CN108892202B - Method for treating chlorothalonil in water by using natural product salicylic acid - Google Patents
Method for treating chlorothalonil in water by using natural product salicylic acid Download PDFInfo
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Images
Classifications
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention provides a method for treating chlorothalonil in water by using a natural product salicylic acid, which comprises the steps of taking a high-pressure mercury lamp as a light source, providing light intensity of 84000lx-93000lx, dissolving salicylic acid into an aqueous solution or directly putting salicylic acid into a water body to be treated, wherein the input amount of the salicylic acid is 0.52mg/L-1.3mg/L, the illumination time is 10-15min, the removal rate of the chlorothalonil after treatment is more than 95%, and a high-toxicity metabolite, namely 4-hydroxychlorothalonil is not generated. The method can efficiently remove chlorothalonil in water, does not produce high-toxicity metabolite 4-hydroxychlorothalonil, and has the advantages of low cost, environmental protection, strong practicability and the like.
Description
Technical Field
The invention relates to the technical field of treatment of pollutants in water, in particular to treatment of an organic pollutant chlorothalonil contained in water. More particularly, the invention relates to a method for treating chlorothalonil in water by using a natural product salicylic acid as an additive, which can comprise pretreatment of pollution of natural water and farmland water, high-concentration production pollution and the like.
Background
The background of the related art of the present invention will be described below, but the description does not necessarily constitute the prior art of the present invention.
Chlorothalonil is a non-systemic protective broad-spectrum bactericide, belongs to chlorobenzene bactericides, can effectively prevent and treat fungal diseases on fruits, vegetables, grains, economic crops and other crops, is widely used all over the world, and can also be used as an antifouling paint additive. The action mechanism is that the enzyme can combine with protein containing cysteine in the glyceraldehyde triphosphate dehydrogenase in the fungal cells to act, thereby destroying the activity of the enzyme and destroying the metabolism of the fungal cells to make the fungal cells lose vitality. Chlorothalonil has a great toxicity to microorganisms, fishes and amphibians in water, and has a certain mutagenic effect. In addition, the residual chlorothalonil in the environment can generate a metabolite 4-OH chlorothalonil which has higher toxicity and is more stable and difficult to migrate compared with the parent chlorothalonil in the biodegradation and photochemical degradation processes. The high frequency of using the chlorothalonil can cause the chlorothalonil to pollute the water environment. Biodegradation and chemical degradation are the main methods for treating chlorothalonil in water at present. However, the degradation of chlorothalonil in water by the metabolic activity of microorganisms easily produces high-grade 4-hydroxychlorothalonil, and the biodegradation process needs to be adjusted to a microbial degradable state by other process conditions, so that the treatment cost is increased. The novel material with unknown environmental safety is used for treating environmental pollutants, so that secondary pollution is easily caused and the environmental risk is increased. In addition, there are other treatment techniques, including for example activated carbon adsorption and coagulation, which do not ultimately degrade the chlorothalonil precursor. In addition, 4-hydroxychlorothalonil, which is highly toxic, is also produced by ordinary photodegradation.
In addition, proanthocyanidins extracted from natural plants have been used in the production of chlorothalonil in water. The toxicity-enhancing metabolic pathway can be effectively changed by adding the natural extract procyanidin, but the method has the advantages of higher requirement on the concentration of added substances, higher cost, longer degradation half-life period and certain influence on the environment.
Therefore, there is still a need for a method for degrading chlorothalonil in water, which overcomes the aforementioned problems, and is environmentally friendly, efficient and nontoxic.
Disclosure of Invention
The present invention has been made to solve the above problems. The invention provides a method for treating chlorothalonil in water by using a natural product salicylic acid.
According to one aspect of the invention, a method for treating chlorothalonil in water by using natural product salicylic acid is provided, a high-pressure mercury lamp is used as a light source, the light intensity is 840001x-930001x, the salicylic acid is dissolved into an aqueous solution or directly put into a water body to be treated, the input amount of the salicylic acid is 0.52mg/L-1.3mg/L, the illumination time is 10-15min, the removal rate of the chlorothalonil after treatment is more than 95%, and a highly toxic metabolite, namely 4-hydroxychlorothalonil, is not generated.
Preferably, the water body to be treated is natural water body or sewage, the pH value is 4.5-9.5, the temperature of the water body to be treated is 25 +/-2 ℃, and the concentration of chlorothalonil in the water body is less than 0.5 mg/L.
