A method for treating phenolic pollutants using peroxidase-catalyzed chloramines

Abstract

This invention provides a method for treating phenolic pollutants using chloramine based on peroxidase catalysis, comprising the following steps: adding chloramine and peroxidase to an aqueous solution containing phenolic pollutants to obtain a mixed solution; reacting under stirring conditions to obtain treated water. This method, by adding a small amount of peroxidase, can effectively catalyze the degradation of phenolic pollutants by chloramine. Compared with using chloramine alone, the degradation effect on phenolic organic pollutants in water is significantly improved, which has important practical significance for removing industrial and domestic wastewater rich in organic pollutants. The water treatment method provided by this invention has a simple reaction mechanism, mild reaction conditions, high catalytic efficiency, strong selectivity, and low cost, and can realize large-scale industrial production and utilization, showing broad application prospects in water pollution control and water environment remediation.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, and particularly relates to a method for treating phenolic pollutants based on peroxidase-catalyzed chloramine. Background Technology

[0002] Water is a fundamental resource for the survival and growth of all living things, and an indispensable element for economic development and daily life. The sustainable use of water resources has a profound impact on national development. Due to continuous economic progress and ongoing urbanization, water scarcity and pollution problems are becoming increasingly prominent. Therefore, wastewater treatment is a problem and challenge facing the world.

[0003] Phenolic compounds are common organic pollutants in water bodies, and most of them are biologically toxic to organisms and human cells and are widely present. For example, bisphenol A (BPA), as an important organic chemical raw material, is used in the production of some polymer materials and other chemical products, and is also widely used in many consumer products, including food packaging, paper products, water pipes, toys, medical facilities, and electronic devices. It has been reported that phenolic pollutants are widely detected in aquatic environments, and the resulting human health and ecological risks have attracted considerable attention.

[0004] Chloramine, as a reagent with weak oxidizing properties, is generally used in drinking water disinfection. However, its widespread application is severely limited due to its weak ability to inactivate microorganisms and remove organic matter. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a method for treating phenolic pollutants based on peroxidase-catalyzed chloramine, which has a high degradation rate for phenolic pollutants.

[0006] This invention provides a method for treating phenolic pollutants using peroxidase-catalyzed chloramine, comprising the following steps:

[0007] Chloramine and peroxidase were added to an aqueous solution containing phenolic pollutants to obtain a mixed solution. The solution was then reacted under stirring to obtain treated water.

[0008] This invention involves adding peroxidase and chloramine to a solution of phenolic pollutants. The chloramine, activated by the enzyme, degrades the organic pollutants in the water. This invention provides a new approach to the use of chloramine and enhances its disinfection capabilities.

[0009] In this invention, phenolic contaminants include, but are not limited to, one or more of halogenated phenols, bisphenol A (BPA), phenol, and parabens; the concentration of phenolic contaminants in the aqueous solution is 10–500 μmol / L; specifically, the concentration of phenolic contaminants in the aqueous solution is 10 μmol / L, 15 μmol / L, 20 μmol / L, 25 μmol / L, 30 μmol / L, 35 μmol / L, 40 μmol / L, 45 μmol / L, 50 μmol / L, 55 μmol / L, 60 μmol / L, 65 μmol / L, 70 μmol / L, 75 μmol / L, 80 μmol / L, 85 μmol / L, 90 μmol / L, 95 μmol / L, 100 μmol / L, 200 μmol / L, 300 μmol / L, 400 μmol / L, or 500 μmol / L.

[0010] The peroxidase described in this invention is selected from one or more of lignin peroxidase, chloride peroxidase, horseradish peroxidase, glutathione peroxidase, cytochrome C peroxidase, manganese peroxidase, and myeloperoxidase. This invention utilizes the above-mentioned peroxidases to catalyze chloramine, achieving more efficient and selective degradation of phenolic organic pollutants compared to chloramine alone. The method provided by this invention requires no additional reagents or equipment; simply adding a small amount of the above-mentioned enzymes significantly improves the degradation rate of pollutants.

[0011] In this invention, the mass ratio of chloramine to peroxidase is 0.5 to 50:1, preferably 3 to 20:1.

[0012] In this invention, the mass ratio of chloramine to phenolic pollutants is 0.5 to 40:1, preferably 2 to 20:1.

