CN113371799B - Electrochemical disinfection method based on singlet oxygen - Google Patents
Electrochemical disinfection method based on singlet oxygen Download PDFInfo
- Publication number
- CN113371799B CN113371799B CN202110693443.3A CN202110693443A CN113371799B CN 113371799 B CN113371799 B CN 113371799B CN 202110693443 A CN202110693443 A CN 202110693443A CN 113371799 B CN113371799 B CN 113371799B
- Authority
- CN
- China
- Prior art keywords
- water
- treated
- electrochemical
- electrode
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F2303/04—Disinfection
Abstract
A singlet oxygen-based electrochemical disinfection method relates to an electrochemical disinfection method. The invention aims to solve the problem that chlorinated organic disinfection byproducts and inorganic disinfection byproducts containing chlorate are easily generated in the existing electrochemical disinfection method. The method comprises the following steps: the electrode which generates hypochlorous acid in situ is used as an anode, and the hypochlorous acid generated by the sequencing batch or flow-through electrochemical reaction and hydrogen peroxide are used for generating singlet oxygen and killing microorganisms in water. The invention is used for the electrochemical disinfection of singlet oxygen.
Description
Technical Field
The present invention relates to an electrochemical disinfection method.
Background
In the water treatment process, disinfection is indispensable, because it can effectively kill pathogenic microorganisms in water, and greatly reduce the pathogenic risk of aquatic diseases. Chlorine disinfectants have been used for centuries and are the most common disinfectants for drinking water treatment. Of course, the use of chlorine also faces difficulties, for example, the formation of harmful disinfection by-products such as chloroform and haloacetic acid during the disinfection process.
The electrochemical disinfection has the advantages of environmental protection, convenient use, cleanness and high efficiency. Meanwhile, the on-line generated disinfection species avoid the transportation, storage and addition of the disinfectant. Based on the electrochemical disinfection technology, the electrochemical disinfection technology has high application potential in a distributed drinking water treatment system, a point-of-use drinking water system and a rural small drinking water supply system. The main principles of electrochemical disinfection include the direct action of the electric field, active chlorine and other active species.
However, the active chlorine generated in electrochemical disinfection still exposes the treated water surface to the risk of overproof chlorinated disinfection by-products, since chloride ions are ubiquitous in water. At the same time, bromide and iodide ions that may be present in the water may also produce bromoiodo disinfection byproducts that are more toxic than chloro disinfection byproducts. In addition, there are other negative effects of the presence of chloride ions. For example, when a BDD anode is used, there is a high perchlorate formation potential. These organic and inorganic chlorine disinfection by-products limit the use of electrochemical disinfection technology in water treatment.
Disclosure of Invention
The invention aims to solve the problem that chlorinated organic disinfection byproducts and inorganic disinfection byproducts containing chlorate are easily generated in the existing electrochemical disinfection method, and further provides a singlet oxygen-based electrochemical disinfection method.
The electrochemical disinfection method based on the singlet oxygen is carried out according to the following steps:
the method comprises the following steps of (1) taking an electrode for generating hypochlorous acid in situ as an anode, generating singlet oxygen by using hypochlorous acid generated by a sequencing batch electrochemical reaction and hydrogen peroxide, and killing microorganisms in water;
when the cathode is a graphite felt electrode, stainless steel or titanium; arranging an anode and a cathode in an electrochemical reactor, wherein the distance between the two electrodes is 1-20 cm, and the volume ratio of the area of the electrodes to the water to be treated is 1cm 2 Adding water to be treated into an electrochemical reactor (10-200 mL), aerating air or oxygen into the electrochemical reactor at a reaction temperature of 3-30 ℃, an aeration amount of 60-200 mL/min, a voltage of 2-30V and a current density of 2.5mA/cm 2 ～10mA/cm 2 Under the condition of (1), carrying out electrochemical treatment for 10-120 min; the water to be treated contains chloride ionsAnd hydrogen peroxide; the concentration of chloride ions in the water to be treated is 0.5 mmol/L-500 mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 0.1 mmol/L-5 mmol/L; the pH value of the water to be treated is 6.5-8.5;
when the cathode is a gas diffusion electrode, the anode and the cathode are arranged in a gas diffusion electrochemical reactor, the distance between the two electrodes is 1 cm-20 cm, and the volume ratio of the area of the electrodes to the water to be treated is 1cm 2 Adding water to be treated into an electrochemical reaction chamber, introducing air or oxygen into a gas diffusion chamber at a flow rate of 60-200 mL/min, at a reaction temperature of 3-30 ℃, at a voltage of 2-30V and at a current density of 2.5mA/cm, wherein the volume of the water to be treated is 10-200 mL 2 ～10mA/cm 2 Under the condition of (1), carrying out electrochemical treatment for 10-120 min; the water to be treated contains chloride ions; the concentration of chloride ions in the water to be treated is 0.5mmol/L to 1000mmol/L; the pH value of the water to be treated is 6.5-8.5.
The electrochemical disinfection method based on the singlet oxygen is carried out according to the following steps:
the electrode which generates hypochlorous acid in situ is taken as an anode, and the hypochlorous acid generated by the through-flow electrochemical reaction and hydrogen peroxide are utilized to generate singlet oxygen which is used for killing microorganisms in water;
the cathode is a graphite felt electrode, stainless steel or titanium; setting anode and cathode in electrochemical reactor, the distance between two electrodes is 1-20 cm, the ratio of flow speed of water to be treated to area of electrode is 1mL/s (2-20) cm 2 Introducing water to be treated from a water inlet of an electrochemical reactor, leading the water to pass through a cathode and then an anode, and leading the water to pass through the cathode and the anode at the reaction temperature of 3-30 ℃, the voltage of 2-30V and the current density of 2.5mA/cm 2 ～10mA/cm 2 Electrochemical treatment under the condition of (1), and finally flowing out of a water outlet of the electrochemical reactor; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 0.5 mmol/L-500 mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 0.1 mmol/L-5 mmol/L; the pH value of the water to be treated is 6.5-8.5.
