Method for controlling generation potential of chlorination disinfection by-products through photosensitization effect of persulfate reinforced algae organic matters and application of method

Abstract

The invention belongs to the technical field of environmental remediation and pollution treatment, and particularly relates to a method for controlling the generation potential of chlorination disinfection by-products through the photosensitization effect of persulfate enhanced algae organic matter and application of the method. According to the method, the sunlight photosensitization effect of the algae organic matter is enhanced by adopting persulfate to control the generation potential of the disinfection by-product, and the control effect of the generation potential of the algae source disinfection by-product is greatly improved on the basis of the prior art. Economical and sustainable sunlight is used as a driving source, traditional ultraviolet light driving is replaced, and the economic effect and feasibility of the technology are further improved. According to the invention, algae and organic matters in water are synergistically removed, the water treatment effect is obviously improved, and the water quality is improved. Meanwhile, by reducing generation of disinfection by-products, safety of water treatment is improved, safety of drinking water and other water is guaranteed, sunlight is used as driving force, use of chemical reagents and energy consumption of ultraviolet light equipment are reduced, and the device has the advantages of being environmentally friendly and sustainable.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental restoration and pollution control, and specifically relates to a method for controlling the generation potential of chlorination disinfection by-products by strengthening the photosensitization effect of algae organic matter with persulfate and an application thereof. Background Art

[0002] In recent years, blue algae outbreaks have frequently caused the water quality of rivers and lakes to decline around the world, posing a huge challenge to water treatment. Organic matter (AOM) produced by algae growth, including algae intracellular organic matter (IOM) and algae extracellular organic matter (EOM), is an important precursor of chlorination disinfection by-products (DBPs), which is directly related to the health of drinking water to a large extent. Chlorination disinfection by-products have carcinogenic, teratogenic and mutagenic effects. Long-term intake may increase the risk of cancer and fetal malformations, affect liver and kidney function, and may cause neurological problems. Chloroform chlorination disinfection by-products are included in the 14 new pollutants that are under key control in my country. In the newly revised and current "Standards for Drinking Water Hygiene GB5749-2022" in my country, chlorination disinfection by-products have been raised from unconventional indicators to conventional indicators for drinking water. Therefore, controlling the generation of chlorination disinfection by-products has become a vital part of ensuring safe and healthy drinking water.

[0003] Algae are the main photosynthetic organisms in natural water bodies. The chromophores in algae organic matter are found to be important natural photosensitizers in water. They can absorb photons and generate a series of active substances under the radiation of ultraviolet light and sunlight, including triplet excited states ( 3 AOM*), hydroxyl radical (·OH), singlet oxygen ( 1 O 2 ) etc. Through the photosensitization effect of algae organic matter, the degradation of residual new pollutants in water can be promoted. Therefore, microalgae photosensitization is a clean, low-carbon and promising technology for the degradation of new pollutants. IOM and EOM can generate triplet excited states ( 3 IOM*, 3 The photosensitization effect of active species such as DBPs (DBPs EOM*), hydroxyl radicals, and singlet oxygen, while degrading pollutants in water, some active species will also have some impact on the changes in the generation potential of algal organic matter itself and algal disinfection by-products. However, there are currently few reports on DBPs control technology involving photosensitization effects.

[0004] Studies have shown that the photosensitization effect of a single algae organic matter has a certain effect on controlling the generation of algae-derived chlorination disinfection by-products. However, since it is easily affected by other ions, pollutants, light intensity and other factors in the water, the photosensitization effect of algae organic matter on algae-derived chlorination disinfection by-products is limited and unstable. Therefore, the development of a method based on persulfate-enhanced photosensitization effect of algae organic matter to control the generation potential of algae-derived disinfection by-products is of great strategic significance for strengthening the control of new pollutants. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a method for controlling the generation potential of chlorination disinfection by-products by enhancing the photosensitization effect of algae organic matter with persulfate in order to solve the problems existing in the prior art.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A method for controlling the generation potential of chlorination disinfection byproducts by strengthening the photosensitization effect of algae organic matter with persulfate, which uses persulfate to strengthen the sunlight photosensitization effect of algae organic matter to achieve control of the generation potential of chlorination algae source disinfection byproducts.

[0008] Furthermore, the persulfate-enhanced sunlight photosensitization effect is manifested in an increase in the content of triplet excited state active species produced by algae organic matter.

[0009] It is worth noting that the sunlight photosensitization effect of algae organic matter is that algae organic matter will undergo photosensitization reaction under the irradiation of sunlight to generate active oxygen species (such as singlet oxygen 1 O 2 and triplet excited states of algae organic matter 3 AOM*). These reactive oxygen species can further oxidize and decompose organic matter, enhancing the water treatment effect. However, the solar photosensitization effect of algae organic matter alone is not ideal in controlling the generation potential of chlorinated algae source disinfection byproducts.

