Photoelectrochemical device, method for purifying seawater

Abstract

The application belongs to the technical field of seawater purification, and particularly relates to a photoelectrochemical device and a seawater purification method. The application provides a photoelectrochemical device, which comprises a reactor assembly (1), an electrode assembly (2) and an ultraviolet lamp assembly (3). The reactor assembly (1) comprises a reactor body and a reactor top cover. The electrode assembly (2) and the ultraviolet lamp assembly (3) are fixed on the reactor top cover. The application realizes degradation of new pollutants in water bodies through ultraviolet light combined with electrochemical advanced oxidation technology, and has the advantages of low cost, economic environmental protection and high degradation efficiency compared with electrochemical technology and photolysis technology. The application can adjust the reactor capacity, electrolysis conditions, electrode plate spacing and size according to water quality conditions and actual conditions, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of seawater purification technology, specifically relating to a photoelectrochemical device and a seawater purification method. Background Technology

[0002] In recent years, new pollutants have been frequently detected in water bodies, and their stability and bioaccumulation have gradually attracted public attention. These new pollutants originate from people's daily lives, and their types are constantly increasing with technological advancements. Norfloxacin, ofloxacin, ciprofloxacin, and flumethinazole, among other commonly used antibiotics, are widely used in mariculture areas. Benzophenones, camphor derivatives, and cinnamic acid derivatives, among other sunscreens, have high residue levels in seawater from beaches and exhibit significant toxic effects on various marine organisms. These new pollutants enter drinking water at low concentrations through the water cycle, ultimately affecting human health. Therefore, the treatment of these new pollutants has become a matter of widespread concern.

[0003] Currently, among technologies for treating new pollutants, the UV / Chlorine system has attracted widespread attention due to its ability to generate more selective reactive substances (RCS) such as Cl·, Cl2·, and ClO· compared to hydroxyl radicals. However, the continuous consumption of hypochlorous acid during the reaction leads to a decrease in the concentration of active substances, hindering the sustained degradation of new pollutants. Furthermore, the high cost of transporting and purchasing hypochlorous acid impedes the practical application of this technology. Electrochemical anode chlorination technology (EC / Cl...) - It can utilize Cl in water. - In-situ chlorine production generates hydroxyl radicals, but its effectiveness in removing some new pollutants is poor. Therefore, there is a need to develop an economical, environmentally friendly method that can both continuously produce chlorine to achieve sustained degradation of new pollutants and efficiently generate RCS radicals, with broad application prospects. Summary of the Invention

[0004] The purpose of this invention is to provide a photoelectrochemical device and a seawater purification method. The electrochemical device provided by this invention can achieve continuous degradation of pollutants with high degradation efficiency, and is economical and environmentally friendly.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a photoelectrochemical device, comprising a reactor assembly 1, an electrode assembly 2, and an ultraviolet lamp assembly 3;

[0007] The reactor assembly 1 includes a reactor body and a reactor top cover;

[0008] The electrode assembly 2 and the ultraviolet lamp assembly 3 are fixed on the top cover of the reactor.

[0009] Preferably, the reactor body is a cylindrical double-layered glass; a circulating water bath inlet / outlet 7 is provided on the outer wall of the reactor body;

[0010] The photoelectrochemical device further includes a circulating water bath assembly 6; the circulating water bath assembly 6 includes a circulating water pump 22 and a rubber tube 23.

[0011] The circulating water pump 22 is connected to the circulating water bath inlet and outlet 7 via a rubber hose 23.

[0012] Preferably, the reactor top cover is made of polytetrachloroethylene, and the reactor top cover is provided with a first through hole 8, a second through hole 9 and a third through hole 10;

[0013] The first through hole 8 is used to fix the ultraviolet lamp assembly 3; the second through hole 9 is used to fix the electrode assembly 2; and the third through hole 10 is used for sampling and detection.

[0014] Preferably, the electrode assembly 2 includes a PEEK electrode clip 11, a ruthenium-iridium-titanium electrode sheet 12, a stainless steel plate 13, a wire 14, and a DC power supply 15;

[0015] The ruthenium-iridium-titanium electrode sheet 12 and the stainless steel plate 13 are connected to the DC power supply 15 in sequence via PEEK electrode clip 11 and wire 14, respectively.

