CN113287630A - Red tide algae algaecide based on procyanidine activated persulfate and application thereof - Google Patents
Red tide algae algaecide based on procyanidine activated persulfate and application thereof Download PDFInfo
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- CN113287630A CN113287630A CN202110614548.5A CN202110614548A CN113287630A CN 113287630 A CN113287630 A CN 113287630A CN 202110614548 A CN202110614548 A CN 202110614548A CN 113287630 A CN113287630 A CN 113287630A
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- red tide
- algaecide
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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 an algaecide based on procyanidin activated persulfate, which is prepared from 9-48% by mass of procyanidin, 45-83% by mass of persulfate, 2-5% by mass of a dispersant and 3-5% by mass of an auxiliary material. When in use, the red tide algae algaecide is mixed with seawater or fresh water to prepare a uniform solution, and the uniform solution is sprayed on the surface of a red tide water body and can effectively remove the red tide after natural sedimentation. The algaecide has high efficiency, green and sustainability, can effectively improve the potential environmental impact of the existing heterogeneous algaecide, and remarkably improves the efficiency of treating red tide water body through an inactivation-apoptosis-sedimentation algaecide mechanism.
Description
Technical Field
The invention belongs to the field of control and treatment of red tide, and particularly relates to a red tide algae algaecide based on proanthocyanidin activated persulfate and application thereof.
Background
Red tide, also known as red tide, is also known as "harmful algae" or "red ghost" internationally. The method is a harmful ecological phenomenon that some phytoplankton, protozoan or bacteria in seawater are explosively proliferated or highly aggregated to cause water body discoloration under specific environmental conditions, and can bring about the problems of fish death, water quality pollution and the like. Since the 21 st century, red tide disasters occur in the country on average 70-80 times per year, and become one of the main marine disasters. Therefore, the research and development of the efficient, green and sustainable red tide algae removal agent has important significance and urgent need.
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. At present, the treatment method of red tide is mainly divided into a physical method, a chemical method and a biological 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; chemical methods include chemical killing methods and flocculation methods. 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 is that the cost of spreading a large amount of clay is high, the effect is slow, and secondary rebound is possible to cause pollution.
Compared with the influence of a large amount of spraying by a heterogeneous flocculation method on the environment, the homogeneous process with less influence on the environment is selected to be more beneficial to the treatment, prevention and control of the red tide. The advanced oxidation of natural flavone is concerned by scholars at home and abroad in recent years, various pollutants can be effectively degraded by activating persulfate through natural flavonoid substances, and the process also has potential application value to red tide algae, but no relevant research report is found.
Disclosure of Invention
The invention aims to provide a red tide algae algaecide based on procyanidin activated persulfate and application thereof, which can effectively solve 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.
The technical scheme of the invention is as follows:
a red tide algae algaecide based on procyanidine activated persulfate is prepared by uniformly 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.
The persulfate is sodium persulfate, potassium hydrogen persulfate or ammonium persulfate.
The content of the procyanidin is 75-99% of the industrial grade.
When in use, the red tide algae algaecide is mixed with seawater or fresh water to prepare a concentration, and the concentration is sprayed on the surface of a red tide water body, so that the solution naturally settles for 3-24 hours and 0.001-0.5g L-1 of the red tide algae algaecide in the red tide water body, and the red tide algae is effectively removed.
The red tide algae is spherical phaeocystis, red tide yizhuan algae, Skeletonema costatum or prorocentrum donghaiense.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts an advanced oxidation process of activating persulfate by procyanidine, and utilizes sulfate radicals and hydroxyl free radicals generated in the advanced oxidation process to inhibit the activity of red tide algae so as to inactivate and settle. 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 24h, and the removal efficiency of the algaecide provided by the invention can reach more than 80% within 16h
3. Compared with the existing algaecide, the algaecide of the invention has obvious advantages of 0.4g L-1The algaecide can achieve more than 80 percent of removal effect, and the using amount of the existing heterogeneous algaecide needs 0.5g L-1The above. 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, the procyanidin, the persulfate, the dispersing agent and the auxiliary materials have small influence on the aquatic environment, and the procyanidin is a natural organic matter in the nature, so that the biological compatibility of the algaecide is good.