[0010] The present invention uses persulfate to strengthen the sunlight photosensitization effect of algae organic matter, thereby achieving control of the potential for the generation of chlorination disinfection byproducts. This method activates persulfate through sunlight and synergizes with the photosensitization effect of algae organic matter. The addition of persulfate greatly increases the steady-state concentration of reactive oxygen species produced by the photosensitization effect of algae organic matter, thereby more efficiently removing algae organic matter from water, controlling disinfection byproduct precursors, and reducing the generation of algae-derived disinfection byproducts.

[0011] In particular, on the one hand, the present invention can efficiently remove precursors of algae-derived disinfection byproducts. Traditional single technologies (such as ultraviolet light-driven persulfate oxidation or photosensitization of individual algae organic matter) have certain limitations in removing algae organic matter, and the present invention can significantly improve the removal effect by coupling the two technologies. On the other hand, the present invention can effectively reduce the generation of DBPs. Traditional chlorination disinfection methods will produce a large amount of DBPs, and the present invention can significantly reduce the generation of these byproducts by strengthening the photosensitization effect of algae organic matter with persulfate. At the same time, the present invention can also effectively reduce processing costs, use sunlight as a driving force, reduce dependence on chemical reagents and ultraviolet light equipment, and reduce the operating costs and environmental impact of water treatment.

[0012] Furthermore, the algae are cyanobacteria, and the algae organic matter includes one or more of algae intracellular organic matter IOM and algae extracellular organic matter EOM.

[0013] Considering that cyanobacteria are one of the most common algae in water bodies, they are widely distributed in rivers, lakes and reservoirs, and have the characteristics of rapid reproduction, which easily forms algal blooms and has a serious impact on the quality of water bodies. In particular, cyanobacterial cells contain a large amount of organic matter, which is an important precursor substance for the formation of disinfection by-products. Therefore, in order to specifically degrade the organic matter produced by cyanobacteria themselves, reduce the generation of by-products during the disinfection process, and then effectively remove the soluble organic matter contributed by cyanobacteria in the water body and improve the water quality, the present invention strengthens the sunlight photosensitization effect of cyanobacterial organic matter through persulfate, reduces the precursors of disinfection by-products, degrades the organic matter released by cyanobacteria, and reduces the precursor substances for the formation of disinfection by-products, thereby further controlling the generation potential of algae-derived disinfection by-products.

[0014] In addition, algae organic matter AOM includes algae extracellular organic matter EOM and algae intracellular organic matter IOM. IOM will be released into the water in large quantities when the cell structure or activity is destroyed, while EOM is the organic matter released into the environment during the normal life cycle of algae cells. Through the solar self-sensitization effect of the two algae organic matters enhanced by persulfate, both algae organic matters as important precursors of disinfection by-products can be effectively degraded, thereby achieving efficient control of chlorination disinfection by-products.

[0015] Furthermore, the cyanobacteria include one or more of Microcystis aeruginosa and Anabaena.

[0016] It is worth noting that Microcystis aeruginosa and Anabaena are common harmful blue algae species in water bodies and are widely distributed in many freshwater bodies. They often cause algal blooms, posing a serious threat to the water environment and ecosystem. The present invention utilizes the sunlight photosensitization effect of Microcystis aeruginosa organic matter and Anabaena organic matter, which can not only degrade algae organic matter, i.e., the precursor substance for the generation of algae-derived disinfection by-products, and reduce the generation of disinfection by-products from the source, but also use sunlight as energy, with low operating costs and good economic benefits. And no secondary pollution will be generated, which is conducive to the long-term healthy development of the water ecosystem. In particular, the addition of persulfate in the present invention greatly increases the active oxygen species produced by the photosensitization effect of Microcystis aeruginosa or Anabaena organic matter, thereby improving the ability to oxidize and decompose organic matter in the water body, thereby effectively enhancing the water treatment effect.

[0017] Furthermore, the persulfate is peroxydisulfate (PDS).

[0018] It is worth noting that the present invention uses peroxydisulfate represented by potassium persulfate.

[0019] The prior art only discloses the use of ultraviolet light to drive persulfate to control the generation potential of algae-derived disinfection byproducts, and has never mentioned the effect of persulfate on the photosensitization effect of algae organic matter. The present invention not only pays attention to the photosensitization effect of algae organic matter under light, but also pays attention to the role of persulfate in enhancing the photosensitization reaction of algae organic matter under sunlight, thereby effectively strengthening the photosensitization effect of algae organic matter, and using the synergistic multiplication effect of the two to achieve efficient control of drinking water chlorination disinfection byproducts.

