Integrated fluoride removal agent generating device

Abstract

The application discloses an integrated defluorination agent generating device, wherein an anode chamber and a cathode chamber are in internal communication, and both the anode chamber and the cathode chamber are filled with sulfuric acid solution to prepare a defluorination agent. The cathode chamber is sealed and connected through a rubber ring, and a cathode is arranged in the cathode chamber and fixed on the left side of a reactor below a substrate liquid surface through titanium wires and the rubber ring. The anode chamber is sealed and connected through a rubber ring, and an air anode is arranged in the anode chamber and fixed on the right side of the reactor through titanium wires and the rubber ring. An external circuit of the anode chamber and the cathode chamber is connected through electric conductive wires, and a resistor is connected to the electric conductive wires. In the anode chamber, divalent iron ions are generated, and in the cathode chamber, hydrogen peroxide is generated to oxidize ferrous ions into trivalent iron ions. When the iron ions are hydrolyzed, the hydrolysis product is polymerized to obtain a liquid polymerized ferric sulfate product. The application realizes the integration of a cathode and an anode of a microbial fuel cell, improves the production efficiency of the polymerized ferric sulfate and reduces the engineering investment cost.

Description

Technical Field

[0001] This invention belongs to the field of defluorinating agent generation and fuel cell technology, specifically relating to an integrated defluorinating agent generating device. Background Technology

[0002] Fluorine pollution refers to the pollution caused by fluorine and its compounds to the environment. It mainly originates from emissions from aluminum smelting, phosphate rock processing, phosphate fertilizer production, iron and steel smelting, and coal combustion. Hydrogen fluoride and silicon tetrafluoride are the main gaseous pollutants. Fluorine-containing wastewater from industries such as electroplating and metal processing, as well as washing water from the treatment of fluorine-containing waste gas, will cause water pollution after discharge. The deposition of fluorine-containing dust or its leaching by precipitation can pollute soil and groundwater.

[0003] Fluorine is an essential trace element for the human body, and adequate fluoride in drinking water (0.5–1.0 mg / L) is essential for maintaining bone and teeth development. However, long-term consumption of water with a fluoride content higher than 1.5 mg / L can have negative effects on the human body. Excessive fluoride intake can interfere with the activity of various enzymes in the body, disrupt the metabolic balance of calcium and phosphorus, and lead to fluorosis, characterized by brittle teeth, tooth discoloration, and bone and joint deformities.

[0004] Therefore, how to effectively treat fluoride-containing wastewater is an important issue. Chemical precipitation is the most commonly used method for treating high-concentration fluoride-containing wastewater. However, for high-concentration fluoride-containing wastewater, chemical precipitation often fails to meet discharge standards. To ensure that the effluent fluoride ion concentration meets the standards, industrial processes often employ a multi-step "chemical precipitation + coagulation clarification" method. The reagents used are usually lime and polyferric sulfate (PFS). PFS is a novel inorganic iron salt coagulant commonly used in urban water supply purification and industrial wastewater treatment. It is a widely used, low-cost, easy-to-operate, highly effective, safe, and non-toxic water treatment agent. Through hydrolysis, it produces polynuclear complexes, which, through adsorption, bridging, and cross-linking, promote the coagulation of colloidal particles in wastewater. PFS can overcome the shortcomings of lime, such as slow coagulation and low solubility, and is therefore widely used in the water treatment field. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an integrated defluorinating agent generator. This invention employs an iron-air fuel cell configuration and focuses on the preparation of polyferric sulfate via the hydrogen peroxide oxidation method, simplifying the defluorinating agent preparation process and reducing engineering investment costs.

[0006] To achieve the above objectives, the specific technical solution adopted by the present invention is as follows:

[0007] An integrated defluorinating agent generating device is provided, wherein the reactor is provided with an anode chamber and a cathode chamber, which are connected and both chambers are filled with sulfuric acid solution; and the reactor is provided with wires, resistors, and an external signal acquisition instrument.

[0008] The anode chamber is equipped with an iron anode, titanium wire, and rubber ring.