[0016] Preferably, the ultraviolet lamp assembly 3 includes an LED lamp 16 and a quartz glass protective lamp cover 17.

[0017] Preferably, the photoelectrochemical device further includes a heat dissipation component 4; the heat dissipation component 4 includes a blower 18 and a vent pipe 19; the vent pipe 19 is placed in the quartz glass protective lamp cover 17.

[0018] Preferably, the photoelectrochemical device further includes a magnetic stirring assembly 5, which includes a rotor 20 and a magnetic stirrer 21, with the reactor body placed on the magnetic stirrer 21.

[0019] This invention also provides a method for purifying seawater, using the photoelectrochemical device described above, comprising the following steps:

[0020] The seawater to be purified is introduced into reactor assembly 1, and purified by the combined action of electrolysis and ultraviolet irradiation using electrode assembly 2 and ultraviolet lamp assembly 3.

[0021] Preferably, the distance between the ruthenium-iridium-titanium electrode sheet 12 and the stainless steel plate 13 in the electrode assembly 2 is 3 to 6 cm;

[0022] The electrolysis voltage is 2.46–2.69 V, and the current density is 1–5 mA / cm². 2 ;

[0023] The ultraviolet light used for the ultraviolet irradiation is 285nm.

[0024] Preferably, the purification is carried out under stirring conditions, and the stirring speed is 400 rpm;

[0025] The purification temperature is 15–30°C.

[0026] This invention provides a photoelectrochemical device, comprising a reactor assembly 1, an electrode assembly 2, and an ultraviolet lamp assembly 3. The reactor assembly 1 includes a reactor body and a reactor top cover. The electrode assembly 2 and the ultraviolet lamp assembly 3 are fixed to the reactor top cover. This invention achieves the degradation of new pollutants in water through a combination of ultraviolet light and advanced electrochemical oxidation technology. Compared with electrochemical and photolysis technologies, it has the advantages of low cost, economic efficiency, environmental friendliness, and high degradation efficiency. The reactor capacity, electrolysis conditions, electrode spacing, and dimensions can be adjusted according to water quality conditions and actual circumstances, and this invention has broad application prospects. Attached Figure Description

[0027] Figure 1 A schematic diagram of the photoelectrochemical device provided by the present invention;

[0028] Figure 2 This is a front view of electrode assembly 2 in this invention;

[0029] Figure 3 This is a front view of the ultraviolet lamp assembly 2 and the heat dissipation assembly 4 in this invention;

[0030] Figure 4 This is a front view of the reactor assembly 1, the magnetic stirring assembly 5, and the circulating water bath assembly 6 in this invention;

[0031] Figure 5 This is a top view of the reactor top cover in this invention;

[0032] Figure 6 This is a schematic diagram illustrating the reaction principle of seawater purification in this invention;

[0033] Figure 7 This is a diagram illustrating the degradation effect of the present invention on antibiotics (enrofloxacin) in seawater;

[0034] Among them: 1-reactor assembly, 2-electrode assembly, 3-UV lamp assembly, 4-heat dissipation assembly, 5-magnetic stirring assembly, 6-circulating water bath assembly, 7-water bath inlet and outlet, 8-first through hole, 9-second through hole, 10-third through hole, 11-PEEK electrode clamp, 12-ruthenium iridium titanium electrode sheet, 13-stainless steel plate, 14-wire, 15-DC power supply, 16-LED lamp, 17-quartz glass protective lamp cover, 18-blower, 19-vent pipe, 20-rotor, 21-magnetic stirrer, 22-circulating water pump, 23-rubber hose. Detailed Implementation

[0035] This invention provides a photoelectrochemical device, comprising a reactor assembly 1, an electrode assembly 2, and an ultraviolet lamp assembly 3;

[0036] The reactor assembly 1 includes a reactor body and a reactor top cover;

[0037] The electrode assembly 2 and the ultraviolet lamp assembly 3 are fixed on the top cover of the reactor.