Preferably, the input amount of the salicylic acid is 1.3mg/L, the illumination time is 15min, the removal rate of the chlorothalonil after treatment is 97%, and a highly toxic metabolite, namely 4-hydroxychlorothalonil, is not generated.
Preferably, the molar concentration ratio of chlorothalonil and salicylic acid may be any one of the following: 1: 0.5, 1: 1, 1:2, 1:3, 1: 5.
Preferably, the molar concentration ratio of chlorothalonil and salicylic acid is 1: 5.
The method for treating chlorothalonil in water by using the natural product salicylic acid can efficiently remove chlorothalonil in water, does not generate a highly toxic metabolite, namely 4-hydroxychlorothalonil, and has the technical effects of low cost, environmental protection and strong practicability.
Drawings
The features and advantages of the present invention will become more readily appreciated from the detailed description section provided below with reference to the drawings, in which:
FIG. 1 is a high performance liquid chromatography detection result chart of chlorothalonil in distilled water by salicylic acid under a high-pressure mercury lamp;
FIG. 2 is a comparison of photochemical degradation of chlorothalonil in the absence of salicylic acid and with the addition of salicylic acid under sunlight.
Detailed Description
Exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The description of the exemplary embodiments is for purposes of illustration only and is not intended to limit the invention, its application, or uses.
It is known that salicylic acid (CAS: 6972-7) is a plant secondary metabolite, an important signal molecule in plant biotic and abiotic stress resistance, can induce a variety of plants to generate continuous resistance, and also induce the generation and regulation of many relevant plant resistance enzymes. The salicylic acid can also promote the increase of the lignin content in the plant body, induce the generation of plant defensin and enhance the disease resistance of the plant. Furthermore, most importantly, salicylic acid is not harmful to humans and the environment.
In view of the above, the inventor of the present application has developed a method for treating chlorothalonil in water by using salicylic acid based on the above characteristics of salicylic acid, so as to overcome the defects in the prior art, and provide a method for treating chlorothalonil in water with low cost and more environmental protection.
The sources of the raw materials employed in the examples detailed below are illustrated below: the salicylic acid is 2-hydroxybenzoic acid, available from Shanghai Bailingwei science and technology Limited. The used Chlorothalonil standards are all named 2, 4, 5, 6-tetrachloroisophthalonitrile, English name is Chlorothalonil, and are purchased from Shanghai Bailingwei science and technology Limited. The acetonitrile used is chromatographically pure at a level of 99.9% or more, and is available from Tiandi corporation, Inc., USA (TEDIA for short). The methanol is pure by primary chromatography, the content is more than 99.9 percent, and the methanol is purchased from Tianjin Si you Fine chemicals Co.
Example 1
In this example, the inventors of the present application provided light irradiation under which salicylic acid was used for the treatment of chlorothalonil in distilled water using a high-pressure mercury lamp as a light source.
The chlorothalonil standard substance is prepared into chlorothalonil standard solution with the concentration of 500.0mg/L by using acetonitrile, and the Salicylic Acid (SA) is prepared into five kinds of salicylic acid standard solutions with the concentrations of 130.0mg/L, 260.0mg/L, 520.0mg/L, 780.0mg/L and 1300.0mg/L by using methanol. Respectively adding 10.0uL of chlorothalonil standard solution into six groups of quartz glass tubes, wherein each group comprises three tubes; adding salicylic acid standard solution with concentration of 130.0mg/L into the first group respectively, wherein the concentration of the salicylic acid standard solution is 10.0 mu L; adding salicylic acid standard solution with concentration of 260.0mg/L into the second group respectively to obtain 10.0 μ L; adding salicylic acid standard solution with concentration of 520.0mg/L into the third group respectively to obtain 10.0 μ L; adding salicylic acid standard solution 10.0 μ L with concentration of 780.0mg/L into the fourth group; adding salicylic acid standard solution with concentration of 1300.0mg/L into the fifth group respectively to obtain 10.0 μ L; the sixth group was set as blank control. Using secondary redistilled water to fix the volume of the reaction system in each quartz glass tube to 10mL to obtain six groups of to-be-irradiated