[0009] The cathode chamber contains an air cathode, titanium wire, and rubber ring.

[0010] The anode chamber is located at the left end of the reactor, and the cathode chamber is located at the right end of the reactor. Rubber rings are installed to prevent the influence of the external environment. The two chambers are connected internally and fixed by iron strips and matching bolts.

[0011] Inside the anode chamber, the iron anode is fixed to the left-side plexiglass block by titanium wire and rubber ring, with electrical wires connected to the titanium wire.

[0012] Inside the cathode chamber, the air cathode is fixed to the right-side plexiglass block by titanium wire and rubber ring, with electrical wires connected to the titanium wire.

[0013] The anode and cathode chambers are constructed of high-strength plexiglass, with dimensions ranging from 5 to 10 cm and a total effective volume ranging from 27 to 512 ml.

[0014] The volume ratio of the cathode chamber to the anode chamber in the reactor is 1:1.

[0015] The reactor is connected by a long iron bar and matching bolts. The ratio of the length of the iron bar to the length of the defluorinating agent generator is 1:1.2 to 1:1.5.

[0016] The air cathode is equipped with a catalyst layer, carbon cloth, carbon base layer, and diffusion layer, with an area ratio of 1:1.2 to 1:1.5 with the square organic glass block.

[0017] The ratio of the outer diameter of the rubber ring to the inner side length of the defluorinating agent generator is 1:1.

[0018] The resistance range of the external circuit is 5Ω~100Ω.

[0019] The ratio of iron anode area to anode chamber volume is 1 cm². 2 (3~5)cm 3 .

[0020] The titanium wire is about 3-5 cm long, and its height ratio to the defluorinating agent generator is 0.4-0.6.

[0021] To extend the continuous operating time of the device, the thickness of the iron sheet was increased to 2-6 mm.

[0022] The matrix solution in the reactor is H2SO4, and under stable operating conditions, the molar ratio of ferrous ions to sulfate ions is 0.7~0.8.

[0023] Its working principle is as follows: In the anode chamber, the iron anode loses electrons and generates ferrous ions. In the cathode chamber, the air cathode gains electrons and generates hydrogen peroxide. In an acidic environment, hydrogen peroxide is a strong oxidant that can oxidize ferrous iron to ferric iron. When the acidity decreases to a certain level, ferrous ions are no longer oxidized, and ferric ions undergo hydrolysis. The hydrolysis products are polymerized to obtain polyferric sulfate solution.

[0024] When polyferric sulfate is added to fluoride-containing wastewater, it forms positively charged colloidal particles that neutralize the negatively charged fluoride ions in the water. This causes the colloidal particles to aggregate into larger flocculent precipitates and generate hydroxides and derivatives with strong adsorption properties. These compounds adsorb and settle fluoride in the water, thus removing fluoride ions.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] In this integrated defluorinating agent generating device, the reactor contains an anode chamber and a cathode chamber, which are connected and filled with sulfuric acid solution. Outside the reactor are electrical wires, a resistor, and an external signal acquisition device. The anode chamber contains an iron anode, titanium wire, and a rubber ring. The cathode chamber contains an air cathode, titanium wire, and a rubber ring. The anode chamber is located at the left end of the reactor, and the cathode chamber at the right end. A rubber ring is used to prevent external environmental influences. The two chambers are internally connected and fixed by an iron strip and matching bolts. Inside the anode chamber, the iron anode is fixed to the left-side plexiglass block by titanium wire and a rubber ring, with an electrical wire connected to the titanium wire. Inside the cathode chamber, the air cathode is fixed to the right-side plexiglass block by titanium wire and a rubber ring, with an electrical wire connected to the titanium wire. The anode and cathode chambers are constructed of high-strength plexiglass, and the reactor is connected by an iron strip and matching bolts. The air cathode contains a catalyst layer, carbon cloth, a carbon base layer, and a diffusion layer. The matrix of the solution in the reactor is H2SO4, and under stable operating conditions, the molar ratio of ferrous ions to sulfate ions is 0.7~0.8.