The invention has the beneficial effects that:
1. the invention uses hydrogen peroxide to quench hypochlorous acid generated by the anode, reduces the steady-state concentration of active chlorine and keeps a very low range, and generates singlet oxygen to kill microorganisms. When the cathode in the sequencing batch electrochemical reaction is a graphite felt electrode and no hydrogen peroxide exists in the water to be treated, the concentration of hypochlorous acid is increased and decreased firstly through hydrogen peroxide generated by the cathode, the total exposure concentration is kept at a lower level, and when the hydrogen peroxide is externally added in advance, the concentration of the hypochlorous acid can be lower than 0.8 mu mol/L, and the inactivation rate of 5 logs of escherichia coli is obtained within 60 min;
2. the invention is especially suitable for a dispersed water treatment system adopting hydrogen peroxide, and the purposes of removing hydrogen peroxide and sterilizing can be simultaneously achieved by using anodic oxidation hydrogen peroxide when chloride ions exist in water.
3. The method of the invention does not need to add chemical agents additionally, only needs to consume electric power, and can realize the disinfection of the water to be treated only by the raw water containing a certain amount of chloride ions, and the method has better practicability because the chloride ions are the most common ions in the water.
4. The hydrogen peroxide and the hypochlorous acid can react quickly, and the existence of the hydrogen peroxide can reduce the steady-state concentration of the hypochlorous acid, so that the chlorination in the disinfection treatment water and the generation of chlorate-containing disinfection byproducts are greatly reduced.
5. The hydrogen peroxide can also react with hypobromous acid and hypoiodic acid quickly, so the method has certain advantages in controlling halogenated disinfection byproducts of the electrochemical disinfection of the halogen-containing water.
The invention is used for a singlet oxygen based electrochemical disinfection method.
Drawings
FIG. 1 is a schematic diagram of the formation of perchlorate and chlorinated disinfection by-products in conventional electrochemical disinfection;
FIG. 2 is a diagram of a sequencing batch apparatus for a singlet oxygen based electrochemical sterilization process with a graphite felt electrode, stainless steel or titanium as the cathode in accordance with the present invention;
FIG. 3 is a graph showing the efficiency of chlorous acid production by an iridium ruthenium titanium oxide electrode under different currents in a comparative experiment, wherein 1 is 2.5mA/cm 2 And 2 is 3.75mA/cm 2 3 is 5mA/cm 2 ；
FIG. 4 is a graph of hydrogen peroxide production efficiency of a graphite felt electrode under different currents in a fifth comparative experiment, wherein 1 is 2.5mA/cm 2 And 2 is 3.75mA/cm 2 And 3 is 5mA/cm 2 ；
FIG. 5 is a graph of logarithmic deactivation rates of Escherichia coli by the electrochemical sterilization method, wherein 1 is a first comparative experiment, 2 is a second comparative experiment, 3 is a third comparative experiment, and 4 is a first example;
FIG. 6 is a data graph of lower hypochlorous acid concentration in the presence of hydrogen peroxide, wherein 1 is electrochemical disinfection in which hydrogen peroxide is not contained in to-be-treated water in a comparative experiment, and 2 is electrochemical disinfection in which hydrogen peroxide is contained in to-be-treated water in examples;
FIG. 7 is a schematic diagram of the near infrared emission of singlet oxygen;
FIG. 8 is a diagram of the near infrared emission of singlet oxygen, b 1 For the comparison of singlet oxygen produced in experiment three, b 2 Singlet oxygen generated for comparative experiment seven;
FIG. 9 is a diagram of a sequencing batch apparatus for a singlet oxygen based electrochemical sterilization process according to the present invention with a gas diffusion electrode as the cathode;
FIG. 10 is a graph showing the current density of 3.75mA/cm in the comparative experiment 2 The efficacy chart of hydrogen peroxide production under the condition of (1);
FIG. 11 is a diagram of a flow-through apparatus for the singlet oxygen-based electrochemical sterilization process of the present invention;
FIG. 12 is a graph showing the effect of removing the logarithm of E.coli in the three-pass flow system of the example.
Detailed Description
The first embodiment is as follows: the electrochemical disinfection method based on the singlet oxygen is implemented according to the following steps:
taking an electrode which generates hypochlorous acid in situ as an anode, generating singlet oxygen by using hypochlorous acid generated by the sequencing batch electrochemical reaction and hydrogen peroxide, and killing microorganisms in water;
when the cathode is a graphite felt electrode, stainless steel or titanium; arranging an anode and a cathode in an electrochemical reactor, wherein the distance between the two electrodes is 1-20 cm, and the area and the position to be treated of the electrodesThe volume ratio of the treated water is 1cm 2 Adding water to be treated into an electrochemical reactor (10-200 mL), aerating air or oxygen into the electrochemical reactor at a reaction temperature of 3-30 ℃, an aeration amount of 60-200 mL/min, a voltage of 2-30V and a current density of 2.5mA/cm 2 ～10mA/cm 2 Under the condition of (1), carrying out electrochemical treatment for 10-120 min; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 0.5 mmol/L-500 mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 0.1 mmol/L-5 mmol/L; the pH value of the water to be treated is 6.5-8.5;
when the cathode is a gas diffusion electrode, the anode and the cathode are arranged in a gas diffusion electrochemical reactor, the distance between the two electrodes is 1 cm-20 cm, and the volume ratio of the area of the electrodes to the water to be treated is 1cm 2 Adding water to be treated into an electrochemical reaction chamber, introducing air or oxygen into a gas diffusion chamber at a flow rate of 60-200 mL/min, at a reaction temperature of 3-30 ℃, at a voltage of 2-30V and at a current density of 2.5mA/cm, wherein the volume of the water to be treated is 10-200 mL 2 ～10mA/cm 2 Under the condition of (2), carrying out electrochemical treatment for 10-120 min; the water to be treated contains chloride ions; the concentration of chloride ions in the water to be treated is 0.5mmol/L to 1000mmol/L; the pH value of the water to be treated is 6.5-8.5.
Singlet oxygen is oxygen in an electron excited state, and has a stronger oxidizing power than oxygen, and thus has attracted much attention in the environmental field. Singlet oxygen has good disinfection capacity, and in a photochemical system, singlet oxygen can be continuously generated through the reaction of dissolved oxygen and a photosensitizer which excites a triplet state, so that pathogenic microorganisms can be effectively killed, and the singlet oxygen is a main active species in sunlight disinfection.