[0038] In this invention, the reactor body is preferably a cylindrical double-layered glass; a circulating water bath inlet / outlet 7 is preferably provided on the outer wall of the reactor body. In this invention, the photoelectrochemical device also preferably includes a circulating water bath assembly 6; the circulating water bath assembly 6 preferably includes a circulating water pump 22 and a rubber tube 23; the circulating water pump 22 is connected to the circulating water bath inlet / outlet 7 via the rubber tube 23. In this invention, the circulating water pump 22 is connected to the inlet / outlet 7 on both sides of the reactor body via the rubber tube 22, and a constant temperature is achieved during the reaction process through water bath heating.

[0039] In this invention, the reactor top cover is preferably made of polytetrachloroethylene, and the reactor top cover is preferably provided with a first through hole 8, a second through hole 9 and a third through hole 10; the first through hole 8 is used to fix the ultraviolet lamp assembly 3; the second through hole 9 is used to fix the electrode assembly 2; and the third through hole 10 is used for sampling and detection.

[0040] In this invention, the electrode assembly 2 preferably includes a PEEK electrode clip 11, a ruthenium-iridium-titanium electrode sheet 12, a stainless steel plate 13, a wire 14, and a DC power supply 15; the ruthenium-iridium-titanium electrode sheet 12 and the stainless steel plate 13 are preferably connected to the DC power supply 15 sequentially via the PEEK electrode clip 11 and the wire 14, respectively. In this invention, the thickness of the ruthenium-iridium-titanium electrode sheet 12 and the stainless steel plate 13 is preferably 1 mm, and their size is preferably 1 × 4 cm.

[0041] In this invention, the ruthenium-iridium-titanium electrode 12 and the stainless steel plate 13 serve as the anode and cathode of the device, respectively, and the size of the electrode plates can be adjusted according to actual application. The ruthenium-iridium-titanium electrode 12 is a DSA electrode. Compared with commonly used inert electrodes (BDD, etc.), this electrode can directly oxidize chloride ions to Cl2 on its surface and generate HClO / OCl- in the ion diffusion layer on the anode surface and the reaction solution. It has high catalytic activity, good electrochemical stability, and low electrolysis energy consumption, which can effectively save energy and achieve higher chlorine production efficiency. In this invention, the voltage of the DC power supply 15 is preferably 12V. In this invention, the ruthenium-iridium-titanium electrode 12 and the stainless steel plate 13 need to be cleaned in a timely manner and maintained regularly after use to ensure chlorine production efficiency.

[0042] In this invention, the ultraviolet lamp assembly 3 preferably includes an LED lamp 16 and a quartz glass protective lamp cover 17. In this invention, the quartz glass protective lamp cover 17 has good light transmittance.

[0043] In this invention, the photoelectrochemical device preferably includes a heat dissipation component 4; the heat dissipation component 4 preferably includes a blower 18 and a vent pipe 19; the vent pipe 19 is preferably placed inside the quartz glass protective lamp cover 17. In this invention, the blower 18 transmits airflow through the vent pipe 19 to the ultraviolet lamp assembly 3 to prevent the LED lamp temperature from becoming too high and affecting its performance.

[0044] In this invention, the photoelectrochemical device preferably includes a magnetic stirring assembly 5, which preferably includes a rotor 20 and a magnetic stirrer 21, and the reactor body is preferably placed on the magnetic stirrer 21. In this invention, the rotation of the rotor 21 drives the water to flow, ensuring that the water in the reactor is homogeneous.

[0045] This invention also provides a method for purifying seawater, using the photoelectrochemical device described above, comprising the following steps:

[0046] The seawater to be purified is introduced into reactor assembly 1, and purified by the combined action of electrolysis and ultraviolet irradiation using electrode assembly 2 and ultraviolet lamp assembly 3.

[0047] In this invention, the distance between the ruthenium-iridium-titanium electrode sheet 12 and the stainless steel plate 13 in the electrode assembly 2 is preferably 3-6 cm. In this invention, the electrolysis voltage is preferably 2.46-2.69 V, and the current density is preferably 1-5 mA / cm². 2 .

[0048] In this invention, the preferred ultraviolet light wavelength used for ultraviolet irradiation is 285 nm. Irradiation with 285 nm ultraviolet light is preferred because it has a higher degradation rate for most pollutants than commonly used wavelengths of 265 nm and 254 nm, and it also exhibits the highest molar absorptivity for chlorine. Furthermore, during the purification process, the reactor body is preferably wrapped with tin foil to prevent LED light radiation from emitting onto the human body, thereby improving light efficiency.