[0027] In the anode chamber, the iron anode loses electrons to generate ferrous ions (Fe2+). In the cathode chamber, the air cathode gains electrons, producing hydrogen peroxide. Under acidic conditions, hydrogen peroxide is a strong oxidizing agent that can oxidize ferrous ions to ferric ions (Fe3+). When the acidity decreases to a certain level, ferrous ions are no longer oxidized, and ferric ions undergo hydrolysis. The hydrolysis products are polymerized to obtain liquid polyferric sulfate. When polyferric sulfate is added to fluoride-containing wastewater, it forms positively charged colloidal particles that neutralize the negatively charged fluoride ions in the water. This causes the particles to aggregate into larger flocculent precipitates and generate strongly adsorbent hydroxides and derivatives, which adsorb and settle fluoride in the water, thus removing fluoride ions.

[0028] Unlike the traditional hydrogen peroxide oxidation method for preparing polyferric sulfate, which requires controlled hydrogen peroxide addition and involves intermittent operation, impacting production efficiency, this invention provides a continuous supply of ferrous ions and hydrogen peroxide. This eliminates the need for frequent intermittent operation; only timely replacement of the anode and cathode materials and replenishment of sulfuric acid concentration in the matrix are required to achieve continuous polyferric sulfate production, thus improving efficiency. Furthermore, this device simultaneously generates electricity, reducing engineering investment costs and representing an environmentally friendly biofuel cell with significant economic and environmental benefits. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the integrated defluorinating agent generating device of the present invention.

[0030] Figure 2 This is a frontal view of the integrated defluorinating agent generating device of the present invention.

[0031] Figure 3 This is a partial schematic diagram of the cathode of the integrated defluorinating agent generating device of the present invention.

[0032] In the diagram: A-Anode chamber, B-Cathode chamber; 1-Anode, 2-Cathode, 3-Titanium wire, 4-Rubber ring, 5-Electrical wire, 6-Resistor, 7-Catalyst layer, 8-Carbon cloth, 9-Carbon base layer, 10-Diffusion layer, 11-Electrical signal acquisition instrument, 12-Iron strip, 13-Matching bolt. Detailed Implementation

[0033] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Unless otherwise specified or conflicting, the preferred embodiments can be combined in any way.

[0034] like Figure 1 and Figure 2 As shown, combined with Figure 3 The integrated defluorinating agent generating device of the present invention has an anode chamber A and a cathode chamber B inside the reactor, both of which are filled with sulfuric acid solution; and an electric wire 5, a resistor 6, and an external signal acquisition instrument 11 are installed outside the reactor.

[0035] The anode chamber A is equipped with an iron anode 1, a titanium wire 3, and a rubber ring 4.

[0036] An air cathode 2, a titanium wire 3, and a rubber ring 4 are installed in cathode chamber B.

[0037] The anode chamber A is located at the left end of the reactor, and the cathode chamber B is located at the right end of the reactor. A rubber ring 4 is installed to avoid the influence of the external environment. The two chambers are connected internally and fixed by a long iron strip 12 and matching bolts 13.

[0038] Inside the anode chamber A, the iron anode 1 is fixed to the left side of the plexiglass block by titanium wire 3 and rubber ring 4, and an electrical wire 5 is connected to the titanium wire 3.

[0039] Inside cathode chamber B, air cathode 2 is fixed to the right-side plexiglass block by titanium wire 3 and rubber ring 4, and electrical wire 5 is connected to titanium wire 3.

[0040] Preferred, refer to Figure 1 and Figure 2 The anode chamber A and cathode chamber B are constructed of high-strength organic glass, with a size range of 5~10cm and a total effective volume range of 27~512ml.

[0041] Preferred, refer to Figure 1 and Figure 2 The volume ratio of the cathode chamber B to the anode chamber A in the reactor is 1:1.

[0042] Preferred, refer to Figure 1 and Figure 2 The reactor is connected by an iron strip 12 and matching bolts 13. The length ratio of the iron strip 12 to the length of the defluorinating agent generator is 1:1.2 to 1:1.5.