[0013] In specific embodiments, the mass ratio of chloramine, peroxidase, and phenolic pollutants is 3.2:0.5:1.0, 4.8:0.5:1.0, 1.6:0.5:1.0, 3.2:0.3:1.0, or 1.6:0.3:1.0.

[0014] The present invention adjusts the pH value to a range of 2–9, preferably 3–7, specifically, pH values ​​of 3, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, or 7.0. The present invention significantly enhances the oxidizing capacity of chloramine and effectively degrades phenolic pollutants by adding a small amount of peroxidase to an aqueous solution containing phenolic pollutants at pH = 2–9.

[0015] In this invention, the reaction temperature is 15 to 50°C; specifically, the reaction temperature is 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C.

[0016] The degradation reaction of the catalytic system in this invention also includes: taking samples of the mixed solution at regular intervals for high performance liquid chromatography (HPLC) testing to calculate the degradation rate of phenolic pollutants; and when the degradation rate reaches 100% or a stable value, the catalytic degradation reaction ends.

[0017] This invention provides a method for treating phenolic pollutants using chloramine based on peroxidase catalysis, comprising the following steps: adding chloramine and peroxidase to an aqueous solution containing phenolic pollutants to obtain a mixed solution; reacting under stirring conditions to obtain treated water. This method, by adding a small amount of peroxidase, can effectively catalyze the degradation of phenolic pollutants by chloramine. Compared with using chloramine alone, the degradation effect on organic pollutants in water is significantly improved, which has important practical significance for removing industrial and domestic wastewater rich in organic pollutants. The water treatment method provided by this invention has a simple reaction mechanism, mild reaction conditions, high catalytic efficiency, strong selectivity, and low cost, and can realize large-scale industrial production and utilization, showing broad application prospects in water pollution control and water environment remediation. Attached Figure Description

[0018] Figure 1 This is a comparison of the degradation rate of bisphenol A by chloramine treatment alone at pH=5 and by enzymatic chloramine systems with different mass addition ratios.

[0019] Figure 2 A comparison of the degradation rates of bisphenol A at different pH values ​​between chloramine treatment alone and enzymatic chloramine system treatment at a certain mass addition ratio in an experiment. Detailed Implementation

[0020] To further illustrate the present invention, the following detailed description of a method for treating phenolic pollutants based on peroxidase-catalyzed chloramine is provided in conjunction with embodiments, but these descriptions should not be construed as limiting the scope of protection of the present invention.

[0021] Example 1

[0022] Horseradish peroxidase was prepared using deionized water, and a standardized chloramine solution was prepared for later use. Chloramine solution and enzyme solution were added separately to 30 mL of an aqueous solution containing 10 μmol / L bisphenol A (pH=5) to obtain a mixed solution. The mass ratio of chloramine, horseradish peroxidase, and bisphenol A was 3.2:0.5:1.0. The reaction was carried out under uniform stirring at 25℃. Small amounts of the reaction solution were taken at regular intervals and analyzed using high-performance liquid chromatography (HPLC) to calculate the degradation rate of bisphenol A. The study showed that the degradation rate of bisphenol A reached 100% after 1 hour of reaction.

[0023] Example 2

[0024] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the mass ratio of chloramine, enzyme, and bisphenol A added is 4.8:0.5:1.0. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0025] Example 3

[0026] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the mass ratio of chloramine, enzyme, and bisphenol A added is 1.6:0.5:1.0. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0027] Example 4

[0028] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the mass ratio of chloramine, enzyme, and bisphenol A added is 3.2:0.3:1.0. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 75%.

[0029] Example 5

[0030] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the mass ratio of chloramine, enzyme, and bisphenol A added is 1.6:0.3:1.0. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 72%.

[0031] Figure 1 This is a comparison chart showing the degradation rate of bisphenol A by the enzymatic chloramine system used in Examples 1-5 and Comparative Example 1. Figure 1 It can be seen that by adding peroxidase, chloramine can effectively catalyze the degradation of phenolic pollutants, and the degradation effect on organic pollutants in water is greatly improved compared with the use of chloramine alone.

[0032] Example 6

[0033] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the pH of the aqueous solution containing phenolic pollutants was adjusted to 4.0. The results showed that after 1 hour of reaction, the degradation rate of bisphenol A was 100%.

