Series-parallel connection combined bromine extraction electrolytic bath and bromine extraction equipment

Abstract

The utility model belongs to the technical field of bromine extraction electrolytic baths, and particularly relates to a series-parallel connection combined bromine extraction electrolytic bath and bromine extraction equipment. The electrolytic bath is packaged and formed through a bath body packaging structure, an electrolytic ion membrane is arranged in the middle of the interior of the electrolytic bath, the electrolytic bath is divided into a cathode chamber and an anode chamber through the electrolytic ion membrane, and electrolytic plates are arranged on the two sides of the electrolytic ion membrane; a cathode water inlet pipe is arranged in the middle of the cathode chamber, a cathode gas outlet pipeline is arranged at the top, and a cathode liquid outlet pipeline is arranged at the bottom; an anode gas outlet pipeline is arranged at the top of the anode chamber; and an anode liquid outlet pipeline is arranged at the bottom. The electrolytic cells can be connected in series or in parallel, bromide ions with different concentrations can be treated, and the treatment capacity can be adjusted according to the water volume; the problem of enrichment of hydrogen in the electrolytic bath is solved, and the pressure in the electrolytic bath is balanced; the function tank achieves the effects of gas-liquid separation, temperature control and water inlet adjusting and buffering.

Description

Technical Field

[0001] The utility model belongs to the technical field of bromine extraction electrolyzers, and particularly relates to a bromine extraction electrolyzer with a series-parallel combination and a bromine extraction device. Background Technique

[0002] Bromine is an important chemical raw material. Since it was discovered and successfully separated from seawater, its demand has been on the rise. Currently, the raw materials for bromine extraction mainly include seawater, salt lake brine, underground brine, intermediate brine in salt production, and mother liquor after salt production. Among them, underground brine and salt lake brine are the dominant resources with the highest bromine production and the best quality.

[0003] Since the 1960s, with the progress of modern technology and the development of exploration technology, the development and utilization of underground brine have been fully developed. However, in addition to bromide ions (Br-), underground brine also contains a large number of other ions. In particular, the concentration of chloride ions (Cl-) can be as high as 30 - 200 g / L, which makes it a technically challenging problem to selectively extract bromine from underground brine.

[0004] Currently, the most widely used bromine extraction methods in industry are the air blowing method and the steam distillation method. However, these two methods have deficiencies in terms of energy consumption, equipment investment, floor area, safety performance, and resource utilization rate. New bromine extraction methods such as the solvent extraction method, the ion exchange resin method, and the membrane method are also difficult to industrialize due to their respective problems (such as strict requirements for extractants, short resin life and poor selectivity, membrane fouling, etc.).

[0005] The electrooxidation bromine extraction technology is based on the different standard oxidation-reduction potentials of Br- and Cl-. By selecting a suitable working electrode potential, the selective oxidation and extraction of Br- can be achieved. Since the standard oxidation-reduction potential of Br- is 0.271 V lower than that of Cl-, when the working electrode potential is controlled between 1.087 - 1.358 V (i.e., higher than the standard oxidation-reduction potential of Br- and lower than the standard oxidation-reduction potential of Cl-), Br- in the solution can be oxidized while Cl- cannot be oxidized, thus realizing the selective electrooxidation of Br-. The electrooxidation method for bromine extraction has advantages such as excellent selectivity, simple production process, clean production process, and low energy consumption, and is receiving increasing attention.

[0006] However, there are still many problems that need to be improved in this technology, such as how the electrolyzer processes bromide ions with different concentrations, how to solve the problem of hydrogen enrichment in the electrolyzer, how to balance the pressure in the electrolyzer; and how the functional tank realizes gas-liquid separation. Summary of the Invention

[0007] To solve the problems raised in the above-mentioned background art, the present utility model provides a bromine extraction electrolytic cell and a bromine extraction device with a series-parallel combination. The electrolytic cell can be connected in series or in parallel, can handle bromide ions with different concentrations, and can adjust the treatment capacity according to the amount of water; it solves the problem of hydrogen enrichment in the electrolytic cell and balances the pressure in the electrolytic cell; the functional tank realizes the functions of gas-liquid separation, temperature control, and inlet water regulation and buffering; it is not only used for bromine extraction and chlorine preparation, but also can be used for sewage treatment.