[0020] Furthermore, the method of using persulfate to enhance the photosensitization effect of algae organic matter to control the generation potential of chlorination disinfection byproducts comprises the following specific steps:

[0021] S1. adding persulfate to a water body containing algae organic matter to obtain a mixed solution;

[0022] S2, adjusting the pH value of the mixed solution obtained in step S1 to 7±0.1 using a buffer solution to obtain a neutral stock solution;

[0023] S3, homogenizing the neutral stock solution at a constant temperature, and simultaneously using sunlight to react;

[0024] S4. After the photoreaction is completed, the pH value of the reaction system is adjusted to 7±0.1, and NaClO reagent is added with a ratio of TOC: free Cl=1:5, and chlorination is performed in the dark. After chlorination, ascorbic acid is added for quenching to obtain treated water.

[0025] The traditional chlorination disinfection method will produce a large amount of DBPs. The present invention uses persulfate to enhance the activation of the sunlight photosensitization effect of algae organic matter, and synergistically reduces the generation of disinfection by-products. Compared with the photosensitization effect of algae organic matter alone, the control effect of algae-derived disinfection by-products is greatly improved. In addition, the use of sunlight as a driving force reduces the dependence on chemical reagents and ultraviolet light equipment, reduces the operating cost and environmental impact of water treatment, can effectively reduce the treatment cost, and improve the environmental protection and sustainability of the water treatment process.

[0026] Furthermore, in step S1, the concentration of algae organic matter in the water body is 2-10 mg / L in terms of TOC, and the concentration of persulfate is 0.001-0.005 mol / L.

[0027] Furthermore, the buffer solution in step S2 is a phosphate buffer solution.

[0028] Furthermore, the sunlight in step S3 includes real sunlight or 300W xenon lamp simulating sunlight, and the temperature of the constant temperature reaction is 25±2°C.

[0029] And, the light-proof chlorination reaction temperature in step S4 is 25°C.

[0030] It is worth noting that after the solution containing algae organic matter was irradiated with sunlight alone and then subjected to chlorination disinfection treatment, due to the photosensitization effect of algae-derived organic matter under sunlight, the generation potential of disinfection by-products was controlled to a certain extent during the reaction process, and after persulfate was added to the system, the generation potential control effect of disinfection by-products was greatly improved. This is because when sunlight is irradiated alone, active species such as triplet excited states, hydroxyl radicals, and singlet oxygen are generated in the system, and after the addition of persulfate, the content of triplet excited state substances in the system is significantly increased. The triplet excited state is an indicative active species of the photosensitization effect, which further confirms that the addition of persulfate promotes the photosensitization effect of algae organic matter. Therefore, persulfate strengthens the photosensitization effect of algae organic matter, so that the generation potential of algae-derived disinfection by-products is better controlled.

[0031] The second object of the present invention is to provide an application of the above-mentioned method of using persulfate to enhance the photosensitization effect of algae organic matter to control the generation potential of chlorination disinfection by-products.

[0032] The invention discloses an application of a method for controlling the generation potential of chlorination disinfection byproducts by strengthening the photosensitization effect of algae organic matter with persulfate, and is aimed at controlling the disinfection byproducts generated in the process of water treatment and disinfection of drinking water sources containing algae organic matter.

[0033] Compared with the prior art, the present invention adopts the technology of strengthening the photosensitization effect of algae organic matter by persulfate to control the potential of chlorination disinfection byproducts. On the basis of the existing photosensitization effect of algae organic matter, the content of the main active species such as triplet excited state substances in the system is greatly improved, thereby effectively improving the control effect of the potential of algae source disinfection byproducts. And the economically sustainable sunlight is used as the driving source to replace the traditional ultraviolet light drive, which further improves the economic effect and feasibility of the technology. Therefore, the present invention more efficiently removes algae and organic matter in water through the strengthening effect of persulfate on the photosensitization effect of algae organic matter, significantly improves the effect of water treatment, and improves the quality of water. At the same time, by reducing the generation of disinfection byproducts, the safety of water treatment is improved, the safety of drinking water and other water is guaranteed, and the use of sunlight as the driving force reduces the use of chemical reagents and the energy consumption of ultraviolet light equipment, which has the advantages of environmental protection and sustainability.