Hydrogen peroxide and hypochlorous acid can generate singlet oxygen approximately one hundred percent under the condition of medium alkalinity, but the reaction is rarely reported in the field of water treatment. It is therefore also possible to achieve an electrochemical inactivation of microorganisms with singlet oxygen.
Electrochemically generating hydrogen peroxide for decentralized water treatment: the hydrogen peroxide is easy to be electrochemically synthesized and activated in situ to degrade micro-pollutants, the residual hydrogen peroxide in the treated water needs to be removed before distribution, and in addition, disinfection is also necessary for the microbial safety of the water. Therefore, when chloride ions exist in water, the purpose of removing hydrogen peroxide and disinfecting can be achieved simultaneously by quenching hydrogen peroxide by anodic oxidation and killing microorganisms by singlet oxygen generated by oxidizing hydrogen peroxide by hypochlorous acid generated in situ by the anode.
In the present embodiment, hydrogen peroxide generated at the cathode is used to quench hypochlorous acid generated at the anode to generate singlet oxygen for sterilization (see fig. 2). The technology converts active chlorine disinfection in electrochemical disinfection into singlet oxygen disinfection, and keeps playing other disinfection functions of an electrochemical system, so that the steady-state concentration of active chlorine in the system is kept in a very low range. Since the generation of a large amount of active chlorine is the key to the generation of perchloric acid and chlorinated disinfection byproducts (as shown in figure 1), the technology can better control the generation of the disinfection byproducts. Therefore, the method has good application and industrialization prospects.
The disinfection technology can be used for disinfection of industrial water systems such as distributed drinking water treatment systems, point-of-use drinking water systems, rural small drinking water treatment systems and seawater. The water flow is in a continuous or batch type with the anode and cathode in one reactor or in a sequence of two reactors. The water to be disinfected passes through the reactor, microorganisms are inactivated in the reactor by the generated singlet oxygen, and the treated water flows out from the outlet of the reactor.
The beneficial effects of the embodiment are as follows:
1. in the embodiment, hydrogen peroxide is used for quenching hypochlorous acid generated by the anode, so that the steady-state concentration of active chlorine is reduced and kept in a very low range, and singlet oxygen is generated to kill microorganisms. When the cathode in the sequencing batch electrochemical reaction is a graphite felt electrode, and no hydrogen peroxide exists in the water to be treated, the concentration of hypochlorous acid is increased and then decreased only through hydrogen peroxide generated by the cathode, the total exposure concentration is maintained at a lower level, and when the hydrogen peroxide is added in advance, the concentration of the hypochlorous acid can be lower than 0.8 mu mol/L, and the inactivation rate of 5 logs of escherichia coli is obtained in 60 min;
2. the embodiment is particularly suitable for a dispersed water treatment system adopting hydrogen peroxide, and when chloride ions exist in water, the hydrogen peroxide is oxidized by using the anode, so that the purposes of removing the hydrogen peroxide and sterilizing can be achieved simultaneously.
3. According to the method, chemical agents do not need to be added additionally, only power is consumed, and the water to be treated can be disinfected only by the raw water containing a certain amount of chloride ions, and the chloride ions are the most common ions in the water, so that the method has good practicability.
4. The hydrogen peroxide and the hypochlorous acid can react quickly, and the existence of the hydrogen peroxide can reduce the steady-state concentration of the hypochlorous acid, so that the chlorination in the disinfection treatment water and the generation of chlorate-containing disinfection byproducts are greatly reduced.
5. The hydrogen peroxide can also react with hypobromous acid and hypoiodic acid quickly, so the method has certain advantages in controlling halogenated disinfection byproducts of the electrochemical disinfection of the halogen-containing water.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the anode is a platinum-titanium electrode, a boron-doped diamond film electrode or an iridium-ruthenium-titanium oxide electrode; the gas diffusion electrode is a graphite electrode modified by one or more of carbon nano tubes, polytetrafluoroethylene and carbon black. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the iridium ruthenium titanium oxide electrode is specifically carried out according to the following steps:
(1) placing the titanium sheet in a mixed liquid containing hydrofluoric acid and nitric acid, and carrying out ultrasonic treatment for 30-180 min to obtain the titanium sheet with the oxide film removed; the concentration of hydrofluoric acid in the mixed liquid containing hydrofluoric acid and nitric acid is 0.1-1 mol/L, and the molar ratio of hydrofluoric acid to nitric acid is (0.5-2): 1; (2) respectively taking the titanium sheet with the oxide film removed as a cathode and an anode to carry out cathode ruthenium plating treatment, taking a ruthenium trichloride solution with the concentration of 1 mmol/L-20 mmol/L as an electrolyte, electroplating for 5 min-30 min at the temperature of 5-30 ℃ and under the voltage of-3V-1V, taking out and drying after electroplating to obtain a ruthenium-plated titanium sheet; (3) the method comprises the steps of performing cathode iridium plating treatment by taking a ruthenium-plated titanium sheet as a cathode and a titanium sheet with an oxide film removed as an anode, electroplating for 5-30 min by taking an ammonium chloroiridate solution with the concentration of 1-20 mmol/L as an electrolyte under the conditions of the temperature of 5-30 ℃ and the voltage of-3V-1V, taking out and drying after electroplating, and finally calcining at high temperature for 30-200 min under the conditions of a nitrogen atmosphere and the calcining temperature of 300-500 ℃ to obtain the iridium ruthenium titanium oxide electrode. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the gas diffusion electrode is specifically carried out according to the following steps: (1) respectively carrying out ultrasonic treatment on the graphite felt electrode in ethanol and water for 20-40 min, and then drying at the temperature of 50-80 ℃ to obtain a cleaned electrode; (2) mixing carbon black powder and polytetrafluoroethylene nano powder, then adding the mixture into an ethanol solution, and performing ultrasonic dispersion and mixing to obtain a mixture, uniformly coating the mixture on two sides of the cleaned electrode, wherein the coating thickness is 0.01-1 mm, and obtaining the coated electrode; the mass ratio of the carbon black powder to the polytetrafluoroethylene nano powder is 1 (1-5); the volume ratio of the mass of the carbon black powder to the ethanol solution is 1g (2-5) mL; (3) and drying the coated electrode at the temperature of 50-80 ℃, finally placing the electrode in a muffle furnace, and sintering the electrode for 30-180 min at the temperature of 330-350 ℃ to obtain the gas diffusion electrode. The other is the same as in the first or second embodiment.