[0008] To achieve the above object, the present utility model provides the following technical solution: A bromine extraction electrolytic cell with a series-parallel combination, comprising an electrolytic cell, an electrolytic plate, and an electrolytic ion membrane; the electrolytic cell is encapsulated and formed through a tank body encapsulation structure, an electrolytic ion membrane is arranged in the middle of the electrolytic cell, and is separated into a cathode chamber and an anode chamber by the electrolytic ion membrane, and electrolytic plates are arranged on both sides of the electrolytic ion membrane;

[0009] A cathode water inlet pipe is arranged in the middle of the cathode chamber, a cathode gas outlet pipe is arranged at the top, and a cathode liquid outlet pipe is arranged at the bottom;

[0010] An anode water inlet pipe is arranged in the middle of the anode chamber, an anode gas outlet pipe is arranged at the top; an anode liquid outlet pipe is arranged at the bottom.

[0011] As a preferred solution, a cathode ear is connected to the electrolytic plate on one side of the cathode chamber; an anode ear is connected to the electrolytic plate on one side of the anode chamber.

[0012] As a preferred solution, the electrolytic plate adopts a composite electrolytic plate of titanium-based iridium dioxide and tantalum pentoxide.

[0013] A bromine extraction device, the bromine extraction device includes a bromine extraction electrolytic cell with a series-parallel combination, a cathode pump, an anode pump, and a functional tank. The cathode gas outlet pipe of the bromine extraction electrolytic cell is connected to the upper end of the functional tank for discharging hydrogen and balancing the gas pressure generated during electrolysis; the cathode liquid outlet pipe of the bromine extraction electrolytic cell is connected to the bottom end of the functional tank for liquid reflux to achieve pH stability; the cathode water inlet pipe of the bromine extraction electrolytic cell is connected to the liquid outlet of the bottom end of the functional tank through a cathode pump, and the anode water inlet pipe of the bromine extraction electrolytic cell is connected to the liquid outlet of the bottom end of the functional tank through an anode pump.

[0014] As a preferred solution, a hydrogen outlet is arranged at the top of the functional tank, a raw water inlet pipe is connected to the outer wall of the upper end of the functional tank, a grid support frame is arranged above the raw water inlet pipe inside the functional tank, a gas-liquid grid is arranged on the grid support frame, a water-cooled coil is arranged on the inner wall of the functional tank, the bottom end and the upper end of the water-cooled coil are respectively connected to a water-cooled outlet and a water-cooled inlet extending out of the back of the functional tank, and a liquid level gauge is arranged on one outer wall of the functional tank; a cleaning bottom valve is also arranged at the bottom end of the functional tank.

[0015] Compared with the prior art, the beneficial effects of the present utility model are:

[0016] In the present utility model, a certain voltage is provided to the electrolytic plate. Under the action of an electric field, a reduction reaction occurs at the cathode, generating a large amount of hydrogen gas. The gas enters the functional tank through the cathode gas outlet pipe for gas-liquid separation. When the hydrogen gas with water vapor passes through the gas-liquid grid, the liquid is isolated, achieving gas-liquid separation. The cathode liquid returns to the functional tank through electrolysis; an oxidation reaction occurs at the anode, generating bromine gas and bromine element. Some organic substances are also oxidized during the electrolysis process. The gas is in pressure balance with the stripping tower through the anode gas outlet pipe. The liquid completed by electrolysis enters the stripping tower through the anode liquid outlet pipe for bromine stripping, realizing the separation of bromine element.

[0017] The electrolytic cell of the present utility model can be connected in series or in parallel, can handle bromide ions with different concentrations, and can adjust the treatment capacity according to the water volume; it solves the problem of hydrogen gas enrichment in the electrolytic cell and balances the pressure in the electrolytic cell; the functional tank realizes the functions of gas-liquid separation, temperature control, and inlet water regulation and buffering; it is not only used for bromine extraction and chlorine preparation, but also can be used for sewage treatment. Description of the Drawings

[0018] Figure 1 It is a schematic structural diagram of the electrolytic cell in the present utility model;

[0019] Figure 2 It is a schematic structural diagram of the functional tank in the present utility model;

[0020] Figure 3 is Figure 2 A schematic cross-sectional view of the longitudinal section;

[0021] Figure 4 It is a schematic three-dimensional structural diagram of the whole of the present utility model;

[0022] Figure 5 It is a schematic structural diagram of the back of the whole of the present utility model.