[0034] Compared with the photosensitization effect of algae organic matter alone, the photosensitization technology of algae organic matter after sulfate enhancement has higher efficiency in removing algae and organic matter, and can significantly improve the water treatment effect. In addition, by reducing the use of chemical reagents and lowering equipment requirements, the present invention has high economic efficiency and is suitable for application in various water treatment scenarios. Therefore, the present invention is suitable for various water environments, has broad application prospects, and can play an important role in the fields of drinking water treatment, sewage treatment, swimming pool water treatment, and industrial wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0036] Figure 1 This is the control effect of the xenon lamp simulating sunlight irradiation on the generation potential of algal disinfection by-products in Experimental Example 1 of the present invention, wherein ANIOM is the intracellular organic matter system of Anabaena, MAIOM is the intracellular organic matter system of Microcystis aeruginosa, IOM in the legend is the intracellular organic matter system, IOM+light is the intracellular organic matter plus light system, and IOM+PS+light is the intracellular organic matter + potassium persulfate + light system.

[0037] Figure 2This is the control effect of the xenon lamp simulating sunlight irradiation to drive persulfate oxidation on the generation potential of algal disinfection by-products in Experimental Example 1 of the present invention, wherein ANEOM is the extracellular organic matter system of Anabaena, MAEOM is the extracellular organic matter system of Microcystis aeruginosa, EOM in the legend is the extracellular organic matter system, EOM+light is the extracellular organic matter plus light system, and EOM+PS+light is the extracellular organic matter + potassium persulfate + light system.

[0038] Figure 3 This is the change result of total organic carbon TOC in Experimental Example 1 of the present invention.

[0039] Figure 4 This is the control effect of natural light irradiation driven persulfate oxidation on the generation potential of algal disinfection by-products in Experimental Example 1 of the present invention, wherein ANIOM is the intracellular organic matter system of Anabaena, MAIOM is the intracellular organic matter system of Microcystis aeruginosa, IOM in the legend is the intracellular organic matter system, IOM+light is the intracellular organic matter plus light system, and IOM+PS+light is the intracellular organic matter + potassium persulfate + light system.

[0040] Figure 5 This is the control effect of natural light irradiation driven persulfate oxidation on the generation potential of algal disinfection by-products in Experimental Example 1 of the present invention, wherein ANEOM is the extracellular organic matter system of Anabaena, MAEOM is the extracellular organic matter system of Microcystis aeruginosa, EOM in the legend is the extracellular organic matter system, EOM+light is the extracellular organic matter plus light system, and EOM+PS+light is the extracellular organic matter + potassium persulfate + light system.

[0041] Figure 6 In Experimental Example 2 of the present invention, three-dimensional fluorescent EEM was used to explore the effect of xenon lamp simulating sunlight on the changes in the components of extracellular organic matter of Microcystis aeruginosa or extracellular organic matter of Microcystis aeruginosa + potassium persulfate system, wherein extracellular organic matter of Microcystis aeruginosa: (a) 0 min; extracellular organic matter of Microcystis aeruginosa + light: (b) 10 min, (c) 30 min, (d) 60 min; extracellular organic matter of Microcystis aeruginosa + potassium persulfate + light: (e) 10 min, (f) 30 min, (g) 60 min.

[0042] Figure 7 In Experimental Example 2 of the present invention, three-dimensional fluorescent EEM was used to explore the xenon lamp simulation of extracellular organic matter of Anabaena: (a) 0 min; extracellular organic matter of Anabaena + light: (b) 10 min, (c) 30 min, (d) 60 min; extracellular organic matter of Anabaena + potassium persulfate + light: (e) 10 min, (f) 30 min, (g) 60 min.

[0043] Figure 8In Experimental Example 2 of the present invention, three-dimensional fluorescent EEM was used to explore the effect of xenon lamp simulating sunlight on the changes in the components of intracellular organic matter of Microcystis aeruginosa or intracellular organic matter of Microcystis aeruginosa + potassium persulfate system, wherein intracellular organic matter of Microcystis aeruginosa: (a) 0 min; intracellular organic matter of Microcystis aeruginosa + light: (b) 10 min, (c) 30 min, (d) 60 min; intracellular organic matter of Microcystis aeruginosa + potassium persulfate + light: (e) 10 min, (f) 30 min, (g) 60 min.

[0044] Fig. 9 In Experimental Example 2 of the present invention, three-dimensional fluorescent EEM was used to explore the effect of xenon lamp simulating sunlight on the changes in the components of the intracellular organic matter of Anabaena or the intracellular organic matter of Anabaena + potassium persulfate system, wherein the intracellular organic matter of Anabaena: (a) 0 min; the intracellular organic matter of Anabaena + light: (b) 10 min, (c) 30 min, (d) 60 min; the intracellular organic matter of Anabaena + potassium persulfate + light: (e) 10 min, (f) 30 min, (g) 60 min.