[0034] Example 7

[0035] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the pH of the aqueous solution containing phenolic pollutants was adjusted to 6.0. The results showed that after 1 hour of reaction, the degradation rate of bisphenol A was 87%.

[0036] Example 8

[0037] The method for preparing the catalytic system mixed solution was the same as in Example 1, except that the pH of the aqueous solution containing phenolic pollutants was adjusted to 7.0. The results showed that after 1 hour of reaction, the degradation rate of bisphenol A was 71%.

[0038] Figure 2 The graph shows a comparison of the degradation rates of bisphenol A by the catalytic system mixtures of Examples 1, 6-8, and Comparative Example 1 at different pH values. It can be seen that the catalytic system exhibits higher degradation efficiency for phenolic pollutants in the presence of peroxidase and under acidic conditions with pH ≤ 5.

[0039] Example 9

[0040] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the peroxidase is replaced with chloroperoxidase. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0041] Example 10

[0042] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the peroxidase is changed to lignin peroxidase. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 96%.

[0043] Example 11

[0044] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the peroxidase is changed to cytochrome C peroxidase. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0045] Example 12

[0046] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the reaction temperature is changed to 30°C. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0047] Example 13

[0048] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the reaction temperature is changed to 40°C. The results show that after 1 hour of reaction, the degradation rate of bisphenol A is 100%.

[0049] Example 14

[0050] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the phenolic pollutant is replaced with phenol. The results show that after 1 hour of reaction, the degradation rate of phenol is 100%.

[0051] Example 15

[0052] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that the phenolic pollutant is replaced with methylparaben. The results show that after 1 hour of reaction, the degradation rate of methylparaben is 100%.

[0053] Comparative Example 1

[0054] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that only chloramine and organic pollutants (bisphenol A, phenol, or methylparaben) are added to the water, and the mass ratio of chloramine to organic pollutants is 4.8:1. The results show that after 2 hours of reaction, the degradation rate of bisphenol A, phenol, or methylparaben is less than 10%.

[0055] Comparative Example 2

[0056] The method for preparing the catalytic system mixed solution is the same as in Example 1, except that peroxidase and organic pollutants (bisphenol A, phenol, or methylparaben) are added only to the water, and the mass ratio of peroxidase to organic pollutants is 1:2. The results show that after 1 hour of reaction, the degradation rates of bisphenol A, phenol, or methylparaben are all less than 5%.

[0057] As shown in the above embodiments, this invention provides a method for treating phenolic pollutants using chloramine based on peroxidase catalysis, comprising the following steps: adding chloramine and peroxidase to an aqueous solution containing phenolic pollutants to obtain a mixed solution, reacting under stirring conditions to obtain treated water. This method, by adding a small amount of peroxidase, can effectively catalyze the degradation of phenolic pollutants by chloramine. Compared with using chloramine alone, the degradation effect on organic pollutants in water is significantly improved, which has important practical significance for removing industrial and domestic wastewater rich in organic pollutants. The water treatment method provided by this invention has a simple reaction mechanism, mild reaction conditions, high catalytic efficiency, strong selectivity, and low cost, and can realize large-scale industrial production and utilization, showing broad application prospects in water pollution control and water environment remediation.

[0058] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for treating phenolic pollutants using peroxidase-catalyzed chloramine, comprising the following steps: Chloramine and peroxidase were added to an aqueous solution containing phenolic pollutants to obtain a mixed solution. The solution was then reacted under stirring to obtain treated water.

2. The method according to claim 1, characterized in that, The peroxidase is selected from one or more of lignin peroxidase, chloride peroxidase, horseradish peroxidase, glutathione peroxidase, cytochrome C peroxidase, manganese peroxidase, and myeloperoxidase.

3. The method according to claim 1, characterized in that, The mass ratio of chloramine to peroxidase is 0.5 to 50:

1.

4. The method according to claim 1, characterized in that, The mass ratio of chloramine to phenolic pollutants is 0.5 to 40:

1.

5. The method according to claim 1, characterized in that, The pH range of aqueous solutions containing phenolic pollutants is 2 to 9.

6. The method according to claim 1, characterized in that, The reaction temperature is 15–50℃.

7. The method according to claim 1, characterized in that, Phenolic contaminants include, but are not limited to, one or more of halogenated phenols, bisphenol A, phenol, and parabens; The concentration of phenolic pollutants in aqueous solutions ranges from 10 to 500 μmol / L.

Images