilic dendritic molecule C with positive charges 18 -KK 2 Therefore, the volume of the flocculating constituent is increased, the descending speed of the flocculating constituent is accelerated, a large number of algae cells are swept in the descending process, and the amphiphilic dendritic molecule C can be further reduced 18 -KK 2 Is used in the amount required.
Preferably, after the addition of the material is completed, the material is rapidly stirred at 400 rpm for 1 minute, then at 100 rpm for 14 minutes, and finally allowed to stand for 15 minutes.
If sepiolite solution with the concentration of 40-320 mug/mL is singly used for removing microcystis aeruginosa, the removal rate after 1 hour is less than 10%; if 6. Mu.g/mL C is used alone 18 -KK 2 The removal rate can reach more than 95% after 30 minutes after removing algae, but the algae cells after flocculation sedimentation are easy to generate resuspension phenomenon when being subjected to external force. After the composite algicide is used, only 4 mug/mL of C is needed 18 -KK 2 The removal rate of the algae cells can reach over 96% within 15min, and the settled algae cells are not easy to re-suspend, so that the water body is clear.
The composite algicide has obvious algicide effect, less algicide consumption, shorter time and high algicide efficiency. Meanwhile, the algae removal method of the invention is convenient to operate, and C is directly used 18 -KK 2 The method is used in combination with sepiolite, so that the algae removal method is simpler and easier to operate, and is more convenient, practical and efficient than the prior art.
Drawings
FIG. 1 shows the use of amphiphilic dendrimer C alone 18 -KK 2 Different C's when removing algae 18 -KK 2 Relationship between concentration and algae removal effect;
FIG. 2 is a graph showing the relationship between different sepiolite concentrations and algae removal effects;
wherein the curve B is the relationship between different sepiolite concentrations and the algae removal effect when sepiolite is used alone; curve A is at 4 μg/mL C 18 -KK 2 In the composite algicide, the concentration of sepiolite has influence on the algicide effect.
Detailed Description
The present invention will be further specifically described below by way of examples in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1: amphiphilic dendrimer C 18 -KK 2 Removing microcystis aeruginosa
At a plurality of algae concentrations of 3.0X10 9 Adding amphiphilic dendrimer C into each/mL water body sample with pH of 7.0 18 -KK 2 So that the final concentrations are 0. Mu.g/mL, 1. Mu.g/mL, 2. Mu.g/mL, 3. Mu.g/mL, 4. Mu.g/mL, 5. Mu.g/mL, 6. Mu.g/mL and 7. Mu.g/mL, respectively, and the mixture is rapidly stirred at 400 rpm for 1 minute, and then at 100 rpm for 14 minutes, and after standing for 30 minutes, the algae removal efficiency is observed and detected, and the result is shown in FIG. 1.
For amphiphilic dendrimer C 18 -KK 2 Observing the algae removal process of a water body sample with the final concentration of 6 mug/mL, and observing that algae cells in the water body begin to aggregate together in the rapid stirring process; during slow stirring, the increase of flocculate can be observed, and the volume of flocculate is larger and larger; after standing for 30 minutes, the algae cell floccules settle to the water bottom, the water body becomes clear, the algae liquid is sucked below the liquid level (2 cm) to measure the chlorophyll a content, and the algae removal efficiency can reach 95.28 percent.
Example 2: composite algicide for removing microcystis aeruginosa
At a plurality of algae concentrations of 3.0X10 9 Sepiolite is added into each mL of water body sample with pH of 7.0 to make the final concentration of the sepiolite be 40mg/L, 80mg/L, 120mg/L, 160mg/L, 200mg/L, 240mg/L, 280mg/L and 320mg/L respectively, and then amphiphilic tree-like substance is addedMolecule C 18 -KK 2 The final concentration is 4 mug/mL, and the algae cells in the water body can be observed to start to agglomerate together during the stirring process after being rapidly stirred for 1 minute at the speed of 400 revolutions per minute; stirring at a speed of 100 rpm for 14 min, the increase of flocculate is observed, the volume of flocculate is larger and larger, and the volume ratio of flocculate is only added with C 18 -KK 2 In the embodiment 1 of the method, after the algae cell floccules are settled to the bottom of water after being kept stand for 15 minutes, the water body becomes clear, and the algae removal efficiency of the water body sample with the final concentration of the sepiolite of 200mg/L can reach 96.03 percent. The algae removal effect is shown in figure 2.
This is because, after addition of sepiolite, sepiolite and algal cells having negative charges are simultaneously attached to amphiphilic dendrimer C having positive charges 18 -KK 2 Therefore, the volume of the flocculating constituent is increased, the descending speed of the flocculating constituent is accelerated, and a large amount of algae cells are swept in the descending process, so that C is needed 18 -KK 2 The amount is much smaller.
Comparative example 3
Example 1 was compared with the algae removal effect of other common flocculants and the results are shown in table 1.
TABLE 1
Comparative example 4
The algaecide effect of example 2 was compared with that of other common clay composite algaecides, and the results are shown in table 2.
TABLE 2
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.