A sea surface floating electrochemical device for offshore oil pollution treatment

Abstract

The present invention belongs to the field of electrochemical water treatment and provides a floating electrochemical device for offshore oil pollution treatment. The device comprises a solar panel, a fixing nail, a solar panel positive electrode, a solar panel negative electrode, a solar controller, a solar controller positive electrode, a solar controller negative electrode, screws, a battery, a battery positive electrode terminal, a battery negative electrode terminal, a fixing bracket, a wooden board, a gas diffusion electrode, a ruthenium-iridium-titanium electrode, an LPC-FeOCl catalyst layer, a wire, a conductive copper foil, an aeration pump, a waterproof insulating mat, and an aeration tube. The device uses a gas diffusion electrode loaded with an LPC-FeOCl catalyst as the cathode and a ruthenium-iridium-titanium electrode as the anode. The solar panel provides power for the electrochemical reaction. The gas diffusion electrode uses oxygen in the air to synthesize H2O2, and the FeOCl activates H2O2 to produce OH, forming an electro-Fenton system. The device has low energy consumption, is green and pollution-free, and is simple to operate. It can effectively degrade oil pollutants, further addressing the problem of offshore water pollution.

Description

Technical Field

[0001] The invention belongs to the field of electrochemical water treatment and relates to a sea surface floating electrochemical device for offshore oil pollution treatment. Background Art

[0002] In recent years, offshore crude oil and heavy oil spills have become frequent. Oily pollutants leaking into seawater can rapidly spread across the surface, blocking oxygen exchange between seawater and air, suffocating marine life and harming the marine environment, disrupting marine ecosystems, and ultimately threatening human health. Traditional physical adsorption and biodegradation technologies, such as those used for treating these pollutants, suffer from difficulties in degradation, secondary pollution, and low treatment efficiency. Therefore, there is an urgent need to develop efficient, stable, and environmentally friendly treatment technologies.

[0003] Electro-Fenton technology combines electrocatalytic oxygen reduction to produce H2O2 with the Fenton reaction. O2 is reduced to H2O2 at the cathode, and Fe 2+ It reacts with H2O2 to produce ·OH, which then degrades refractory organic pollutants, and has the advantages of being clean and efficient. 2+ Homogeneous electro-Fenton is limited by pH and produces iron sludge, which limits its wide application. Heterogeneous electro-Fenton uses iron-based materials to replace dissolved Fe 2+ It has a wide pH range, avoids the formation of iron sludge, and has broad application prospects. FeOCl is a good alternative material with a high ability to activate H2O2 to produce OH.

[0004] In summary, heterogeneous electro-Fenton technology offers the advantages of being green, pollution-free, efficient, stable, and easy to operate, making it a promising approach for addressing nearshore water pollution. However, current heterogeneous electro-Fenton catalysts are complex to prepare, difficult to precisely synthesize, and expensive. Furthermore, oily waste often floats on the sea surface, where power supply is inconvenient. Therefore, the present invention prepares a two-dimensional carbon material for efficient electrocatalytic oxygen reduction to produce H2O2, and activates H2O2 with FeOCl to produce ·OH. Based on this, a device capable of floating on the sea surface and treating marine pollutants was designed. Summary of the Invention

[0005] In response to the recent problem of marine oil pollution, the present invention provides an electrochemical device that can float on the sea surface. The device uses solar panels to power the electro-Fenton reaction, thereby achieving the purpose of purifying near-shore water quality and thus solving the problem of marine pollution.

