CN113287629A - Arbutin-activated persulfate-based red tide algae algaecide and application thereof - Google Patents
Arbutin-activated persulfate-based red tide algae algaecide and application thereof Download PDFInfo
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- CN113287629A CN113287629A CN202110614546.6A CN202110614546A CN113287629A CN 113287629 A CN113287629 A CN 113287629A CN 202110614546 A CN202110614546 A CN 202110614546A CN 113287629 A CN113287629 A CN 113287629A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a red tide algae algaecide based on arbutin activated persulfate and application thereof, wherein the red tide algae algaecide is formed by mixing 7.3-84.5 wt% of arbutin, 10.5-87.7 wt% of persulfate, 2-3 wt% of dispersant and 2-3 wt% of auxiliary materials, and when the red tide algae algaecide is used, the red tide algae algaecide is mixed with seawater or fresh water to prepare a solution which is sprayed on the surface of a red tide water body, and the red tide is effectively removed after natural sedimentation for 8-24 hours. The efficient, green and sustainable red tide algae removal agent effectively improves the potential influence of the existing heterogeneous phase algae removal agent on the environment, inhibits the activity of red tide algae by utilizing the homogeneous phase advanced oxidation process of arbutin activated persulfate, enables the algae cells to settle, and remarkably improves the efficiency of treating red tide water bodies through an inactivation-apoptosis-settlement algae removal mechanism.
Description
Technical Field
The invention relates to a method for treating seawater red tide pollution, in particular to a red tide algae algaecide based on arbutin activated persulfate and application thereof.
Background
Red tide is an ecological abnormal phenomenon that some microalgae, protozoa or bacteria are explosively proliferated or gathered to a certain level under certain environmental conditions to cause water body discoloration or harm to other organisms in the ocean. In the marine system, microalgae play an important role not only in providing food to other aquatic organisms at the bottom of the food chain, but also in the global carbon cycle, and they absorb carbon dioxide from the atmosphere through photosynthesis, thereby performing a carbon sequestration effect. However, under certain conditions, certain species proliferate explosively and accumulate or produce toxins to form harmful algal blooms, which are generally called red tides because they cause the water to appear red. In recent years, the aforementioned Harmful ecological phenomena are collectively called Harmful Algal Bloms (HAB) by the international scientific community.
In recent years, as the level of carbon dioxide rises, the global climate becomes warm, and the eutrophication degree of water body becomes more and more serious, the occurrence scale and frequency of harmful algal blooms generally tend to increase year by year. The frequently-occurring harmful algal blooms not only can cause massive death of marine organisms to reduce the yield of marine fishery on a large scale, but also can indirectly influence human health through the enrichment of red tide toxins, and can break the dynamic balance of marine ecological environment. Since the 70 s of the 20 th century, more than 3000 red tide disasters occurred in coastal waters in China, and the economic loss caused by each year is as high as billions of RMB. Therefore, the prevention and control of red tide disasters are necessary for the development of marine ecology and human health in China. Because of the great harm of red tide to the economy and human health, the treatment measures of red tide have been the focus of attention and research. The method can be roughly divided into two research directions, wherein one research direction is to reduce the occurrence frequency of the red tide by early detection and early warning before the occurrence of the red tide disaster; the other is that after a disaster occurs, the influence area of the red tide is reduced by treating red tide organisms, so that the harm of the red tide is weakened, and the treatment measures can be roughly divided into a biological method, a physical method and a chemical method. The physical method is mainly to remove algae by using mechanical equipment and applying air flotation, ultrasonic waves, stirring, adsorption and the like; biological methods use zooplankton, macrophytes, microorganisms, and filter-feeding shellfish to inhibit or eliminate microalgae; the chemical method mainly comprises a medicament killing method and a flocculation method. The flocculation sedimentation method has prominent research results, and particularly, a great deal of research is carried out at home and abroad on the flocculation aspect of the modified clay. However, the method has certain defects, and the red tide removing biological capacities of different types of clay minerals and even the same type of clay minerals are greatly different; different application modes also significantly affect the ability of clay to remove red tide organisms; the key points are that the cost of scattering a large amount of clay is high, the effect is slow, secondary rebound is possible to generate pollution, and the growth of marine organisms is influenced by the large amount of clay.