Drawings
FIG. 1 is a graph showing the efficiency of red tide algaecide with different concentrations 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 is 0.4g 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 four different formulations for removing prorocentrum donghaiense, wherein the initial concentration of prorocentrum donghaiense has a biological density of 107cells L-1。
Detailed Description
The red tide algae algaecide is prepared by uniformly mixing procyanidine, persulfate, a dispersant and auxiliary materials. In the red tide algae algaecide, the dosage of the procyanidin, the persulfate and the dispersant can be adjusted according to the characteristics of the water body, such as the change of salinity and biomass. Usually, the mass percent of the procyanidin is between 9 and 48 percent, the mass percent of the persulfate is between 45 and 83 percent, and the mass percent of the dispersant is between 2 and 5 percent, which is the best. When in use, the red tide algae algaecide is mixed with seawater (or fresh water) to prepare a uniform solution with a certain concentration (0.001-0.5g 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 9% of procyanidine, 83% of sodium persulfate, 4% of polyethylene glycol and 4% of potassium nitrate in 1L of seawater to obtain an algaecide solution 1;
control 2: uniformly mixing procyanidin 9 wt%, polyethylene glycol 4 wt% and potassium nitrate 4 wt% in 1L seawater to obtain algaecide solution 2;
control 3: uniformly mixing 83 mass percent of sodium persulfate, 4 mass percent of polyethylene glycol and 4 mass percent of potassium nitrate in 1L of seawater to obtain an algaecide solution 3;
blank 4: polyethylene glycol with the mass content of 4% and potassium nitrate with the mass content of 4% are uniformly mixed in 1L of seawater to be used as the algaecide solution 4.
4 parts of red tide water body with the phaeocystis globosa growing thereon, 9L of each red tide water body are respectively sprayed with the red tide algae algaecide solution, 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 liquid is 0.4g L-1. And (5) after standing for 16h, observing the change of the density of the spherical phaeocystis fuscus in the algae liquid.
The algae removal efficiency of different algaecides is shown in figure 1, and the result shows that when the algaecide system contains procyanidin and sodium persulfate, the spherical phaeocystis globosa can be effectively removed, and the removal rate reaches 95%.
Example 2
The red tide algae algaecide solution is prepared by uniformly mixing 22% of procyanidine, 73% of potassium hydrogen peroxymonosulfate, 2% of gelatin and 3% of potassium sulfate in 1L of seawater.
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 0.05g L-1、0.1g L-1、0.2g L-1、0.3g L-1、0.4g L-1. Standing for 6h, and observing the density change of red tide heterocurvula in the algae liquid.
The algae removal efficiency of the algaecide with different concentrations is shown in figure 2, and the result shows that when the concentration of the algaecide in the red tide is 0.3g L-1And above, for biological densities up to 108cells L-1The removal rate of the red tide heterocurvula can reach more than 90 percent.
Example 3
The red tide algae algaecide solution is prepared by uniformly mixing 34% of procyanidine, 60% of ammonium persulfate, 2% of alginic acid and 4% of sodium gluconate in 1L of seawater.
Taking 6 parts of red tide water body with prorocentrum donghaiense, spraying 9L of red tide water body with the above red tide algae algaecide solution, wherein the initial concentration biological density of prorocentrum donghaiense in algae solution is 107cells L-1The concentrations of algaecide in the algae solution are 0 and 0.05g L respectively-1、0.1g L-1、0.15g L-1、0.2g L-1、0.25g L-1And standing for 10h, and observing the density change of the prorocentrum donghaiense in the algae liquid.
The algae removal efficiency of the algaecide with different concentrations is shown in figure 3, and the result shows that when the concentration of the algaecide in the red tide reaches 0.25g L-180% of prorocentrum donghaiense can be removed.
Example 4
Mixing procyanidin 48 wt% and persulfuric acid 45 wt%Sodium, 4% of sodium dodecyl sulfate and 3% of sodium nitrate are uniformly mixed in 1L of seawater to obtain 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 algaecide in the algae solution is 0.1g L-1. After standing for 5h, more than 95% 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 the procyanidine activated persulfate is characterized by being prepared by uniformly mixing the following components in percentage by mass:
9 to 48 percent of procyanidine,
45 to 83 percent of persulfate,
2 to 5 percent of dispersant,
3 to 5 percent of auxiliary materials,
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, oxone, or ammonium persulfate.
3. The red tide algae algaecide of claim 1, wherein the procyanidin technical grade is 75-99%.
4. Use of the red tide algae algaecide according to any one of claims 1-3, wherein: the red tide algae algaecide is mixed with seawater or fresh water to prepare concentration, and the concentration is sprayed on the surface of a red tide water body, so that the solution naturally settles for 3-24 hours and the red tide algae is effectively removed, wherein the concentration of the red tide algae algaecide in the red tide water body is 0.001-0.5g L-1.
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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| CN202110614548.5A CN113287630A (en) | 2021-06-02 | 2021-06-02 | Red tide algae algaecide based on procyanidine activated persulfate and application thereof |
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Citations (4)
| 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 |
| 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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2021
- 2021-06-02 CN CN202110614548.5A patent/CN113287630A/en active Pending
Patent Citations (4)
| 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 |
| 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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