[0006] The technical solution of the present invention:

[0007] A floating electrochemical device for offshore oil pollution treatment, comprising a solar power generation panel, a solar panel positive electrode, a solar panel negative electrode, a solar controller, a solar controller positive electrode, a solar controller negative electrode, a battery, a battery positive electrode terminal, a battery negative electrode terminal, a fixing bracket, a gas diffusion electrode, a ruthenium-iridium-titanium electrode, a wire, a conductive copper foil, an aeration pump, a waterproof insulating pad, and an aeration pipe;

[0008] The solar panel is fixed on a wooden board, the back of which is made of an anti-aging and waterproof backboard, and the frame is an oxidized aluminum alloy frame; the positive pole of the solar panel is connected to the positive pole of the first solar controller through a wire, and the negative pole of the solar panel is connected to the negative pole of the first solar controller through a wire;

[0009] The battery is fixed on the wooden board through a fixing bracket; the positive terminal of the battery is connected to the positive pole of the second solar controller through a wire, and the negative terminal of the battery is connected to the negative pole of the second solar controller through a wire;

[0010] The solar controller has an LCD screen that can display the voltage and power level, and has menu keys and adjustment keys to adjust the charge and discharge parameters. The solar controller is fixed to the wooden board with screws and is used to detect the battery voltage. The distance between the solar controller and the battery is less than 30cm.

[0011] Two gas diffusion electrodes and two ruthenium-iridium-titanium electrodes loaded with LPC-FeOCl catalyst layers are alternately fixed under the wooden board to improve electron transmission efficiency. The two gas diffusion electrodes loaded with LPC-FeOCl catalyst layers are connected using conductive copper foil to form the cathode of the electrochemical device floating on the sea surface. The two ruthenium-iridium-titanium electrodes are connected using conductive copper foil to form the anode of the electrochemical device floating on the sea surface. The anode is connected to the positive electrode of the third solar controller, and the cathode is connected to the negative electrode of the third solar controller.

[0012] Both the conductors and the conductive copper foil are provided with waterproof devices.

[0013] There are two aeration pumps, which aerate the air for the two gas diffusion electrodes through the aeration pipes.

[0014] A waterproof insulating pad is provided between the cathode and the anode to avoid short circuit.

[0015] The LPC-FeOCl catalyst layer is made by mixing LPC material with FeOCl. LPC material is a two-dimensional layered carbon material with a large specific surface area. The LPC-FeOCl catalyst preparation steps are as follows:

[0016] (1) The LPC catalyst was prepared using the same method as Yangyang Liu's published article "Electrosynthesis of chlorine from seawater-like solution through single-atom catalysts." First, Zn-MOFs nanosheets were obtained by ultrasonication, and then carbonized to obtain a two-dimensional LPC material. The carbonization temperature was 650°C-950°C. FeOCl powder was obtained by calcining FeCl3·6H2O in a muffle furnace.

[0017] (2) The LPC catalyst and FeOCl powder were ultrasonically dispersed in ethanol at a mass ratio of 1:10, filtered, and dried to obtain the LPC-FeOCl catalyst.

[0018] The working principle of the device is: the solar panel provides electricity, the gas diffusion cathode can in situ electrosynthesize H2O2 through oxygen in the air, H2O2 reacts with FeOCl in a Fenton-like reaction to produce ·OH, which can efficiently and quickly degrade marine oil and various difficult-to-degrade pollutants. The ruthenium, iridium and titanium anode can also directly electro-oxidize and degrade some small molecular pollutants.

[0019] Beneficial effects of the present invention: The present invention provides an electrochemical device that can float on the sea surface. The cathode catalyst uses natural seawater as the electrolyte, efficiently and stably produces H2O2, which is catalytically decomposed to produce ·OH. The device uses solar panels to provide electricity for the electro-Fenton reaction, overcoming the problem of power supply difficulties on the sea surface. It has the advantages of being green and pollution-free, simple to operate, and low in energy consumption. It can effectively degrade oil pollutants on the sea surface and solve the problem of offshore water pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a three-dimensional structural diagram above the wooden board of a sea surface floating electrochemical device for offshore oil pollution treatment according to the present invention.

[0021] Figure 2 This is a three-dimensional structural diagram below the wooden board of a sea surface floating electrochemical device for offshore oil pollution treatment according to the present invention.

[0022] Figure 3 The diagram is a top view of a sea surface floating electrochemical device for offshore oil pollution treatment according to the present invention.

[0023] Figure 4 The present invention is a bottom view of a sea surface floating electrochemical device for offshore oil pollution treatment.