The fifth concrete implementation mode is as follows: the difference between this embodiment and one of the first to fourth embodiments is: the water to be treated is drinking water, seawater or industrial water; the microorganism is bacteria or virus. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the electrochemical disinfection method based on the singlet oxygen is implemented according to the following steps:
the electrode which generates hypochlorous acid in situ is taken as an anode, and the hypochlorous acid generated by the through-flow electrochemical reaction and hydrogen peroxide are used for generating singlet oxygen and killing microorganisms in water;
the cathode is a graphite felt electrode, stainless steel or titanium; setting anode and cathode in electrochemical reactor, the distance between two electrodes is 1-20 cm, the ratio of flow speed of water to be treated to area of electrode is 1mL/s (2-20) cm 2 Introducing water to be treated from a water inlet of an electrochemical reactor, leading the water to pass through a cathode and then an anode, and leading the water to pass through the cathode and the anode at the reaction temperature of 3-30 ℃, the voltage of 2-30V and the current density of 2.5mA/cm 2 ～10mA/cm 2 Electrochemical treatment under the condition of (1), and finally flowing out of a water outlet of the electrochemical reactor; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 0.5 mmol/L-500 mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 0.1 mmol/L-5 mmol/L; the pH value of the water to be treated is 6.5-8.5.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the anode is a platinum-titanium electrode, a boron-doped diamond film electrode or an iridium-ruthenium-titanium oxide electrode. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the present embodiment differs from one of the sixth or seventh embodiments in that: the iridium ruthenium titanium oxide composite electrode is specifically prepared according to the following steps:
(1) placing the titanium sheet in a mixed liquid containing hydrofluoric acid and nitric acid, and carrying out ultrasonic treatment for 30-180 min to obtain the titanium sheet with the oxide film removed; the concentration of hydrofluoric acid in the mixed liquid containing hydrofluoric acid and nitric acid is 0.1-1 mol/L, and the molar ratio of hydrofluoric acid to nitric acid is (0.5-2) to 1; (2) respectively taking the titanium sheet with the oxide film removed as a cathode and an anode to carry out cathode ruthenium plating treatment, taking a ruthenium trichloride solution with the concentration of 1 mmol/L-20 mmol/L as an electrolyte, electroplating for 5 min-30 min at the temperature of 5-30 ℃ and under the voltage of-3V-1V, taking out and drying after electroplating to obtain a ruthenium-plated titanium sheet; (3) the method comprises the steps of performing cathode iridium plating treatment by using a ruthenium-plated titanium sheet as a cathode and a titanium sheet with an oxidation film removed as an anode, electroplating for 5-30 min by using an ammonium chloroiridate solution with the concentration of 1-20 mmol/L as an electrolyte at the temperature of 5-30 ℃ and the voltage of-3V-1V, taking out and drying after electroplating, and finally calcining at high temperature for 30-200 min under the conditions of a nitrogen atmosphere and the calcining temperature of 300-500 ℃ to obtain the iridium ruthenium titanium oxide electrode. The others are the same as the sixth or seventh embodiments.
The specific implementation method nine: this embodiment is different from the sixth to eighth embodiment in that: the water to be treated is drinking water, seawater or industrial water. The others are the same as the sixth to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the sixth to ninth embodiments in that: the microorganism is bacteria or virus. The others are the same as in the sixth to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
referring to fig. 2, the electrochemical disinfection method based on singlet oxygen is specifically described, and is carried out according to the following steps:
taking an electrode which generates hypochlorous acid in situ as an anode, generating singlet oxygen by using hypochlorous acid generated by the sequencing batch electrochemical reaction and hydrogen peroxide, and killing microorganisms in water;
the cathode is a graphite felt electrode, the anode and the cathode are arranged in the electrochemical reactor, the distance between the two electrodes is 2.5cm, and the volume ratio of the area of the electrodes to the water to be treated is 1cm 2 10mL, adding water to be treated into an electrochemical reactor, aerating oxygen into the electrochemical reactor, and controlling the reaction temperature at 20 ℃, the aeration amount at 60mL/min, the voltage at 6V and the current density at 3.75mA/cm 2 Under the condition of (1), carrying out electrochemical treatment for 60-120 min; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 10mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 1mmol/L; the pH value of the water to be treated is 7;
the electrode is fixed by a polytetrafluoroethylene electrode clamp, the size of the cathode and the anode is 5cm multiplied by 4cm, the electrochemical reactor is a cylindrical glass reactor, the volume is 300mL, and the volume of water to be treated is 200mL;
the anode is an iridium ruthenium titanium oxide electrode; the iridium ruthenium titanium oxide composite electrode is specifically prepared according to the following steps:
(1) placing the titanium sheet in a mixed liquid containing hydrofluoric acid and nitric acid, and carrying out ultrasonic treatment for 60min to obtain the titanium sheet with the oxide film removed; the concentration of hydrofluoric acid in the mixed liquid containing hydrofluoric acid and nitric acid is 0.5mol/L, and the molar ratio of the hydrofluoric acid to the nitric acid is 1:1; (2) respectively taking the titanium sheet with the oxide film removed as a cathode and an anode to carry out cathode ruthenium plating treatment, taking ruthenium trichloride solution with the concentration of 5mmol/L as electrolyte, electroplating for 20min at the temperature of 20 ℃ and under the voltage of-2V, taking out and drying after electroplating, and obtaining a ruthenium-plated titanium sheet; (3) and performing cathode iridium plating treatment by using the ruthenium-plated titanium sheet as a cathode and the titanium sheet with the oxide film removed as an anode, electroplating for 20min by using an ammonium chloroiridate solution with the concentration of 5mmol/L as an electrolyte at the temperature of 20 ℃ and the voltage of-2V, taking out and drying after electroplating, and finally calcining at high temperature for 120min under the conditions of a nitrogen atmosphere and the calcining temperature of 350 ℃ to obtain the iridium ruthenium titanium oxide electrode.