The advanced oxidation process is a removal method which is widely applied in water pollution treatment in recent years, and has the characteristics of quick effect, low cost and small influence on the environment, so that the advanced oxidation process is widely concerned. The research that the advanced oxidation process is applied to the harmful algal blooms in the fresh water has been reported partially, but the work of the advanced oxidation process for treating the red tide algae is not seen. Persulfate is a common oxidant receptor, can be activated under the conditions of heat, ultrasound, ultraviolet, transition metal and the like to generate free radicals, acts on algae cells to inactivate the algae cells, and is removed by sedimentation. Arbutin, also known as arbutin, is a natural phenolic compound extracted from bearberry leaves of Ericaceae, is safe, nontoxic and has practical application value in marine environment. The research on removing red tide algae by arbutin activated persulfate has not been reported, and the advanced oxidation process has great research and practical application values due to the low cost and good biocompatibility of arbutin and persulfate.
Disclosure of Invention
The invention aims to provide a red tide algae algaecide based on arbutin activated persulfate and application thereof, which are used for effectively solving the problems of large spraying amount, large environmental influence, slow effect, easy rebound and easy secondary pollution of the existing heterogeneous red tide algae algaecide.
Therefore, the invention adopts the following technical scheme:
the red tide algae algaecide based on arbutin activated persulfate is characterized by being prepared by mixing the following components in percentage by mass:
wherein:
the dispersing agent is one or more of carrageenan, gelatin, alginic acid, hydroxypropyl cellulose, sodium dodecyl sulfate, polyethylene glycol, polypropylene glycol and alkyl monoglycoside;
the auxiliary materials are one or more of sodium chloride, sodium nitrate, sodium sulfate, sodium gluconate, potassium chloride, potassium nitrate and potassium sulfate.
Wherein the persulfate is sodium persulfate, potassium hydrogen persulfate or ammonium persulfate; the tannic acid is industrial grade, and the purity is 85-99%.
The application method of the red tide algae algaecide comprises the steps of preparing the red tide algae algaecide into a solution, spraying the solution on the surface of a red tide water body to enable the concentration of the red tide algae algaecide in the red tide water body to be 0.01-0.2g/L, and naturally settling for 8-24 hours to effectively remove the red tide algae. Wherein the red tide algae is phaeocystis globosa, red tide yizhuan algae, Skeletonema costatum or prorocentrum donghaiense.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts the advanced oxidation process of arbutin activated persulfate, and utilizes sulfate radicals and hydroxyl radicals generated in the advanced oxidation process to inhibit the activity of red tide algae, thereby inactivating and settling. Compared with the existing heterogeneous flocculation algaecide with more applications, the algaecide disclosed by the invention solves the problem that the existing algaecide only flocculates red tide algae and has small influence on activity. The risk of secondary rebound of red tide is reduced.
2. Compared with the existing algaecide, the algaecide provided by the invention inhibits the activity of red tide algae by utilizing a high-grade oxidation process, so that the effective time is shorter than that of a heterogeneous flocculation process, the effective time of the existing algaecide is more than 24 hours, and the removal efficiency of the algaecide can reach more than 80% within 8 hours
3. Compared with the existing algaecide, the algaecide of the invention has obvious advantages, the removal effect of more than 90% can be achieved by 0.06g L-1, and the use amount of the existing heterogeneous algaecide is more than 0.5g L-1. And because the invention is a homogeneous system, the problem that the seawater environment is turbid and the aquatic environment is influenced due to large input amount of the heterogeneous system is solved.
4. In the algaecide formula adopted by the invention, the arbutin, persulfate, dispersant and auxiliary materials have small influence on the aquatic environment, and the arbutin is a natural organic matter in the nature, so that the biological compatibility of the algaecide is good.
5. The red tide algae algaecide developed by the invention has high efficiency, greenness and sustainability, effectively improves the potential environmental impact of the existing heterogeneous algaecide, and inhibits the activity of red tide algae by utilizing the homogeneous advanced oxidation process of arbutin activated persulfate so as to settle algae cells; the efficiency of treating the red tide water body is obviously improved through an algae removal mechanism of inactivation, apoptosis and sedimentation.