[0024] In the figure: 1 solar panel, 2 fixing nails, 3 solar panel positive electrode, 4 solar panel negative electrode, 5 solar controller, 6 first solar controller positive electrode, 7 first solar controller negative electrode, 8 second solar controller positive electrode, 9 second solar controller negative electrode, 10 third solar controller positive electrode, 11 third solar controller negative electrode, 12 screws, 13 battery, 14 battery positive electrode terminal, 15 battery negative electrode terminal, 16 fixing bracket, 17 wooden board, 18 gas diffusion electrode, 19 ruthenium-iridium-titanium electrode, 20 LPC-FeOCl catalyst layer, 21 wire, 22 conductive copper foil, 23 aeration pump, 24 waterproof insulation layer, 25 aeration pipe. DETAILED DESCRIPTION

[0025] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and technical solutions.

[0026] Example 1

[0027] A mixed solution of N,N-dimethylformamide (512 mL), ethanol (32 mL), and ultrapure water (32 mL) was prepared. 2 g of terephthalic acid was added to the mixed solution and sonicated for dissolution. Subsequently, 1.68 g of ZnCl₂ and 12.8 mL of triethylamine solution were added and sonicated at room temperature for 12 h. The product was centrifuged, washed three times with ethanol, dried under vacuum at 60°C, and ground into a powder. The resulting powder was calcined at 750°C for 3 h in a tube furnace under an N₂ atmosphere. After cooling to room temperature, the calcined product was mixed with 1.21 M HCl, stirred at room temperature for 24 h, filtered, washed until neutral, and dried to obtain the LPC catalyst. The LPC catalyst can efficiently produce H₂O₂. 20 g of FeCl₃·6H₂O was ground into a powder in a mortar. The resulting powder was placed in a crucible and calcined at 220°C in a muffle furnace for 1 h to obtain FeOCl powder. LPC catalyst and FeOCl powder were ultrasonically dispersed in ethanol at a mass ratio of 1:10, filtered, and dried to obtain an LPC-FeOCl catalyst. The LPC-FeOCl catalyst was then added to a mixture of ethanol, water, and 5% membrane solution (ethanol:water:5% membrane solution ratio:14:6:1) to prepare a catalyst slurry, which was then evenly dispersed on a gas diffusion electrode to obtain an LPC-FeOCl catalyst-loaded gas diffusion electrode.

[0028] Example 2

[0029] like Figure 1 、 Figure 2As shown, the sea surface floating electrochemical device includes a solar power generation panel 1, a fixing nail 2, a solar panel positive electrode 3, a solar panel negative electrode 4, a solar controller 5, a first solar controller positive electrode 6, a first solar controller negative electrode 7, a second solar controller positive electrode 8, a second solar controller negative electrode 9, a third solar controller positive electrode 10, a third solar controller negative electrode 11, a screw 12, a battery 13, a battery positive electrode terminal 14, a battery negative electrode terminal 15, a fixing bracket 16, a wooden board 17, a gas diffusion electrode 18, a ruthenium iridium titanium electrode 19, an LPC-FeOCl catalyst layer 20, a wire 21, a conductive copper foil 22, an aeration pump 23, a waterproof insulating pad 24, and an aeration pipe 25.

[0030] First, cross-fix the LPC-FeOCl catalyst-loaded gas diffusion electrode and the ruthenium-iridium-titanium electrode obtained in Example 1 under the wooden board. The LPC-FeOCl catalyst-loaded gas diffusion electrode serves as the cathode, and the ruthenium-iridium-titanium electrode serves as the anode. A waterproof insulating pad is placed between the cathode and the cathode. Place the solar panels in series in a suitable position above the wooden board and secure them with fixing nails. Place the battery in a suitable position above the wooden board and secure it with a fixing bracket. Place the solar controller close to the battery and secure it with screws on all sides.