The water to be treated is experimental water distribution, contains 10mmol/L of sodium chloride and 1mmol/L of hydrogen peroxide, contains 2mmol/L of phosphate buffer salt to maintain the reaction pH at 7.0, and is added with escherichia coli with the concentration of 10 7 CFU/mL。
Comparison experiment one: the comparative experiment differs from the first example in that: the water to be treated contains sodium sulfate; the concentration of sodium sulfate in the water to be treated is 6mmol/L, and hydrogen peroxide is not added in the water to be treated; the cathode is a titanium sheet electrode. The rest is the same as the first embodiment.
The water to be treated is experiment water distribution containing 6mmol/L sodium sulfate and 2mmol/L phosphate buffer salt to maintain the reaction pH at 7.0, and Escherichia coli with a concentration of 10 is added 7 CFU/mL。
Comparative experiment two: the difference between this comparative experiment and the first example is that: the water to be treated contains hydrogen peroxide; the concentration of hydrogen peroxide in the water to be treated is 1mmol/L; chloride ions are not added into the water to be treated; and no power supply is switched on in the reaction process. The rest is the same as the first embodiment.
The water to be treatedFor experiment, water was added, containing 1mmol/L hydrogen peroxide and 2mmol/L phosphate buffer to maintain the reaction pH at 7.0, and E.coli was added at a concentration of 10 7 CFU/mL。
A third comparative experiment: the comparative experiment differs from the first example in that: the water to be treated contains sodium sulfate and hydrogen peroxide; the concentration of sodium sulfate in the water to be treated is 6mmol/L, and the concentration of hydrogen peroxide is 1mmol/L. The rest is the same as the first embodiment.
The water to be treated is experimental water distribution, contains 6mmol/L of sodium sulfate, 1mmol/L of hydrogen peroxide and 2mmol/L of phosphate buffer salt to maintain the reaction pH at 7.0, and Escherichia coli with the concentration of 10 is added 7 CFU/mL。
And a fourth comparative experiment: the comparative experiment differs from the first example in that: the cathode is a titanium sheet electrode; the water to be treated contains chloride ions; the concentration of chloride ions in the water to be treated is 10mmol/L; hydrogen peroxide is not added into the water to be treated; aeration is not carried out in the electrochemical reaction process. The rest is the same as the first embodiment.
The water to be treated is experiment water, contains 10mmol/L of sodium chloride and 2mmol/L of phosphate buffer salt so as to maintain the reaction pH at 7.0, and does not contain escherichia coli.
A fifth comparative experiment: the difference between this comparative experiment and the first example is that: the water to be treated contains sodium sulfate; the concentration of sodium sulfate in the water to be treated is 6mmol/L. The rest is the same as in the first embodiment.
The water to be treated is experiment water, contains 6mmol/L sodium sulfate and 2mmol/L phosphate buffer salt to maintain the reaction pH at 7.0, and no colibacillus is added.
A sixth comparative experiment: the comparative experiment differs from the first example in that: the water to be treated contains chloride ions; the concentration of chloride ions in the water to be treated is 10mmol/L, and the water to be treated does not contain hydrogen peroxide; the pH value of the water to be treated is 7. The rest is the same as in the first embodiment.
The water to be treated is experiment water, contains 10mmol/L of sodium chloride and 2mmol/L of phosphate buffer salt so as to maintain the reaction pH at 7.0, and does not contain escherichia coli.
A seventh comparative experiment: the comparative experiment differs from the first example in that: the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 200mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 1mmol/L; the pH value of the water to be treated is 7. The rest is the same as the first embodiment.
The water to be treated is experimental water distribution, contains 200mmol/L of sodium chloride and 1mmol/L of hydrogen peroxide, contains 2mmol/L of phosphate buffer salt to maintain the reaction pH at 7.0, and does not contain escherichia coli.
In order to independently test the chlorous acid production performance of the iridium ruthenium titanium oxide electrode and further perform the chlorous acid production according to a fourth comparative experiment, FIG. 3 is a chlorous acid production efficiency graph of the iridium ruthenium titanium oxide electrode under different currents in the fourth comparative experiment, and 1 is 2.5mA/cm 2 And 2 is 3.75mA/cm 2 And 3 is 5mA/cm 2 . As can be seen from the graph, the iridium ruthenium titanium oxide electrode has good hypochlorous acid generating capability, the generation amount of hypochlorous acid increases with the increase of the current density, and the concentration of hypochlorous acid generated in 120 minutes is about 500. Mu. Mol/L, 800. Mu. Mol/L and 1100. Mu. Mol/L, respectively.
In order to independently test the performance of the graphite felt electrode for generating hydrogen peroxide and further perform the test according to a fifth comparative experiment, fig. 4 is a graph of hydrogen peroxide generation efficiency of the graphite felt electrode under different currents in the fifth comparative experiment, and 1 is 2.5mA/cm 2 And 2 is 3.75mA/cm 2 And 3 is 5mA/cm 2 . As can be seen from the figure, the yield of the hydrogen peroxide under the three current densities is not greatly different, and the maximum yield is 3.75mA/cm 2 The yield at 20 minutes was approximately 520. Mu. Mol/L.
FIG. 5 is a graph of logarithmic deactivation rate of Escherichia coli by electrochemical sterilization method, wherein 1 is a first comparative experiment, 2 is a second comparative experiment, 3 is a third comparative experiment, and 4 is a first example; as can be seen from the figure, the inactivation of Escherichia coli in the sequencing batch reactor is limited by the disinfection capability of hydrogen peroxide alone, while the direct electrical inactivation of Escherichia coli on the electrode is negligible through a comparative test, and as can be seen from the data in FIG. 6, the hypochlorous acid concentration in the first example is substantially lower than 0.8 μ M/L, so that singlet oxygen can effectively inactivate Escherichia coli, and 5 logs of inactivation rate of Escherichia coli are obtained in 60min in the first example.
Fig. 6 is a data graph of the lower hypochlorous acid concentration in the presence of hydrogen peroxide, 1 is electrochemical disinfection in which hydrogen peroxide is not contained in to-be-treated water in the comparative experiment, and 2 is electrochemical disinfection in which hydrogen peroxide is contained in to-be-treated water in the example. As is clear from the figure, when no hydrogen peroxide is present, the concentration of hypochlorous acid is increased and decreased only by hydrogen peroxide generated at the cathode, and the total exposure concentration is maintained at a low level, whereas when hydrogen peroxide is added in advance, the concentration of hypochlorous acid can be lower than 0.8. Mu. Mol/L.