treatment liquids with molar concentration ratios of chlorothalonil and salicylic acid of 1: 0, 1: 0.5, 1: 1, 1:2, 1:3 and 1: 5; meanwhile, six groups of treatment solutions were prepared as dark control groups without irradiation according to the above-mentioned operation methods. And (3) placing the six groups of irradiation treatment solutions and the blank control group under a high-pressure mercury lamp for photodegradation, wherein the light source is a 150W high-pressure mercury lamp, and the indoor temperature is 25 ℃. The photolytic removal rate of chlorothalonil was calculated as [ [ (C0-C1)/C0] × 100) removal rate, [% C0] initial concentration of chlorothalonil, and C1 ] residual concentration of chlorothalonil after treatment
FIG. 1 is a graph showing the effect of different concentrations of salicylic acid (0mg/L, 0.13mg/L, 0.26, 0.52mg/L, 0.78mg/L, 1.3 mg/L) on chlorothalonil (0.5mg/L) under the above conditions, wherein the ordinate is molar concentration of chlorothalonil in water, and the abscissa is photolysis time, and the samples are respectively sampled and detected at the time points of 0min, 3min, 6min, 9min, 12min and 15min of illumination, wherein the minimum removal rate of chlorothalonil in the water of 3min of illumination is 20.1% (salicylic acid concentration 0.130mg/L) and the maximum 72.1% (salicylic acid concentration 1.300mg/L), the minimum removal rate of chlorothalonil in the water of 9min of illumination is 40.7% (salicylic acid concentration 0.130mg/L) and the maximum 98.4% (salicylic acid concentration 1.300mg/L), the illumination treatment is 15min, and the three groups of high concentrations (salicylic acid concentration 0.520mg/L, 0.780mg/L and 0.4 mg/L), 1.300mg/L) of the light treatment solution, the removal rate of the chlorothalonil reaches over 95 percent, such as 97 percent, and the chlorothalonil of six dark control groups is not degraded basically.
Conversion rate of high-toxicity degradation product 4-hydroxy chlorothalonil
After the six groups of irradiation treatment solutions are subjected to the photodegradation treatment, detecting the content of a high-toxicity intermediate product, namely 4-hydroxychlorothalonil, by using a high performance liquid chromatography technology, and calculating the conversion rate of the high-toxicity intermediate product; the conversion rate of the chlorothalonil into the high-toxicity product 4-hydroxy chlorothalonil is obviously reduced by the treatment liquid treated by the salicylic acid. Irradiating by high-pressure mercury lamp for 6min, and converting the chlorothalonil into 4-OH chlorothalonil with the control group of 0.5mg/L of chlorothalonil photolysis liquid at a conversion rate of 12.3%. In the experimental group hydrolysate, when the molar concentration ratio of chlorothalonil to salicylic acid is 1: 0.5, 1: 1, 1:2, 1:3 and 1:5, the conversion rate of converting chlorothalonil into 4-hydroxychlorothalonil is 6.7%, 5.6%, 4.8%, 4.2% and 4.5% respectively.
Example 2
Treating chlorothalonil in distilled water with salicylic acid under sunlight irradiation.
FIG. 2 is a comparison of photochemical degradation of chlorothalonil in the absence of salicylic acid and with the addition of salicylic acid under sunlight. The chlorothalonil standard substance is prepared into chlorothalonil standard liquid with the concentration of 500.0mg/L by using acetonitrile, and the Salicylic Acid (SA) is prepared into standard liquid with the concentration of 260.0mg/L by using methanol. Respectively adding 10.0uL of chlorothalonil standard solution into the two groups of quartz glass tubes, adding 10.0 muL of salicylic acid standard solution with the concentration of 260.0mg/L into one group of quartz glass tubes, and finally metering to 10mL to ensure that the molar concentration ratio of chlorothalonil to salicylic acid is 1: 2. The experimental site is the compound fertilizer (31 degrees in north latitude and 52 minutes in east longitude and 117 degrees in east longitude and 17 minutes in east longitude), the light intensity is 265001x, and the outdoor temperature is 24 ℃ when the light is irradiated. The effect of salicylic acid (0.560mg/L) on chlorothalonil (0.5mg/L) is shown in FIG. 2, where the ordinate of FIG. 2 is the concentration of chlorothalonil in water and the abscissa is the photolysis time. Sampling at time points of natural illumination of 0min, 3min, 6min, 9min, 12min and 15min, and detecting to obtain figure 2, wherein the removal rate of chlorothalonil after illumination treatment for 15min reaches 46.3%. (removal rate [ (C0-C1)/C0] × 100)%, C0 is the initial concentration of chlorothalonil, and C1 is the residual concentration of chlorothalonil after treatment).