[0031] Then, connect the wires in the following order: (1) Connect the positive electrode of the battery to the positive electrode of the second solar controller, and the negative electrode of the battery to the negative electrode of the second solar controller. (2) Connect the anode-ruthenium-iridium-titanium electrode to the positive electrode of the third solar controller, and the cathode-gas diffusion electrode to the negative electrode of the third solar controller. (3) Connect the positive electrode of the solar panel to the positive electrode of the first solar controller, and the negative electrode of the solar panel to the negative electrode of the first solar controller.

[0032] Once connected, the device uses solar panels to generate electricity for the electrochemical reaction. A ruthenium-iridium-titanium electrode serves as the anode, and a gas diffusion electrode loaded with an LPC-FeOCl catalyst serves as the cathode. A two-electron oxygen reduction reaction at the cathode produces H₂O₂, which is catalytically decomposed into OH by the FeOCl, forming a heterogeneous electro-Fenton system. The device floats on the water surface, degrading oil and other organic pollutants.

Claims

1. A floating electrochemical device for offshore oil pollution treatment, characterized in that: The sea-surface floating electrochemical device comprises a solar power generation panel, a solar panel positive electrode, a solar panel negative electrode, a solar controller, a solar controller positive electrode, a solar controller negative electrode, a battery, a battery positive electrode terminal, a battery negative electrode terminal, a fixing bracket, a gas diffusion electrode, a ruthenium-iridium-titanium electrode, a wire, a conductive copper foil, an aeration pump, a waterproof insulating pad and an aeration pipe; The solar panel is fixed on the wooden board; the positive pole of the solar panel is connected to the positive pole of the first solar controller through a wire, and the negative pole of the solar panel is connected to the negative pole of the first solar controller through a wire; The battery is fixed on the wooden board through a fixing bracket; the positive terminal of the battery is connected to the positive pole of the second solar controller through a wire, and the negative terminal of the battery is connected to the negative pole of the second solar controller through a wire; The solar controller has an LCD screen that can display the voltage and power, and has menu keys and adjustment keys to adjust the charge and discharge parameters. The solar controller is fixed to the wooden board with screws and is used to detect the battery voltage. Two gas diffusion electrodes and two ruthenium-iridium-titanium electrodes loaded with LPC-FeOCl catalyst layers are alternately fixed under the wooden board to improve electron transmission efficiency. The two gas diffusion electrodes loaded with LPC-FeOCl catalyst layers are connected using conductive copper foil to form the cathode of the electrochemical device floating on the sea surface. The two ruthenium-iridium-titanium electrodes are connected using conductive copper foil to form the anode of the electrochemical device floating on the sea surface. The anode is connected to the positive electrode of the third solar controller, and the cathode is connected to the negative electrode of the third solar controller. There are two aeration pumps, which aerate the air for the two gas diffusion electrodes through the aeration pipes; A waterproof insulating pad is placed between the cathode and anode to avoid short circuit; The LPC-FeOCl catalyst is obtained by mixing LPC material and FeOCl; the steps are as follows: (1) Prepare a mixed solution of N,N-dimethylformamide, ethanol and ultrapure water; add terephthalic acid to the mixed solution and dissolve it by ultrasonication; then add ZnCl2 and triethylamine solution and treat by ultrasonication at room temperature; The product is obtained by centrifugation, washed with ethanol, dried under vacuum, and ground into powder; the obtained powder is calcined and carbonized in a tube furnace under a nitrogen atmosphere, and after naturally cooling to room temperature, the calcined product is mixed with HCl, stirred at room temperature, filtered and washed until neutral, and dried to obtain the LPC catalyst; FeOCl powder is obtained by calcining FeCl3•6H2O; (2) LPC catalyst and FeOCl powder were ultrasonically dispersed in ethanol at a mass ratio of 1:10, filtered and dried to obtain LPC-FeOCl catalyst.

2. The sea surface floating electrochemical device according to claim 1, characterized in that: The distance between the solar controller and the battery is less than 30 cm.

3. The sea surface floating electrochemical device according to claim 1, characterized in that: The conductor and the conductive copper foil are both provided with waterproof devices.

4. The sea surface floating electrochemical device according to claim 1, characterized in that: The calcination and carbonization temperature is 650℃-950℃.

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