[0045] Fig.10 The figure shows the effect of PS dosage on the generation of disinfection by-products in Experimental Example 1 of the present invention, wherein MAIOM is the intracellular organic matter system of Microcystis aeruginosa, MAEOM is the extracellular organic matter system of Microcystis aeruginosa, ANIOM is the intracellular organic matter system of Anabaena, and ANEOM is the extracellular organic matter system of Anabaena. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] The word "embodiment" used here as an "exemplary" does not necessarily mean that any embodiment described is superior to or better than other embodiments. Unless otherwise specified, the performance index tests in the embodiments of this application are performed using conventional test methods in the art. It should be understood that the terms described in this application are only used to describe specific implementation methods and are not used to limit the content disclosed in this application.

[0048] Unless otherwise specified, the technical and scientific terms used in this document have the same meanings as commonly understood by ordinary technicians in the technical field to which this application belongs; other experimental methods and technical means not specifically specified in this application refer to experimental methods and technical means commonly used by ordinary technicians in this field.

[0049] In order to better illustrate the content of the present application, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that the present application can also be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present application.

[0050] Under the premise of no conflict, the technical features disclosed in the embodiments of the present application can be combined arbitrarily, and the resulting technical solutions belong to the contents disclosed in the embodiments of the present application.

[0051] The present invention proposes a method and application of strengthening the photosensitization effect of algae organic matter by persulfate to control the generation potential of disinfection byproducts from algae, and belongs to the technical field of environmental remediation and pollution control. The present invention adopts persulfate to strengthen the sunlight photosensitization effect of algae organic matter to control the generation potential of disinfection byproducts, and greatly improves the content of triplet excited state substances in the system on the basis of the existing technology, thereby effectively improving the control effect of the generation potential of disinfection byproducts from algae. And using economically sustainable sunlight as a driving source to replace the traditional ultraviolet light drive further improves the economic effect and feasibility of the technology. Therefore, the present invention more efficiently removes algae and organic matter in water through the strengthening effect of persulfate on the photosensitization effect of algae organic matter, significantly improves the effect of water treatment, and improves the quality of water. At the same time, by reducing the generation of disinfection byproducts, the safety of water treatment is improved, the safety of drinking water and other water is guaranteed, and the use of sunlight as a driving force reduces the use of chemical reagents and the energy consumption of ultraviolet light equipment, which has the advantages of environmental protection and sustainability.

[0052] In order to better understand the present invention, the present invention is further specifically described through the following examples, but it should not be understood as limiting the present invention. Some non-essential improvements and adjustments made by technicians in this field according to the above invention content are also considered to fall within the protection scope of the present invention.

[0053] Example 1

[0054] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, comprising the following specific steps:

[0055] S1: 5 mmol / L potassium persulfate was added to water (200 mL) containing 5 mg / L (in terms of TOC) of four algae organic matter (intracellular organic matter of Microcystis aeruginosa, extracellular organic matter of Microcystis aeruginosa, intracellular organic matter of Anabaena, and extracellular organic matter of Anabaena) to obtain a mixed solution;

[0056] S2: adjusting the pH value of the mixed solution with a buffer solution (phosphate buffer solution: sodium dihydrogen phosphate, disodium hydrogen phosphate), and adjusting the pH value of the mixed solution to 7±0.1 to obtain a neutral stock solution;

[0057] S3: Use a constant temperature water bath to maintain the temperature during the illumination experiment at 25±2°C, stir the degraded stock solution with a magnetic stirrer, and use a 300W xenon lamp (without filter, light intensity of 230mW / cm -2 ) irradiating the stock solution with simulated sunlight, so that the algae organic matter in the stock solution undergoes a photosensitization effect and reacts with the potassium persulfate activated by sunlight, so as to control the precursor substances of algae-derived disinfection by-products, thereby further controlling the generation potential of disinfection by-products;

[0058] S4: After xenon lamp irradiation, the pH of 200 mL sample was immediately adjusted to 7.0 ± 0.1, and NaClO reagent (TOC: free Cl = 1: 5) was added. The sample was chlorinated in the dark for 72 h (25 ° C). Ascorbic acid was added to the chlorinated sample for quenching.