[0043] Preferred, refer to Figure 1 and Figure 2 , combined Figure 3 The air cathode 2 is provided with a catalyst layer 7, a carbon cloth 8, a carbon base layer 9, and a diffusion layer 10 from left to right, with an area ratio of 1:1.2 to 1:1.5 with the square organic glass block.

[0044] Preferred, refer to Figure 1 and Figure 2 The ratio of the outer diameter of the rubber ring 4 to the inner side length of the defluorinating agent generator is 1:1.

[0045] Preferred, refer to Figure 1 and Figure 2 The resistance connected to the external circuit is in the range of 5Ω to 100Ω.

[0046] Preferred, refer to Figure 1 and Figure 2 The ratio of the area of ​​iron anode 1 to the volume of anode chamber A is 1 cm². 2 (3~5)cm 3 .

[0047] Preferred, refer to Figure 1 and Figure 2 The titanium wire 3 is about 3-5cm long, and its height ratio to the defluorinating agent generator is 0.4-0.6.

[0048] Preferred, refer to Figure 1 and Figure 2To extend the continuous operating time of the device, the thickness of iron sheet 1 is increased to 2-6 mm.

[0049] Preferred, refer to Figure 1 and Figure 2 The matrix of the solution in the reactor is H2SO4, and under stable operating conditions, the molar ratio of ferrous ions to sulfate ions is 0.7~0.8.

[0050] Preferred, such as Figure 1 and Figure 2 The portion of titanium wire 3 that contacts anode 1 does not enter the solution.

[0051] Preferred, such as Figure 1 and Figure 2 The cathode 2 is circular with a diameter ranging from 3 to 10 cm.

[0052] The dimensions and proportions of the various devices described above in this invention can be set according to actual conditions.

[0053] In this embodiment, the anode chamber A and cathode chamber B are constructed of high-strength plexiglass, with dimensions ranging from 5 to 10 cm and a total effective volume ranging from 27 to 512 ml. The volume ratio of the cathode chamber B to the anode chamber A is 1:1. The reactor is connected and fixed by an iron strip 12 and matching bolts 13, with the length of the iron strip 12 being 1:1.2 to 1:1.5 of the length of the defluorinating agent generator. The air cathode 2 is provided with a catalyst layer 7, carbon cloth 8, carbon base layer 9, and diffusion layer 10, with an area ratio of 1:1.2 to 1:1.5 of the square plexiglass block. The outer diameter ratio of the rubber ring 4 to the inner side length ratio of the defluorinating agent generator is 1:1. The resistance 6 connected to the external circuit ranges from 5 Ω to 100 Ω. The area of ​​the iron anode 1 is 1 cm² of the volume of the anode chamber A. 2 (3~5)cm 3 The titanium wire 3 is approximately 3-5 cm long, with a height ratio of 0.4-0.6 to the height of the defluorinating agent generator. To extend the continuous operation time of the device, the thickness of the iron sheet 1 is increased to 2-6 mm. The solution matrix inside the reactor is H₂SO₄, and under stable operating conditions, the molar ratio of ferrous ions to sulfate ions is 0.7-0.8. The cathode 2 is circular, with a diameter ranging from 3 to 10 cm. The pH in the anode chamber A and cathode chamber B is controlled at 5.5-6.5.

[0054] Through testing, the above-mentioned dimensions and proportions have been found to effectively achieve the experimental objectives of this invention.

[0055] Reference Figure 1 and Figure 2 The process of the defluorinating agent generating device of the present invention is as follows:

[0056] In anode chamber A, iron anode 1 loses electrons to generate ferrous ions. In cathode chamber B, air cathode 2 gains electrons to generate hydrogen peroxide. In an acidic environment, hydrogen peroxide is a strong oxidizing agent that can oxidize ferrous iron to ferric iron. When the acidity decreases to a certain level, ferrous ions are no longer oxidized, and ferric ions undergo hydrolysis. The hydrolysis products are polymerized to obtain liquid polymerized ferric sulfate.