Experiments prove that the technical effects of the invention are embodied in the following aspects:
1. salicylic acid can effectively promote photochemical degradation of chlorothalonil in water under irradiation of two light sources
However, under the illumination of a high-pressure mercury lamp, the photodegradation rate constant of the chlorothalonil is 0.019 mu mol/min, and the photolysis half-life is 34.67 min; when the concentration (mol/L) ratio of the salicylic acid to the chlorothalonil is 5: 1, the degradation rate is increased to 0.441 mu mol/min, the half life is reduced to 1.57min, and the photolysis rate of the chlorothalonil is increased by 23.2 times; when the concentration (mol/L) ratio of the salicylic acid to the chlorothalonil is 2: 1, the degradation rate is 0.205 mu mol/min, the half-life period is 3.38min, and the degradation rate is 10.8 times that of a control group. Under the irradiation of sunlight, the photodegradation rate constant of chlorothalonil is 0.015 mu mol/min, and the photolysis half-life period is 46.2 min; when the concentration (mol/L) ratio of the salicylic acid to the chlorothalonil is 2: 1, the degradation rate of the chlorothalonil is 0.042 mu mol/min, the half-life period is 16.50min, and the degradation rate is increased by 2.8 times. Therefore, the high-pressure mercury lamp and the sunlight can be used as light sources to treat the chlorothalonil in the water by using the salicylic acid, but the technical effect of the method is far greater than that of the method using the sunlight as the light sources by using the high-pressure mercury lamp as the light sources.
2. Effect of salicylic acid in inhibiting generation of highly toxic metabolites of chlorothalonil under irradiation of two light sources
Under the irradiation of a high-pressure mercury lamp and sunlight, the generation of 4-hydroxychlorothalonil (LOD ═ 0.005mg/L) can be detected in a photodegradation product of an aqueous chlorothalonil solution (0.5mg/L), however, when the molar concentration ratio of salicylic acid to chlorothalonil is 5: 1, that is, the molar concentration ratio of chlorothalonil to salicylic acid is 1:5, the conversion rate of chlorothalonil into 4-hydroxychlorothalonil can be reduced by adding salicylic acid and phenol at various time points of the reaction, the higher the concentration of the added substance is, the lower the conversion rate of 4-hydroxychlorothalonil is, and the additive has no photosensitization effect on 4-hydroxychlorothalonil. It is thus shown that the technical effect is optimized when the molar concentration ratio of the salicylic acid to the chlorothalonil is set to 5: 1, i.e. the molar concentration ratio of the chlorothalonil to the salicylic acid is 1: 5.
Although the present invention has been described in detail with reference to the exemplary embodiments, it is to be understood that the present invention is not limited to the specific embodiments described and illustrated in detail herein, and that various changes may be made therein by those skilled in the art without departing from the scope defined by the appended claims, which changes are intended to fall within the scope of the invention.
Claims (4)
1. A method for treating chlorothalonil in water by using a natural product salicylic acid is characterized in that a high-pressure mercury lamp is used as a light source, the light intensity is 84000lx-93000lx, the salicylic acid is dissolved into an aqueous solution or is directly put into a water body to be treated, the concentration of the chlorothalonil is 0.5mg/L, the input amount of the salicylic acid is 0.52mg/L-1.3mg/L, the illumination time is 10-15min, the removal rate of the chlorothalonil after treatment is more than 95%, and a high-toxicity metabolite, namely 4-hydroxychlorothalonil, is not generated.
2. The method for treating chlorothalonil in water by using the natural product salicylic acid as claimed in claim 1, wherein the water body to be treated is natural water body or sewage, the pH value is 4.5-9.5, the temperature of the water body to be treated is 25 +/-2 ℃, and the concentration of the chlorothalonil in the water body is less than 0.5 mg/L.
3. The method for treating chlorothalonil in water by using the natural product salicylic acid as claimed in claim 1 or 2, wherein the input amount of the salicylic acid is 1.3mg/L, the illumination time is 15min, the removal rate of the chlorothalonil after treatment is 97%, and the highly toxic metabolite 4-hydroxychlorothalonil is not generated.
4. The method for treating chlorothalonil in water by using natural product salicylic acid as claimed in claim 1, wherein the molar concentration ratio of the chlorothalonil and the salicylic acid is any one of the following components: 1:2, 1:3, 1: 5.
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| WO2012108198A1 (en) * | 2011-02-10 | 2012-08-16 | ソニー株式会社 | Decontaminant, carbon/polymer composite, decontamination sheet member and filter material |
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| CN101898852A (en) * | 2010-05-26 | 2010-12-01 | 蓝星环境工程有限公司 | Method for treating chlorothalonil pesticide wastewater |
| WO2012108198A1 (en) * | 2011-02-10 | 2012-08-16 | ソニー株式会社 | Decontaminant, carbon/polymer composite, decontamination sheet member and filter material |
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