[0059] Example 2

[0060] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, comprising the following specific steps:

[0061] S1: 5 mmol / L potassium persulfate was added to water (200 mL) containing 5 mg / L (in terms of TOC) of four algae organic matter (intracellular organic matter of Microcystis aeruginosa, extracellular organic matter of Microcystis aeruginosa, intracellular organic matter of Anabaena, and extracellular organic matter of Anabaena) to obtain a mixed solution;

[0062] S2: adjusting the pH value of the mixed solution with a buffer solution (phosphate buffer solution: sodium dihydrogen phosphate, disodium hydrogen phosphate), and adjusting the pH value of the mixed solution to 7±0.1 to obtain a neutral stock solution;

[0063] S3: using a constant temperature water bath to maintain the temperature during the illumination experiment at a stable temperature of 25±2°C, stirring the stock solution to be degraded by a magnetic stirrer, and irradiating the stock solution with real sunlight (five consecutive sunny days in summer), so that the algae organic matter in the stock solution undergoes a photosensitization effect and reacts with the potassium persulfate activated by sunlight, so as to control the precursor substances of algae-derived disinfection by-products, thereby further controlling the generation potential of disinfection by-products;

[0064] S4: After real sunlight irradiation, the pH of 200 mL of the sample was immediately adjusted to 7.0 ± 0.1, and NaClO reagent (TOC: free Cl = 1:5) was added. The sample was chlorinated in the dark for 72 h (25 °C), and ascorbic acid was added to the chlorinated sample for quenching.

[0065] Example 3

[0066] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, wherein the specific steps are the same as those in Example 1, except that 4 mmol / L of potassium persulfate is added in step S1.

[0067] Example 4

[0068] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, wherein the specific steps are the same as those in Example 1, except that 3 mmol / L of potassium persulfate is added in step S1.

[0069] Example 5

[0070] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, wherein the specific steps are the same as those in Example 1, except that 2 mmol / L of potassium persulfate is added in step S1.

[0071] Example 6

[0072] A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, wherein the specific steps are the same as those in Example 1, except that the potassium persulfate added in step S1 is 1 mmol / L.

[0073] Examples 7-10

[0074] A method for controlling the generation potential of chlorination disinfection by-products by enhancing the photosensitization effect of algae organic matter with persulfate, wherein the specific steps are the same as those in Example 2, except that the potassium persulfate added in step S1 is 4-1 mmol / L.

[0075] In order to further demonstrate the beneficial effects of the present invention and to better understand the present invention, the application performance of the method disclosed in the present invention for enhancing the photosensitization effect of algae organic matter with persulfate to control the generation potential of chlorination disinfection by-products is further illustrated by the following comparative examples and experimental examples. However, it should not be construed as a limitation of the present invention. Other measurement experiments or comparative examples performed by those skilled in the art based on the above-mentioned invention content to obtain the method properties and the applications based on the above-mentioned properties are also deemed to fall within the protection scope of the present invention.

[0076] Comparative Example 1

[0077] A method for controlling the generation potential of algae-derived disinfection byproducts by using sunlight photosensitization of a single algae organic matter:

[0078] S1: 5 mg / L (in terms of TOC) of four algae organic matter (intracellular organic matter of Microcystis aeruginosa, extracellular organic matter of Microcystis aeruginosa, intracellular organic matter of Anabaena, and extracellular organic matter of Anabaena) were added to pure water to obtain a mixed solution;

[0079] S2: adjusting the pH value of the mixed solution with a buffer solution (phosphate buffer solution: sodium dihydrogen phosphate, disodium hydrogen phosphate), and adjusting the pH value of the mixed solution to 7±0.1 to obtain a neutral stock solution;

[0080] S3: Use a constant temperature water bath to maintain the temperature during the light experiment at 25±2°C, stir the degradable stock solution with a magnetic stirrer, and use real sunlight (five consecutive sunny days in summer) or a 300W xenon lamp (without filter, light intensity of 230mW / cm -2 ) irradiating the stock solution with simulated sunlight to cause the algae organic matter in the stock solution to undergo a photosensitization effect, thereby controlling the precursor substances of algae-derived disinfection by-products, thereby further controlling the generation potential of disinfection by-products.

[0081] S4: After real sunlight or xenon lamp irradiation, adjust the pH of 200 mL sample immediately (7.0±0.1). Add NaClO reagent (TOC: free Cl = 1:5), chlorinate for 72 hours (25°C) in the dark, and add ascorbic acid to the chlorinated sample for quenching.

[0082] Experimental Example 1: Effects on the Generation Potential of Disinfection Byproducts from Algae

[0083] 1.1 Experimental method for the generation potential of algae-derived disinfection byproducts:

[0084] 25 mL of the quenched sample of Example 1-10 was collected in a brown glass bottle with a lid, and trichloromethane (TCM), dichloroacetonitrile (DCAN) and dichloroacetic acid (DCAA) were quantitatively determined by GC / ECD after liquid-liquid extraction according to the method of USEPA.