[0057] When polyferric sulfate is added to fluoride-containing wastewater, it forms positively charged colloidal particles that neutralize the negatively charged fluoride ions in the water. This causes the colloidal particles to aggregate into larger flocculent precipitates and generate hydroxides and derivatives with strong adsorption properties. These compounds adsorb and settle fluoride in the water, thus removing fluoride ions.

[0058] Unlike the traditional hydrogen peroxide oxidation method for preparing polyferric sulfate, which requires controlled hydrogen peroxide addition and involves intermittent operation, impacting production efficiency, this invention provides a continuous supply of ferrous ions and hydrogen peroxide. This eliminates the need for frequent intermittent operation; only timely replacement of the anode and cathode materials and replenishment of sulfuric acid concentration in the matrix are required to achieve continuous polyferric sulfate production, thus improving efficiency. Furthermore, this device simultaneously generates electricity, reducing engineering investment costs and representing an environmentally friendly biofuel cell with significant economic and environmental benefits.

[0059] Referring to the process of wastewater treatment, the current information of the load 6 is collected by the electrical signal acquisition instrument 11 to monitor the current information generated by the microbial fuel cell in real time.

[0060] In summary, the defluorinating agent generating device of the present invention integrates the production of polyferric sulfate and the recycling of electricity resources, thereby improving the production efficiency of polyferric sulfate and reducing engineering investment costs.

[0061] The embodiments described above can be further combined or replaced, and these embodiments are merely descriptions of preferred embodiments of the present invention, not limitations on the concept and scope of the present invention. Various changes and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the inventive concept are all within the protection scope of the present invention. The protection scope of the present invention is given by the appended claims and any equivalents.

Claims

1. An integrated defluorinating agent generating device, characterized in that, The reactor is equipped with an anode chamber (A) and a cathode chamber (B), both filled with sulfuric acid solution; outside the reactor are electrical wires (5), a resistor (6), and an electrical signal acquisition instrument (11). The anode chamber (A) is equipped with an iron anode (1), a titanium wire (3), and a rubber ring (4); An air cathode (2), a titanium wire (3), and a rubber ring (4) are installed in the cathode chamber (B); The anode chamber (A) is located at the left end of the reactor, and the cathode chamber (B) is located at the right end of the reactor. A rubber ring (4) is installed to avoid the influence of the external environment. The two chambers are connected internally and fixed by a long iron strip (12) and matching bolts (13). Inside the anode chamber (A), the iron anode (1) is fixed to the left organic glass block by a titanium wire (3) and a rubber ring (4), and an electric wire (5) is connected to the titanium wire (3). Inside the cathode chamber (B), the air cathode (2) is fixed to the right side of the plexiglass block by a titanium wire (3) and a rubber ring (4). An electrical wire (5) is connected to the titanium wire (3). The air cathode (2) is provided with a catalyst layer (7), a carbon cloth (8), a carbon base layer (9), and a diffusion layer (10) from left to right. The area ratio of the air cathode (2) to the square plexiglass block is 1:1.2 to 1:1.

5. The matrix solution in the reactor is H2SO4, and under stable operating conditions, the molar ratio of ferrous ions to sulfate ions is 0.7~0.

8.

2. The integrated defluorinating agent generating device according to claim 1, characterized in that, The anode chamber (A) and cathode chamber (B) are constructed of plexiglass, with a size ranging from 5 to 10 cm and a total effective volume ranging from 27 to 512 ml.

3. The integrated defluorinating agent generating device according to claim 1, characterized in that, The volume ratio of the cathode chamber (B) to the anode chamber (A) is 1:

1.

4. The integrated defluorinating agent generating device according to claim 1, characterized in that, The range of the resistor (6) connected to the external circuit is 5Ω~100Ω.

5. The integrated defluorinating agent generating device according to claim 1, characterized in that, The area of ​​the iron anode (1) to the volume of the anode chamber (A) is 1 cm². 2 (3~5)cm 3 .

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