[0049] In this invention, the purification is preferably carried out under stirring conditions, and the stirring speed is preferably 400 rpm. In this invention, the purification temperature is preferably 15-30°C, more preferably 21±2°C.

[0050] In this invention, the purification process is preferably as follows: an ultraviolet lamp assembly 3 is installed on the first through hole 8 of the reactor top cover, an electrode assembly 2 is installed on the second through hole 9, and a third through hole 10 is sealed with a sealing bolt. Place reactor assembly 1 on magnetic stirrer 21 and insert rotor 20. Add seawater to be treated into reactor body and cover reactor top. Adjust rotation speed to make rotor 20 rotate slowly and uniformly. Connect vent pipe 19 connected to blower 18 into UV lamp assembly 3 to deliver air evenly. Connect rubber tube 23 to inlet / outlet 7 on outer wall of reactor body. Turn on circulating water pump 22 and set temperature. Preheat for 20 minutes before reaction starts. Wrap reactor body with tin foil to prevent LED lamp radiation to human body and improve light efficiency. Connect 12V DC power supply 15 to two electrode clips 11 through wire 14. Adjust the distance between ruthenium-iridium-titanium electrode 12 and stainless steel plate 13. Set current density. After controlling temperature to be constant, turn on DC power supply 15 and LED lamp 16 to start reaction. During reaction, the third through hole 10 can be opened for sampling and testing according to the set time.

[0051] In this invention, the preferred purification mechanism is that chloride ions and hydroxide ions in the water generate small amounts of Cl2, Cl·, and ·OH under anodic oxidation, and Cl2 further generates HClO and OCl. - Under alkaline conditions, ultraviolet light promotes the reaction of HClO and OCl. - ClO· is generated, Cl· is converted to Cl2·, and hydroxide ions are converted to ·OH. Meanwhile, the H2O / OH ratio in the water... - O2 is generated under the action of the cathode, and further generated under the promotion of ultraviolet light. 1 O2. Free chlorine (HClO, OCl) produced during this process. - Substances such as Cl2, singlet oxygen, ·OH, Cl·, ClO·, and Cl2· further react with pollutants in water to achieve degradation.

[0052] To further illustrate the present invention, an electrochemical device and a seawater purification method provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0053] Example 1

[0054] use Figure 1 The aforementioned photoelectrochemical device is used for seawater purification;

[0055] The specific process is as follows: Install the ultraviolet lamp assembly 3 on the first through hole 8 of the reactor top cover, install the electrode assembly 2 on the second through hole 9, and seal the third through hole 10 with sealing bolts. Place the reactor assembly 1 on the magnetic stirrer 21 and put in the rotor 20. After adding the seawater to be treated into the reactor body, cover the reactor top cover, adjust the speed to make the rotor 20 rotate slowly and uniformly, and connect the air pipe 19 connected to the blower 18 into the ultraviolet lamp assembly 3 to deliver air evenly; connect the rubber tube 23 to the water inlet and outlet 7 on the outer wall of the reactor body, turn on the circulating water pump 22, set the temperature, and preheat for 20 minutes before the reaction starts; wrap the reactor body with tin foil to prevent LED light radiation to the human body and improve light efficiency.

[0056] Connect the 12V DC power supply 15 to the two electrode clamps 11 through the wire 14, adjust the distance between the ruthenium-iridium-titanium electrode plate 12 and the stainless steel plate 13, set the current density, control the temperature to a constant, and then turn on the DC power supply 15 and the LED light 16 to carry out electrolysis. At the same time, use 285nm ultraviolet light to irradiate and start the purification reaction.

[0057] The rotor rotates at 400 rpm, the distance between the ruthenium-iridium-titanium electrode 12 and the stainless steel plate 13 is 3 cm, the electrode size is 1×4 cm, the thickness is 1 mm, and the current density is 1 mA / cm². 2 The purification temperature is 21±2℃;

[0058] The simulated seawater consisted of: 20 μmol / L enrofloxacin, 24.53 g / L sodium chloride, and 2 mmol / L PBS buffer.