[0085] The results are as follows Fig.10As shown, it can be seen that from the total amount of three disinfection by-products generated, within the range of 1-5mmol / L of potassium persulfate dosage, as the potassium persulfate dosage increases, the generation potential of disinfection by-products DBPs gradually decreases. Among them, the control effect of chloroform TCM is the most obvious. When the dosage of PS reaches 5mmol / L, the control amount of TCM generated by two algae-derived organic matter of Microcystis aeruginosa reaches more than 80%, and the control level of TCM generated by two organic matter of Anabaena is also about 70%. At the same time, the control effect of DCAA is also very obvious. When the dosage of PS reaches 5mmol / L, the control level in the four organic matter systems is in the range of 45%-65%. For DCAN, when the dosage of PS reaches 5mmol / L, an obvious control effect appears in the algae extracellular organic matter EOM system after 5 days of illumination, and the control rate reaches a high level of more than 85%, while in the intracellular organic matter IOM system, the generation potential increases with the increase of dosage.

[0086] 1.2 Simulating the influence of sunlight

[0087] The effect of simulated sunlight and its driving effect on the generation of algae disinfection byproducts was investigated by simulating sunlight irradiation (i.e., Example 1). Figure 1 , 2). (The simulated illumination duration of the experiment is one hour, and the sampling points are: 0min, 10min, 20min, 30min, 45min, 60min).

[0088] The experimental results show that, compared with the comparative example 1, the total amount of DBPs generated by the system with PS can be greatly reduced, and the highest control efficiency of the total disinfection byproduct generation potential of the four algae organic matter is 86.5%. TCM is more sensitive, and the simulated sunlight alone can control its generation potential to a certain extent. The control effect within one hour of simulated sunlight is within the level range of 20%-30%. After the addition of PS, the total amount of TCM generation can be further reduced on the original basis, and the control level is increased to 89%-97% relative to the system without PS. For DCAA, the system has a relatively stable effect on its generation potential, but after the addition of persulfate, its generation is greatly reduced relative to the single sunlight irradiation, and the control efficiency in the four algae organic matter systems is as high as 78.7%. For DCAN, the generation in the EOM simulated sunlight / PS system has a great control effect relative to the single illumination system, and the highest control rate in the extracellular organic matter system of Anabaena is 76%. In the experimental group of intracellular organic matter, the generation amount increased after the addition of PS.

[0089] 1.3 Influence of natural light

[0090] In order to ensure the accuracy of the experiment and its practical application potential, a simulation experiment under natural lighting conditions was also carried out under the condition of direct sunlight (ie, Example 2, Figure 4 , 5). (The experiment was conducted on five consecutive sunny days in summer, the experimental length was 5 days, and the sampling time points were: 0d, 0.5d, 1d, 2d, 3d, 5d).

[0091] The experimental results show that the change trend of the three disinfection byproducts is basically consistent with the trend under the xenon lamp simulation conditions, and under natural light conditions, the three disinfection byproducts show a more obvious control efficiency. The highest control efficiency of the total disinfection byproduct generation potential of the four algae organic matter reaches the level range of 78%-95%, which further illustrates the application potential of the invention. At the same time, the change of TOC is also tested ( Figure 3 ), and found that with the extension of illumination time, the degradation rate of TOC gradually increased, and the degradation efficiency of the system with PS was better than that of the single illumination system.

[0092] Experimental Example 2 Mechanism Analysis

[0093] 2.1 Three-dimensional fluorescence analysis

[0094] AOM and its component changes during illumination were analyzed and studied ( Figures 6 to 9 ) to explore the system's control over DBPs precursors and their relationship with subsequent changes in the potential for disinfection by-product generation.

[0095] The present invention measures the TOC value of EOM and IOM solutions extracted from the end of the logarithmic phase of Microcystis aeruginosa and Anabaena algae respectively, and then dilutes the solution to 5 mg·L -1 Xenon lamp irradiation was performed with and without persulfate, and samples were taken at 0, 10, 30, and 60 min of illumination. After filtering through a 0.45 μm organic filter membrane, an excitation-emission matrix fluorescence spectrum was obtained using a fluorescence spectrophotometer to analyze the changes in the photosensitized components of algae organic matter. The specific parameters were as follows: excitation wavelength range 200 nm to 550 nm, emission wavelength range 250 nm to 600 nm, sampling interval 5 nm, scanning speed 12000 nm min -1 , the excitation and emission unit slits are both 2.5nm, and the PMT voltage is 700V.