Drawings
FIG. 1 is a graph showing the efficiency of red tide algaecide with four different formulations for removing phaeocystis globosa according to the embodiment of the present invention, wherein the initial concentration of phaeocystis globosa has a biological density of 109cells L-1The concentration of the algaecide for red tide algae in the algae liquid is 0.2g L-1。
FIG. 2 is a graph showing the efficiency of red tide algaecide with different concentrations in removing red tide bent algae according to the embodiment of the present invention, wherein the initial concentration of bent algae reaches a biological density of 108cells L-1。
FIG. 3 is a graph showing the efficiency of red tide algaecide with different concentrations in removing prorocentrum donghaiense with the initial concentration of the prorocentrum donghaiense with biological density of 107cells L-1。
Detailed Description
The red tide algae algaecide of the invention is prepared from arbutin, persulfate and certainThe dispersant and the auxiliary materials are uniformly mixed. In the red tide algae algaecide, the dosage of arbutin, persulfate and dispersant can be adjusted according to the characteristics of water body, such as salinity and biomass change. Generally, the mass percent of arbutin is between 7.3 and 84.5 percent, the mass percent of persulfate is between 10.5 and 87.7 percent, and the mass percent of dispersant is between 2 and 3 percent, which is the best. When in use, the red tide algae algaecide based on arbutin activated persulfate is mixed with seawater (or fresh water) to prepare a uniform solution with a certain concentration (0.01-0.2g L)-1) The red tide is sprayed on the surface of a red tide water body, and after a certain period of natural sedimentation, the red tide can be effectively removed.
The invention is further illustrated by the following examples.
Example 1
Experiment 1: uniformly mixing 47.5% by mass of arbutin, 47.5% by mass of sodium persulfate, 2% by mass of polyethylene glycol and 3% by mass of sodium chloride in 1L of seawater to obtain an algaecide solution 1;
control 2: uniformly mixing 47.5% by mass of arbutin, 2% by mass of polyethylene glycol and 3% by mass of sodium chloride in 1L of seawater to obtain an algaecide solution 2;
control 3: uniformly mixing 47.5% of sodium persulfate, 2% of polyethylene glycol and 3% of sodium chloride in 1L of seawater by mass to obtain an algaecide solution 3;
blank 4: polyethylene glycol with the mass content of 2% and sodium chloride with the mass content of 3% are uniformly mixed in 1L of seawater to be used as algaecide solution 4.
4 parts of red tide water body with the phaeocystis globosa growing thereon, 9L of each water body are respectively sprayed with the 4 algaecide solutions, and the initial concentration biological density of the phaeocystis globosa in the algae solution reaches 109cells L-1The concentration of each algaecide in the algae solution was 0.2g L-1. And (5) observing the density change of the spherical phaeocystis fuscus in the algae liquid after standing for 24 hours.
The algae removal efficiency of different algaecides is shown in figure 1, and the result shows that only when tannin and sodium persulfate are simultaneously contained in the algaecide, the biological density can be effectively removed to 109cells L-1The spherical phaeocystisThe removal rate can reach more than 85 percent.
Example 2
Uniformly mixing 10.5% by mass of arbutin, 84.5% by mass of potassium hydrogen persulfate, 3% by mass of carrageenan and 2% by mass of sodium sulfate in 1L of seawater to prepare the red tide algae algaecide solution.
Taking 6 parts of red tide water body with red tide clockweed, spraying the red tide clockweed algaecide solution into 9L of each red tide water body, wherein the initial concentration biological density of the red tide clockweed in the algae solution reaches 108cells L-1The concentrations of the algaecide for red tide algae in the algae liquid are respectively 0 and 0.04g L-1、0.08g L-1、0.12g L-1、0.16g L-1、0.20g L-1And standing for 8h, and observing the density change of the red tide heterocurvula in the algae liquid. The algae removal efficiency of the algaecide at different concentrations is shown in figure 2.
The results show that when the concentration of the algaecide in the red tide is 0.16g L-1And above, for biological densities up to 108cells L-1The removal rate of the red tide heterocurvula can reach more than 80 percent.
Example 3
Uniformly mixing arbutin with the mass content of 87.7%, ammonium persulfate with the mass content of 7.3%, alginic acid with the mass content of 2% and sodium gluconate with the mass content of 3% in 1L of seawater to prepare the red tide algae algaecide solution.