FIG. 7 is a schematic diagram of the near infrared emission of singlet oxygen, FIG. 8 is a schematic diagram of the near infrared emission of singlet oxygen, b 1 For the comparison of singlet oxygen produced in experiment three, b 2 Singlet oxygen generated for comparative experiment seven; in order to detect singlet oxygen generated by an electrochemical system, a near infrared observation system is adopted. The singlet oxygen can be emitted along with the near infrared under 1268nm in the process of relaxation in water, the experimental principle is shown in the figure, and researches find that the chlorine ions are adopted as the electrolyte solution, and when hydrogen peroxide exists, obvious near infrared signals can be detected, thereby proving the generation of the singlet oxygen.
Example two: as described in detail with reference to fig. 9, the difference between the present embodiment and the first embodiment is: the cathode adopts a gas diffusion electrode, water to be treated is added into the electrochemical reaction chamber, and oxygen is introduced into the gas diffusion chamber at the flow rate of 100 mL/min; the water to be treated contains chloride ions; the concentration of chloride ions in the water to be treated is 10mmol/L; the pH value of the water to be treated is 7; the gas diffusion electrode is specifically carried out according to the following steps: (1) respectively carrying out ultrasonic treatment on the graphite felt electrode in ethanol and water for 30min, and then drying at the temperature of 80 ℃ to obtain a cleaned electrode; (2) mixing carbon black powder and polytetrafluoroethylene nano powder, then adding the mixture into an ethanol solution, and performing ultrasonic dispersion and mixing to obtain a mixture, uniformly coating the mixture on two sides of the cleaned electrode, wherein the coating thickness is 1mm, and obtaining the coated electrode; the mass ratio of the carbon black powder to the polytetrafluoroethylene nano powder is 1:3; the volume ratio of the mass of the carbon black powder to the ethanol solution is 1g; (3) and drying the coated electrode at the temperature of 80 ℃, finally placing the electrode in a muffle furnace, and sintering for 1h at the temperature of 350 ℃ to obtain the gas diffusion electrode. The rest is the same as the first embodiment.
And for the independent test, the performance of generating hydrogen peroxide by adopting the gas diffusion electrode is further carried out according to a contrast experiment eight:
eight comparative experiments: the difference between this comparative experiment and example two is that: the water to be treated contains sodium sulfate; the concentration of sodium sulfate in the water to be treated is 6mmol/L. The rest is the same as the first embodiment.
The water to be treated is experiment water, contains 6mmol/L sodium sulfate and 2mmol/L phosphate buffer salt to maintain the reaction pH at 7.0, and no colibacillus is added.
Namely, oxygen enters the left electrochemical reaction chamber from the surface of the electrode uniformly through the right gas diffusion chamber and is reduced into hydrogen peroxide on the surface of the electrode. Due to the existence of the hydrophobic interface of the cathode of the gas diffusion electrode, the hydrogen peroxide generation efficiency can be greatly improved, and the dissolved oxygen in water can be utilized for double-electron reduction. FIG. 10 is a graph showing the current density of 3.75mA/cm in the comparative experiment 2 The efficacy chart of hydrogen peroxide production under the condition of (1); as shown, the yield of hydrogen peroxide is much higher than that of a pure graphite felt electrode by adopting a gas diffusion electrode, and the current density adopted in the fifth comparative experiment is 3.75mA/cm 2 The yield of the hydrogen peroxide solution in 20 minutes is about 520 mu mol/L, and the hydrogen peroxide solution in 20 minutes can generate 4mmol/L in the gas diffusion electrode, so that the efficiency is improved by 8 times.
Oxygen enters the graphite felt electrode through the gas chamber and is electrochemically reduced on the surface of the graphite felt electrode, and the gas diffusion electrode can remarkably improve the yield of hydrogen peroxide and has high current efficiency. Due to the high hydrogen peroxide generation efficiency, the anode can be allowed to generate hypochlorous acid at a high rate and make its steady-state concentration at a low level in the reactor. The reaction structure is suitable for high-concentration sodium chloride inlet water.
Example three:
referring to fig. 11, the electrochemical disinfection method based on singlet oxygen is specifically described, which is performed according to the following steps:
the electrode which generates hypochlorous acid in situ is taken as an anode, and the hypochlorous acid generated by the through-flow electrochemical reaction and hydrogen peroxide are used for generating singlet oxygen and killing microorganisms in water;
the cathode is made of stainless steel; arranging an anode and a cathode in an electrochemical reactor, wherein the distance between the two electrodes is 2.5cm, and the ratio of the flow rate of water to be treated to the area of the electrodes is 1mL/s:20cm 2 Introducing water to be treated from a water inlet of an electrochemical reactor, leading the water to pass through a cathode and then an anode, and leading the reaction temperature to be 20 ℃, the voltage to be 6V and the current density to be 3.75mA/cm 2 Electrochemical treatment under the condition of (1), and finally flowing out of a water outlet of the electrochemical reactor; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 10mmol/L; 1mmol/L of hydrogen peroxide in the water to be treated; the pH value of the water to be treated is 7.
The anode is an iridium ruthenium titanium oxide electrode; the iridium ruthenium titanium oxide composite electrode is specifically prepared according to the following steps:
(1) placing the titanium sheet in a mixed liquid containing hydrofluoric acid and nitric acid, and carrying out ultrasonic treatment for 60min to obtain the titanium sheet with the oxide film removed; the concentration of hydrofluoric acid in the mixed liquid containing hydrofluoric acid and nitric acid is 0.5mol/L, and the molar ratio of the hydrofluoric acid to the nitric acid is 1:1; (2) respectively taking the titanium sheet with the oxide film removed as a cathode and an anode to carry out cathode ruthenium plating treatment, taking a ruthenium trichloride solution with the concentration of 5mmol/L as an electrolyte, electroplating for 20min at the temperature of 20 ℃ and under the voltage of-2V, taking out and drying after electroplating to obtain a ruthenium-plated titanium sheet; (3) and performing cathode iridium plating treatment by using the ruthenium-plated titanium sheet as a cathode and the titanium sheet with the oxide film removed as an anode, electroplating for 20min by using an ammonium chloroiridate solution with the concentration of 5mmol/L as an electrolyte at the temperature of 20 ℃ and the voltage of-2V, taking out and drying after electroplating, and finally calcining at high temperature for 120min under the conditions of a nitrogen atmosphere and the calcining temperature of 350 ℃ to obtain the iridium ruthenium titanium oxide electrode.