[0096] The experimental results show that when xenon lamp irradiation is performed without the addition of persulfate, the content of precursor substances that can generate disinfection by-products gradually decreases with the extension of illumination time, and the fluorescence intensity gradually decreases, which means that the content of DBPs precursor substances is controlled under the photosensitization effect of algae organic matter, thereby reducing the generation potential of disinfection by-products to a certain extent. After the addition of persulfate, the content of precursor substances is further reduced, and the fluorescence intensity almost disappears after 60 minutes of illumination. Corresponding to the test results of disinfection by-products, the generation potential of disinfection by-products has been inhibited to a higher degree.

[0097] 2.2 Analysis of active species

[0098] To further illustrate the mechanism by which persulfate enhances the photosensitization effect of algae organic matter to control the generation potential of chlorination disinfection byproducts, high performance liquid chromatography was used to conduct probe experiments on the active species in the system (Table 1, Table 2).

[0099] In order to determine the generation of different active species, 2,4,6-trimethylphenol (2,4,6-trimethylphenol, TMP, 0.2mM), furfuryl alcohol (FFA, 0.1mM), para-chlorobenzoic acid (p-CBA, 10μM) were added into the reaction system as 3 AOM*, 1 O 2 , ·OH probe compounds. The concentrations of TMP, FFA and p-CBA were analyzed by high performance liquid chromatography. All samples were stored in brown liquid vials. The samples were separated in BrownleeValidated AQ C18 columns (150×4.6mm, 5μm) with an injection volume of 50μL. The selected organic mobile phase was chromatographic grade methanol, and the aqueous phase and buffer were prepared with ultrapure water. Impurities were removed by 0.45μm filter membrane, and bubbles in the mobile phase were removed by ultrasonication for 30min before use.

[0100] Table 1

[0101]

[0102]

[0103] Table 2

[0104]

[0105] By observing the generation of the three active species, it was found that after the addition of persulfate, the contents of the three active species increased significantly, and the steady-state concentrations of the three active species increased by about one order of magnitude. In particular, after the addition of persulfate PS, the triple excited state of algae organic matter ( 3 EOM*, 3 The concentration of IOM*) was greatly increased. After adding persulfate, the EOM system 3 The steady-state concentration of EOM* increased by 3.6 times. 3 The steady-state concentration of IOM* increased by 5.7 times. This also shows that the introduction of persulfate, in addition to exerting its own oxidation efficiency, greatly enhanced the photosensitization effect of algae organic matter under solar radiation. Persulfate enhanced the photosensitization effect of algae and greatly increased the steady-state concentration of three active species including the triple excited state, which is the main reason why the enhanced coupling technology can effectively control the generation potential of algae-derived chlorination disinfection byproducts.

[0106] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate, characterized in that: Persulfate is used to enhance the sunlight photosensitization effect of algae organic matter, so as to control the generation potential of chlorinated algae source disinfection by-products.

2. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 1, characterized in that: The persulfate-enhanced sunlight photosensitization effect is manifested in an increase in the content of triplet excited state active species produced by algae organic matter.

3. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 2, characterized in that: The algae are cyanobacteria, and the algae organic matter includes one or more of algae intracellular organic matter IOM and algae extracellular organic matter EOM.

4. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 3, characterized in that: The cyanobacteria include one or more of Microcystis aeruginosa and Anabaena.

5. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 2, characterized in that: The persulfate is peroxydisulfate.

6. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 2, characterized in that: The specific steps include: S1. adding persulfate to a water body containing algae organic matter to obtain a mixed solution; S2, adjusting the pH value of the mixed solution obtained in step S1 to 7±0.1 using a buffer solution to obtain a neutral stock solution; S3, homogenizing the neutral stock solution at a constant temperature, and simultaneously using sunlight to react; S4. After the photoreaction is completed, the pH value of the reaction system is adjusted to 7±0.1, and NaClO reagent is added with a ratio of TOC: free Cl=1:5, and chlorination is performed in the dark. After chlorination, ascorbic acid is added for quenching to obtain treated water.

7. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 6, characterized in that: In step S1, the concentration of algae organic matter in the water body is 2-10 mg / L in terms of TOC, and the concentration of persulfate is 0.001-0.005 mol / L.

8. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 6, characterized in that: The buffer solution in step S2 is a phosphate buffer solution.

9. The method of controlling the generation potential of chlorination disinfection byproducts by enhancing the photosensitization effect of algae organic matter with persulfate according to claim 6, characterized in that: The sunlight in step S3 includes real sunlight or 300W xenon lamp simulating sunlight, and the temperature of the constant temperature reaction is 25±2°C.

10. Use of the method of enhancing the photosensitization effect of algae organic matter by persulfate to control the generation potential of chlorination disinfection by-products as claimed in any one of claims 1 to 9, characterized in that: Control of disinfection by-products produced during the water treatment and disinfection process of drinking water sources containing algae and organic matter.

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