Spraying red tide water body 6 parts with prorocentrum donghaiense (9L) respectively with the above red tide algae algaecide solution, wherein the initial concentration of prorocentrum donghaiense in the algae solution has biological density of 107cells L-1The concentrations of the algaecide for red tide algae in the algae liquid are respectively 0 and 0.02g L-1、0.04g L-1、0.06g L-1、0.08g L-1、0.1g L-1And standing for 12h, and observing the density change of the prorocentrum donghaiense in the algae liquid.
The algae removal efficiency of the different algaecides is shown in figure 3, and the result shows that when the concentration of the red tide algaecide is 0.06g L-1And above, for biological densities up to 107cells L-1The removal rate of prorocentrum donghaiense can reach more than 90%.
Example 4
Uniformly mixing 65.4% of arbutin, 29.6% of sodium persulfate, 3% of sodium dodecyl sulfate, polypropylene glycol and 2% of sodium nitrate in 1L of seawater to prepare the red tide algae algaecide solution. Spraying red tide algae algaecide solution to 9L of red tide water body with Skeletonema costatum, wherein the initial concentration of Skeletonema costatum in algae solution has biological density of 1010cells L-1The concentration of the algaecide for red tide algae in the algae liquid is 0.01g L-1After standing for 10h, more than 80% of skeletonema costatum can be removed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The red tide algae algaecide based on arbutin activated persulfate is characterized by being prepared by mixing the following components in percentage by mass:
wherein:
the dispersing agent is one or more of carrageenan, gelatin, alginic acid, hydroxypropyl cellulose, sodium dodecyl sulfate, polyethylene glycol, polypropylene glycol and alkyl monoglycoside;
the auxiliary materials are one or more of sodium chloride, sodium nitrate, sodium sulfate, sodium gluconate, potassium chloride, potassium nitrate and potassium sulfate.
2. The red tide algae algaecide of claim 1, wherein: the persulfate is sodium persulfate, potassium hydrogen persulfate or ammonium persulfate.
3. The red tide algae algaecide according to claim 1, wherein the arbutin is technical grade with a purity of 85-99%.
4. Use of the red tide algae algaecide according to any one of claims 1-3, wherein: the red tide algae algaecide is prepared into a solution and sprayed on the surface of a red tide water body, so that the concentration of the red tide algae algaecide in the red tide water body is 0.01-0.2g/L, and the red tide algae is effectively removed by natural sedimentation for 8-24 hours.
5. Use according to claim 5, characterized in that: the red tide algae is spherical phaeocystis, red tide yizhuan algae, Skeletonema costatum or prorocentrum donghaiense.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0096525A2 (en) * | 1982-06-03 | 1983-12-21 | Interox Chemicals Limited | Sanitizer compositions |
| CN103553247A (en) * | 2013-11-20 | 2014-02-05 | 哈尔滨理工大学 | Method for removing algae by using inorganic solid peroxide for inducing peroxymonosulfate to generate singlet oxygen |
| CN104649395A (en) * | 2013-11-19 | 2015-05-27 | 青岛水世界环保科技有限公司 | An efficient flocculant |
| CN105000655A (en) * | 2015-08-05 | 2015-10-28 | 同济大学 | Method for removing algae in water through oxidizing agent activated through ferrous iron |
| CN109942072A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method of natural polyphenol activation persulfate degradating chloro hydrocarbon |
-
2021
- 2021-06-02 CN CN202110614546.6A patent/CN113287629A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0096525A2 (en) * | 1982-06-03 | 1983-12-21 | Interox Chemicals Limited | Sanitizer compositions |
| CN104649395A (en) * | 2013-11-19 | 2015-05-27 | 青岛水世界环保科技有限公司 | An efficient flocculant |
| CN103553247A (en) * | 2013-11-20 | 2014-02-05 | 哈尔滨理工大学 | Method for removing algae by using inorganic solid peroxide for inducing peroxymonosulfate to generate singlet oxygen |
| CN105000655A (en) * | 2015-08-05 | 2015-10-28 | 同济大学 | Method for removing algae in water through oxidizing agent activated through ferrous iron |
| CN109942072A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method of natural polyphenol activation persulfate degradating chloro hydrocarbon |
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