[0059] Example 2

[0060] The procedure was carried out as described in Example 1, wherein the current density was adjusted to 2 mA / cm². 2 .

[0061] Example 3

[0062] The procedure was carried out as described in Example 1, wherein the current density was adjusted to 5 mA / cm². 2 .

[0063] Test Results

[0064] Test results are as follows Figure 7 As shown in Table 1;

[0065] Table 1. Enrofloxacin degradation rate at different current densities

[0066] 0 100％ 100％ 100％ 100％ 1 min 99％ 98％ 96％ 92％ 3 min 99％ 94％ 89％ 80％ 5 min 97％ 92％ 83％ 67％ 10 min 97％ 85％ 73％ 45％ 15 min 95％ 80％ 64％ 28％ 20 min 94％ 77％ 55％ 15％ 30 min 90％ 69％ 40％ 3％ 45 min 87％ 59％ 26％ 0％ 60 min 82％ 52％ 14％ 0％

[0067] from Figure 7 As can be seen from Table 1, in the range of 1–5 mA / cm 2 Within a certain current density range, photoelectric synergy, compared to photolysis alone, can achieve rapid degradation of enrofloxacin.

[0068] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for purifying seawater, characterized in that, The seawater purification method described above is used to purify enrofloxacin from seawater and employs a photoelectrochemical device, comprising the following steps: The seawater to be purified is introduced into the reactor assembly (1), and purified by the combined action of electrolysis and ultraviolet irradiation using the electrode assembly (2) and the ultraviolet lamp assembly (3). The photoelectrochemical device includes a reactor assembly (1), an electrode assembly (2), and an ultraviolet lamp assembly (3). The reactor assembly (1) includes a reactor body and a reactor top cover; The electrode assembly (2) and the ultraviolet lamp assembly (3) are fixed on the top cover of the reactor; The distance between the ruthenium-iridium-titanium electrode sheet (12) and the stainless steel plate (13) in the electrode assembly (2) is 3cm; The electrolysis voltage is 2.46–2.69 V, and the current density is 5 mA / cm². 2 The ultraviolet light wavelength used in the ultraviolet irradiation is 285nm.

2. The purification method according to claim 1, characterized in that, The reactor body is a cylindrical double-layered glass; the outer wall of the reactor body is provided with a circulating water bath inlet and outlet (7). The photoelectrochemical device further includes a circulating water bath assembly (6); the circulating water bath assembly (6) includes a circulating water pump (22) and a rubber tube (23). The circulating water pump (22) is connected to the circulating water bath inlet and outlet (7) via a rubber hose (23).

3. The purification method according to claim 1, characterized in that, The reactor top cover is made of polytetrachloroethylene, and the reactor top cover is provided with a first through hole (8), a second through hole (9) and a third through hole (10). The first through hole (8) is used to fix the ultraviolet lamp assembly (3); the second through hole (9) is used to fix the electrode assembly (2); and the third through hole (10) is used for sampling and detection.

4. The purification method according to claim 1, characterized in that, The electrode assembly (2) includes a PEEK electrode clip (11), a ruthenium-iridium-titanium electrode sheet (12), a stainless steel plate (13), a wire (14), and a DC power supply (15). The ruthenium-iridium-titanium electrode sheet (12) and the stainless steel plate (13) are connected to the DC power supply (15) in sequence via PEEK electrode clip (11) and wire (14).

5. The purification method according to claim 1, characterized in that, The ultraviolet lamp assembly (3) includes an LED lamp (16) and a quartz glass protective lamp cover (17).

6. The purification method according to claim 1, characterized in that, The photoelectrochemical device also includes a heat dissipation component (4); the heat dissipation component (4) includes a blower (18) and a vent pipe (19); the vent pipe (19) is placed in a quartz glass protective lamp cover (17).

7. The purification method according to claim 1, characterized in that, The photoelectrochemical device also includes a magnetic stirring assembly (5), which includes a rotor (20) and a magnetic stirrer (21), with the reactor body placed on the magnetic stirrer (21).

8. The purification method according to claim 1, characterized in that, The purification is carried out under stirring conditions, and the stirring speed is 400 rpm; The purification temperature is 15~30℃.

Images