[0023] Description of the Reference Numerals in the Drawings:

[0024] 1. Electrolytic cell; 2. Electrolytic plate; 3. Electrolytic ion membrane; 4. Tank body encapsulation structure; 5. Cathode water inlet pipe; 6. Cathode liquid outlet pipe; 7. Cathode gas outlet pipe; 8. Anode water inlet pipe; 9. Anode liquid outlet pipe; 10. Anode gas outlet pipe; 11. Hydrogen gas outlet; 12. Grid support frame; 13. Gas-liquid grid; 14. Water-cooled coil; 15. Liquid level gauge; 16. Raw water inlet pipe; 17. Liquid outlet; 18. Cleaning bottom valve; 19. Cathode pump; 20. Anode pump; 21. Functional tank; 22. Water-cooled outlet; 23. Water-cooled inlet; 24. Cathode ear; 25. Anode ear. Detailed Embodiment

[0025] The following will clearly and completely describe the technical solutions in the embodiments of the present utility model in conjunction with the accompanying drawings in the embodiments of the present utility model. Obviously, the described embodiments are only a part of the embodiments of the present utility model, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present utility model without making creative efforts belong to the scope of protection of the present utility model.

[0026] Embodiment 1

[0027] Please refer to Figure 1 , the present utility model provides the following technical solutions: A bromine extraction electrolytic cell with a series-parallel combination, including an electrolytic cell 1, an electrolytic plate 2, and an electrolytic ion membrane 3; the electrolytic cell 1 is formed by encapsulation through a cell encapsulation structure 4, an electrolytic ion membrane 3 is provided in the middle of the electrolytic cell 1, and is separated into a cathode chamber and an anode chamber by the electrolytic ion membrane 3, and electrolytic plates 2 are provided on both sides of the electrolytic ion membrane 3;

[0028] A cathode water inlet pipe 5 is provided in the middle of the cathode chamber, a cathode gas outlet pipe 7 is provided at the top, and a cathode liquid outlet pipe 6 is provided at the bottom;

[0029] An anode water inlet pipe 8 is provided in the middle of the anode chamber, an anode gas outlet pipe 10 is provided at the top, which is connected to a stripping tower for discharging bromine gas to balance the gas pressure generated during electrolysis; an anode liquid outlet pipe 9 is provided at the bottom, which is connected to the stripping tower for bromine stripping to achieve bromine separation.

[0030] In this embodiment, a cathode ear 24 is connected to the electrolytic plate 2 on one side of the cathode chamber; an anode ear 25 is connected to the electrolytic plate 2 on one side of the anode chamber.

[0031] In this embodiment, the electrolytic plate 2 adopts a composite electrolytic plate of titanium-based iridium dioxide and tantalum pentoxide; the material of the electrolytic cell 1 is made of fluoroplastics or polyether ether ketone (KEEP) materials, mainly for extracting bromine or chlorine by electrolyzing bromine-containing or chlorine-containing wastewater; it is prepared from corrosion-resistant materials and can resist the corrosion of bromine or chlorine.

[0032] As Figures 2 - 5 shown, a bromine extraction device, the bromine extraction device includes a bromine extraction electrolytic cell with a series-parallel combination, a cathode pump 19, an anode pump 20, and a functional tank 21. The cathode gas outlet pipe 7 of the bromine extraction electrolytic cell is connected to the upper end of the functional tank for discharging hydrogen to balance the gas pressure generated during electrolysis; the cathode liquid outlet pipe 6 of the bromine extraction electrolytic cell is connected to the bottom end of the functional tank 21 for liquid reflux to achieve pH stability; the cathode water inlet pipe 5 of the bromine extraction electrolytic cell is connected to the liquid outlet 17 at the bottom end of the functional tank 21 through the cathode pump 19, and the anode water inlet pipe 8 of the bromine extraction electrolytic cell is connected to the liquid outlet 17 at the bottom end of the functional tank 21 through the anode pump 20.