The water to be treated is experimental water distribution, contains 10mmol/L of sodium chloride and 1mmol/L of hydrogen peroxide, contains 2mmol/L of phosphate buffer salt,to maintain the reaction pH at about 7.0, and adding Escherichia coli at a concentration of 10 5 CFU/mL。
FIG. 12 is a graph showing the logarithmic removal effect of Escherichia coli in a three-pass flow system according to the example. As shown, E.coli obtained approximately 2.5 log removal.
Claims (1)
1. The electrochemical disinfection method based on the singlet oxygen is characterized by comprising the following steps:
the method comprises the following steps of (1) taking an electrode for generating hypochlorous acid in situ as an anode, generating singlet oxygen by using hypochlorous acid generated by a sequencing batch electrochemical reaction and hydrogen peroxide, and killing microorganisms in water;
the graphite felt electrode is a cathode, an anode and a cathode are arranged in the electrochemical reactor, the distance between the two electrodes is 2.5cm, and the volume ratio of the area of the electrodes to the water to be treated is 1cm 2 10mL, adding water to be treated into an electrochemical reactor, aerating oxygen into the electrochemical reactor, and controlling the reaction temperature at 20 ℃, the aeration amount at 60mL/min, the voltage at 6V and the current density at 3.75mA/cm 2 Under the condition of (1), carrying out electrochemical treatment for 60min to 120min; the water to be treated contains chloride ions and hydrogen peroxide; the concentration of chloride ions in the water to be treated is 10mmol/L, and the concentration of hydrogen peroxide in the water to be treated is 1mmol/L; the pH value of the water to be treated is 7;
the electrode is fixed by a polytetrafluoroethylene electrode clamp, the size of the cathode and the anode is 5cm multiplied by 4cm, the electrochemical reactor is a cylindrical glass reactor, the volume is 300mL, and the volume of water to be treated is 200mL;
the anode is an iridium ruthenium titanium oxide electrode; the iridium ruthenium titanium oxide composite electrode is specifically prepared by the following steps:
(1) placing the titanium sheet in a mixed liquid containing hydrofluoric acid and nitric acid, and carrying out ultrasonic treatment for 60min to obtain the titanium sheet with the oxide film removed; the concentration of hydrofluoric acid in the mixed liquid containing hydrofluoric acid and nitric acid is 0.5mol/L, and the molar ratio of the hydrofluoric acid to the nitric acid is 1:1; (2) respectively taking the titanium sheet with the oxide film removed as a cathode and an anode to carry out cathode ruthenium plating treatment, taking a ruthenium trichloride solution with the concentration of 5mmol/L as an electrolyte, electroplating for 20min at the temperature of 20 ℃ and under the voltage of-2V, taking out and drying after electroplating to obtain a ruthenium-plated titanium sheet; (3) and performing cathode iridium plating treatment by using the ruthenium-plated titanium sheet as a cathode and the titanium sheet with the oxide film removed as an anode, electroplating for 20min by using an ammonium chloroiridate solution with the concentration of 5mmol/L as an electrolyte under the conditions of the temperature of 20 ℃ and the voltage of-2V, taking out and drying after electroplating, and finally calcining for 120min under the conditions of a nitrogen atmosphere and the calcining temperature of 350 ℃ to obtain the iridium ruthenium titanium oxide electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110693443.3A CN113371799B (en) | 2021-06-22 | 2021-06-22 | Electrochemical disinfection method based on singlet oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110693443.3A CN113371799B (en) | 2021-06-22 | 2021-06-22 | Electrochemical disinfection method based on singlet oxygen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113371799A CN113371799A (en) | 2021-09-10 |
| CN113371799B true CN113371799B (en) | 2022-10-04 |
Family
ID=77578433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110693443.3A Active CN113371799B (en) | 2021-06-22 | 2021-06-22 | Electrochemical disinfection method based on singlet oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113371799B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411193B (en) * | 2022-03-28 | 2022-06-10 | 苏州科技大学 | Electrochemical preparation system and preparation method of singlet oxygen |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000254650A (en) * | 1999-03-15 | 2000-09-19 | Permelec Electrode Ltd | Water treatment and water treatment device |
| JP2009050722A (en) * | 2008-11-27 | 2009-03-12 | Sanyo Electric Co Ltd | Disinfection system |
| CN101435084A (en) * | 2008-12-04 | 2009-05-20 | 福州大学 | Titanium anode with coating having alternate laminated structure and preparation thereof |
| AU2009235914A1 (en) * | 2008-04-11 | 2009-10-15 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| CA2632788A1 (en) * | 2008-05-30 | 2009-11-30 | Institut National De La Recherche Scientifique (Inrs) | Degradation of organic toxics by electro-oxidation |
| US8367120B1 (en) * | 2007-10-31 | 2013-02-05 | Reoxcyn Discoveries Group, Inc. | Method and apparatus for producing a stablized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic |
| CN103523897A (en) * | 2013-10-31 | 2014-01-22 | 哈尔滨工业大学 | Water treatment compound agent for removing organic pollutants in oxidation mode with high-activity singlet oxygen and water treatment method thereof |
| WO2014100912A1 (en) * | 2012-12-24 | 2014-07-03 | 北京化工大学 | Gas diffusion electrode and preparation method thereof |
| CN108928892A (en) * | 2018-08-15 | 2018-12-04 | 清华大学 | A method of landfill leachate is handled based on electric Fenton coupling electric flocculation |
| CN109234757A (en) * | 2018-10-18 | 2019-01-18 | 任杰 | A kind of preparation method and application of uniform and stable ruthenium iridium bimetal-doped Ti electrode |
| WO2019050078A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus using electrolysis and heterogeneous catalytic oxidation reaction |
| WO2019050079A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus for simultaneously generating hydrogen peroxide and hypochlorite ion |