[0033] In this embodiment, a hydrogen outlet 11 is provided at the top of the functional tank 21. A raw water inlet pipe 16 is connected to the outer wall of the upper end of the functional tank 21. Inside the functional tank 21, a grid support frame 12 is provided above the raw water inlet pipe 16. A gas-liquid grid 13 is provided on the grid support frame 12. A water-cooled coil 14 is provided on the inner wall of the functional tank 21. The bottom end and the upper end of the water-cooled coil 14 are respectively connected to a water-cooled outlet 22 and a water-cooled inlet 23 that extend out of the back of the functional tank 21. A liquid level gauge 15 is provided on one outer wall of the functional tank 21; a cleaning bottom valve 18 is further provided at the bottom end of the functional tank 21.

[0034] The functional tank 21 is made of fluoroplastics or polyether ether ketone (KEEP) materials and mainly undertakes the following functions:

[0035] Function 1: Gas-liquid separation of hydrogen in the cathode chamber to avoid hydrogen enrichment and balance the pressure in the cathode chamber.

[0036] Function 2: Raw water inlet buffer tank, inlet regulation, and stable inlet flow rates of both the cathode and anode chambers.

[0037] Function 3: Water-cooled heat exchange temperature control.

[0038] The working principle and usage process of the present utility model are as follows:

[0039] During cleaning: Clean water is input into the functional tank 21 through the raw water inlet pipe 16. The cathode pump 19 and the anode pump 20 are turned on to pump clean water into the electrolytic cell 1 for cleaning operations. After cleaning is completed, the cathode liquid and the liquid in the functional tank are discharged through the cleaning bottom valve 18, and the anode liquid is discharged through the anode liquid outlet pipe 9.

[0040] Water inlet of the functional tank: Pretreated raw water is pumped in through the raw water inlet pipe 16. When the liquid level gauge 15 reaches the designed height, the injection of raw water is stopped.

[0041] Water inlet of the electrolytic cell: The cathode pump 19 is used to pump liquid into the cathode chamber, and the anode pump 20 is used to pump liquid into the anode chamber.

[0042] Electrolytic bromine extraction: By applying a certain voltage to the electrolytic plate 2, under the action of the electric field, a reduction reaction occurs at the cathode, generating a large amount of hydrogen. The gas enters the functional tank 21 through the cathode gas outlet pipe 7 for gas-liquid separation. When the hydrogen with water vapor passes through the gas-liquid grid 13, the liquid is separated, realizing gas-liquid separation. The cathode liquid returns to the functional tank 21 after electrolysis. An oxidation reaction occurs at the anode, generating bromine gas and bromine. Some organic substances are also oxidized during the electrolysis process. The gas is pressure-balanced with the stripping tower through the anode gas outlet pipe 10. The liquid after electrolysis enters the stripping tower through the anode liquid outlet pipe 9 for bromine stripping to achieve the separation of bromine.

[0043] Temperature control: Certain heat is generated during electrolysis. High temperature will affect the performance of the electrolyzer 1. Therefore, a water-cooled coil 14 is used for water-cooled heat dissipation, which is interlocked with the temperature sensor installed in the electrolyzer 1, and the temperature is controlled at 50 - 60 °C.

[0044] Series connection of multiple electrolyzers: When the bromide ion content in the solution is relatively high and a single electrolyzer cannot meet the requirements, multiple electrolyzers can be connected in series to meet the actual needs. The specific implementation method is that the anode outlet pipe 9 of the first electrolyzer is connected to the anode inlet pipe 8 of the second electrolyzer. The cathode inlet pipes 5 of the first and second electrolyzers are both connected to the functional tank 21. The corresponding cathode outlet pipes 7 are all connected to the functional tank 21 to achieve pressure balance and rapid release of hydrogen. The corresponding anode outlet pipes 10 are all connected to the stripping tower to achieve pressure balance, and the anodic oxidation solution enters the stripping tower for upward stripping. If more electrolyzers are needed, connect them in series according to this method.

[0045] Parallel connection of multiple electrolyzers: When the water treatment volume is relatively large, the flow rate of a single electrolyzer is too fast and the electrolysis contact residence time is too short. In this case, multiple electrolyzers can be connected in parallel to improve the treatment capacity. The specific implementation method is to connect multiple electrolyzers 1 to the functional tank 21. The corresponding cathode outlet pipes 7 are all connected to the functional tank 21 to achieve pressure balance and rapid release of hydrogen. The corresponding anode outlet pipes 10 are all connected to the stripping tower to achieve pressure balance, and the anodic oxidation solution enters the stripping tower for upward stripping. If more electrolyzers are needed, connect them in parallel according to this method, which can greatly improve the treatment speed of the electrolyzer.

[0046] Series-parallel connection of multiple electrolyzers: When the water treatment volume is large and the bromine content is relatively high, a series-parallel connection method needs to be used for treatment. The specific implementation methods include two ways: series connection first and then parallel connection, and parallel connection first and then series connection. Specifically, different connection methods need to be implemented according to the water quality situation. The implementation method of series connection first and then parallel connection: The anode outlet pipe 9 of the first electrolyzer 1 is connected to the anode inlet pipe 8 of the second electrolyzer 1. The anode outlet pipe 9 of the second electrolyzer 1 is respectively guided to the anode inlet pipes 8 of the third and fourth electrolyzers. The cathode inlet pipes 5 of the first, second, third, and fourth electrolyzers are all connected to the functional tank 21. The corresponding cathode outlet pipes 7 are all connected to the functional tank 21 to achieve pressure balance and rapid release of hydrogen. The corresponding anode outlet pipes 10 are all connected to the stripping tower to achieve pressure balance, and the anodic oxidation solution enters the stripping tower for upward stripping. The implementation method of parallel connection first and then series connection has the same cathode connection, and the anode connection order is reversed.

[0047] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A bromine extraction electrolytic cell with a series-parallel combination, characterized in that: It includes an electrolytic cell (1), electrolytic plates (2) and an electrolytic ion membrane (3); the electrolytic cell (1) is formed by encapsulation through a cell encapsulation structure (4), an electrolytic ion membrane (3) is arranged in the middle of the electrolytic cell (1), and the electrolytic cell (1) is divided into a cathode chamber and an anode chamber by the electrolytic ion membrane (3), and electrolytic plates (2) are arranged on both sides of the electrolytic ion membrane (3). A cathode water inlet pipe (5) is arranged in the middle of the cathode chamber, a cathode gas outlet pipe (7) is arranged at the top, and a cathode liquid outlet pipe (6) is arranged at the bottom. An anode water inlet pipe (8) is arranged in the middle of the anode chamber, an anode gas outlet pipe (10) is arranged at the top, and an anode liquid outlet pipe (9) is arranged at the bottom.

2. The series-parallel combined bromine extraction electrolytic cell according to claim 1, wherein: A cathode ear (24) is connected to the electrolytic plate (2) on one side of the cathode chamber; an anode ear (25) is connected to the electrolytic plate (2) on one side of the anode chamber.

3. The series-parallel combined bromine extraction electrolytic cell according to claim 1, wherein: The electrolytic plate (2) adopts a composite electrolytic plate of titanium-based iridium dioxide and tantalum pentoxide.

4. A bromine extraction device, characterized in that, The bromine extraction device includes the bromine extraction electrolytic cell in series-parallel combination described in any one of claims 1-3, a cathode pump (19), an anode pump (20) and a functional tank (21). The cathode gas outlet pipe (7) of the bromine extraction electrolytic cell is connected to the upper end of the functional tank (21) for discharging hydrogen to balance the gas pressure generated during electrolysis; the cathode liquid outlet pipe (6) of the bromine extraction electrolytic cell is connected to the bottom end of the functional tank (21) for liquid reflux to achieve pH stability; the cathode water inlet pipe (5) of the bromine extraction electrolytic cell is connected to the liquid outlet (17) at the bottom end of the functional tank (21) through the cathode pump (19), and the anode water inlet pipe (8) of the bromine extraction electrolytic cell is connected to the liquid outlet (17) at the bottom end of the functional tank (21) through the anode pump (20).

5. The bromine extraction equipment according to claim 4, characterized in that: A hydrogen outlet (11) is arranged at the top of the functional tank (21). A raw water inlet pipe (16) is connected to the outer wall at the upper end of the functional tank (21). A grid support frame (12) is arranged inside the functional tank (21) above the raw water inlet pipe (16). A gas-liquid grid (13) is arranged on the grid support frame (12). A water-cooled coil pipe (14) is arranged on the inner wall of the functional tank (21). The bottom end and the upper end of the water-cooled coil pipe (14) are respectively connected to a water-cooled outlet (22) and a water-cooled inlet (23) extending out of the back of the functional tank (21). A liquid level gauge (15) is arranged on the outer wall of one side of the functional tank (21); a cleaning bottom valve (18) is further arranged at the bottom end of the functional tank (21).

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