| CN111646552A (en) * | 2020-05-22 | 2020-09-11 | 东华大学 | Flow-through electrochemical system for selectively degrading organic pollutants based on singlet oxygen and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285369A (en) * | 2001-03-23 | 2002-10-03 | Permelec Electrode Ltd | Electrolytic cell for producing hydrogen peroxide solution and hypohalide, and method therefor |
| US20090110749A1 (en) * | 2007-10-30 | 2009-04-30 | Medical Management Research, Inc. | Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic |
| US8663705B2 (en) * | 2007-10-30 | 2014-03-04 | Reoxcyn Discoveries Group, Inc. | Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic |
| JP2011007508A (en) * | 2009-06-23 | 2011-01-13 | Sanyo Electric Co Ltd | Method for measuring concentration of free residual chlorine, and method for generating hypochlorous acid using the same |
| JP2011224424A (en) * | 2010-04-15 | 2011-11-10 | Panasonic Corp | Apparatus for treating water |
| WO2014039929A1 (en) * | 2012-09-07 | 2014-03-13 | Clean Chemistry, Llc | Systems and methods for generation of reactive oxygen species and applications thereof |
| ES2916459T3 (en) * | 2018-10-18 | 2022-07-01 | Blue Safety Gmbh | Electrochemical system for the synthesis of an aqueous solution of oxidizing agent |
-
2021
- 2021-06-22 CN CN202110693443.3A patent/CN113371799B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000254650A (en) * | 1999-03-15 | 2000-09-19 | Permelec Electrode Ltd | Water treatment and water treatment device |
| US8367120B1 (en) * | 2007-10-31 | 2013-02-05 | Reoxcyn Discoveries Group, Inc. | Method and apparatus for producing a stablized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic |
| AU2009235914A1 (en) * | 2008-04-11 | 2009-10-15 | Francois Cardarelli | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
| CA2632788A1 (en) * | 2008-05-30 | 2009-11-30 | Institut National De La Recherche Scientifique (Inrs) | Degradation of organic toxics by electro-oxidation |
| JP2009050722A (en) * | 2008-11-27 | 2009-03-12 | Sanyo Electric Co Ltd | Disinfection system |
| CN101435084A (en) * | 2008-12-04 | 2009-05-20 | 福州大学 | Titanium anode with coating having alternate laminated structure and preparation thereof |
| WO2014100912A1 (en) * | 2012-12-24 | 2014-07-03 | 北京化工大学 | Gas diffusion electrode and preparation method thereof |
| CN103523897A (en) * | 2013-10-31 | 2014-01-22 | 哈尔滨工业大学 | Water treatment compound agent for removing organic pollutants in oxidation mode with high-activity singlet oxygen and water treatment method thereof |
| WO2019050078A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus using electrolysis and heterogeneous catalytic oxidation reaction |
| WO2019050079A1 (en) * | 2017-09-06 | 2019-03-14 | (주) 테크로스 | Water treatment apparatus for simultaneously generating hydrogen peroxide and hypochlorite ion |
| CN108928892A (en) * | 2018-08-15 | 2018-12-04 | 清华大学 | A method of landfill leachate is handled based on electric Fenton coupling electric flocculation |
| CN109234757A (en) * | 2018-10-18 | 2019-01-18 | 任杰 | A kind of preparation method and application of uniform and stable ruthenium iridium bimetal-doped Ti electrode |
| CN111646552A (en) * | 2020-05-22 | 2020-09-11 | 东华大学 | Flow-through electrochemical system for selectively degrading organic pollutants based on singlet oxygen and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Cyanide oxidation by singlet oxygen generated via reaction between H2O2 fron cathodic reduction and OCl- from anodic oxidation;Shichao Tian et al.;《Journal of Colloid and Interface Science》;20160715;第482卷;205-211 * |
| Ti/SnO_2-Sb阳极-空气阴极电催化降解染料废水;赵敏等;《环境工程》;20170430;第35卷(第04期);31-35+96 * |
| 过氧化氢及次氯酸钠的同步电合成及其原位氨氮去除效果;徐大元等;《化工环保》;20100430;第30卷(第2期);168-171 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113371799A (en) | 2021-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4116949B2 (en) | Electrochemical sterilization and sterilization method | |
| Matsunaga et al. | Electrochemical disinfection of bacteria in drinking water using activated carbon fibers | |
| AU2006269410B2 (en) | Methods and apparatus for generating oxidizing agents | |
| CN110759437B (en) | Method for electrochemical-UV composite treatment of refractory organic matters | |
| CN101531411A (en) | Method for electrochemically disinfecting gas diffusion electrode system | |
| US20180319680A1 (en) | Apparatus and Method for Electrodisinfection | |
| JP2004143519A (en) | Water treatment method and water treatment device | |
| CN101746857A (en) | Method and equipment of electrochemical disinfection for water | |
| CN113371799B (en) | Electrochemical disinfection method based on singlet oxygen | |
| Trigueiro et al. | Inactivation, lysis and degradation by-products of Saccharomyces cerevisiae by electrooxidation using DSA | |
| JP4098617B2 (en) | Sterilization method | |
| JP2018196883A (en) | Method for controlling generation of halogen-containing by-products in drinking water treatment | |
| KR102013864B1 (en) | Method for high level oxidation of organic materials using electrolyzed water and uv treatment | |
| US10239772B2 (en) | Recycling loop method for preparation of high concentration ozone | |
| CN212532588U (en) | Device for inactivating algae in ship ballast water by DSA anode electro-catalysis | |
| JP2004313780A (en) | Electrolytic synthesis method of peracetic acid, and method and apparatus for sterilization wash | |
| AU2018224428A1 (en) | System for water disinfection using electroporation | |
| Xu et al. | Electrochemical disinfection using the gas diffusion electrode system | |
| JP3583608B2 (en) | Electrolytic sterilizing apparatus and electrolytic sterilizing method | |
| CN113215595B (en) | Portable hypochlorous acid sterilizing water production device | |
| CN211035348U (en) | Raw material supply device for acidic electrolyzed water generator | |
| KR102008396B1 (en) | Operation manual for an electrolysis water system | |
| Gusmão et al. | A thin layer electrochemical cell for disinfection of water contaminated with Staphylococcus aureus | |
| CN116573732A (en) | Method for removing ARB and ARGs in water by using UV irradiation coupling in-situ chlorine production technology | |
| Jwa et al. | In situ disinfection and green hydrogen production using carbon-based cathodes in seawater electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |