Method and equipment for extracting bromine from bromine-containing high-salinity wastewater

Abstract

The present application relates to bromine extraction technical field, specifically disclose a kind of high-salt wastewater containing bromine extraction method and equipment, comprising the following steps, (S01) take the high-salt wastewater containing bromine of proper amount and inject into electrolytic cell, adjust the pH of high-salt wastewater containing bromine;(S02) after pH adjustment, power oxidation is carried out, after completion, oxidation liquid is obtained;(S03) oxidation liquid is sent into reaction vessel, and again inject the high-salt wastewater containing bromine of proper amount into reaction vessel and mix;(S04) adjust the pH of mixed solution and carry out stirring reaction, obtain bromine-containing feed liquid;(S05) bromine-containing feed liquid is sent into the tube pass of membrane absorption pipe assembly, while inputting alkali absorption liquid into the shell pass of membrane absorption pipe assembly, after absorption is completed, bromine-containing enrichment liquid is obtained;(S06) bromine-containing enrichment liquid in shell pass is sent into bromine storage container, and feed liquid in tube pass is sent into external storage tank.The present application has the characteristics of ideal bromine extraction and reuse effect and no additional environmental pollution.

Description

Technical Field

[0001] This invention relates to the field of bromine extraction technology, and in particular to a method and equipment for extracting bromine from bromine-containing high-salt wastewater. Background Technology

[0002] Bromine is an important chemical raw material, widely used in flame retardants, pharmaceuticals, dyes, photography, and pesticides. my country is the world's third-largest bromine producer, after the United States and Israel, primarily sourcing bromine from underground brine. However, with the depletion of brine resources and increasing demand from downstream products, my country's bromine market is facing a severe supply shortage, leading to increased dependence on imports. In 2020, my country's bromine imports reached 5.37 × 10⁻⁶. 4 my country still relies heavily on bromine imports, and for a considerable period to come, it will continue to depend on imports to some extent. With rapid urbanization and technological advancements, my country has become a major manufacturing nation. Consequently, the amount of solid waste generated is increasing, and hazardous solid waste, if not properly disposed of, can cause serious harm to the environment and human health. Incineration is currently the preferred method for disposing of hazardous waste, and the flue gas produced is typically absorbed using alkali. Since incinerated solid waste often contains elements such as chlorine and bromine, the deacidification wastewater from incineration often contains large amounts of sodium chloride and sodium bromide. Therefore, the recovery of bromine resources is essential.

[0003] Currently, the bromine production industry has been using either steam distillation or air blowing to extract bromine from concentrated seawater or brine. The most widely used method industrially is air blowing, which involves: acidifying and oxidizing brine ions to elemental bromine with chlorine; then blowing the elemental bromine out of the brine with air; absorbing and enriching the elemental bromine in the air with an absorbent to form hydrobromic acid or sodium bromide solution; finally, secondary oxidation with chlorine and steam distillation to obtain the bromine product. Both of these processes have high bromine yields and are technically mature, but the equipment is large, control is difficult, energy consumption is high, resource utilization is low, and problems such as flooding and foam entrainment are prone to occur.

[0004] Existing bromine extraction methods also employ a front-end chlorine oxidation process. However, this method consumes a large amount of chlorine, which can lead to acidic discharge brine. The introduction of chlorine also poses safety hazards such as leakage and explosion, as well as environmental pollution risks, severely restricting the development of the bromine industry.

[0005] Patent document with publication number "CN114875428A" proposes a method for extracting bromine from potassium-extracting brine and producing sodium brine. Using "electro-oxidation-resin adsorption-evaporation crystallization" as the main process, it eliminates the need for chlorine gas to oxidize brine ions and avoids acidity in the feed potassium-extracting brine, thus laying the foundation for bromine extraction and resource utilization from potassium-extracting brine. This method uses electro-oxidation instead of chlorine oxidation, avoiding the storage and transportation safety issues and environmental pollution risks associated with traditional chlorine oxidation. In particular, the electrodes and voltage of the electro-oxidation process significantly affect its effectiveness, and the composition of different bromine-containing brine systems (such as pH and chloride / bromine ion ratio) directly determines the electrolysis voltage and the final product after electro-oxidation.

[0006] Therefore, current treatment methods for bromine-containing wastewater suffer from unsatisfactory bromine extraction and reuse effects and additional environmental pollution. Summary of the Invention

[0007] In order to solve the above-mentioned technical problems existing in the treatment of bromine-containing wastewater, the present invention provides a method and equipment for bromine extraction from bromine-containing high-salt wastewater, which has the characteristics of ideal bromine extraction and reuse effect and no additional environmental pollution.

[0008] The first technical solution of the present invention: a method for extracting bromine from bromine-containing high-salt wastewater, comprising the following steps:

[0009] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater;

[0010] (S02) After the pH is adjusted in step (S01), electro-oxidation is carried out, and an oxidized solution is obtained after completion;

[0011] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed.

[0012] (S04) Adjust the pH of the mixture from step (S03) and stir to obtain a bromine-containing solution;

[0013] (S05) The bromine-containing liquid from step (S04) is fed into the tube side of the membrane absorption tube assembly, and at the same time, the alkaline absorbent is fed into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-containing enriched liquid is obtained.

[0014] (S06) The bromine-enriched solution in the shell side of step (S05) is sent to the bromine storage container, and the feed solution in the tube side of step (S05) is sent to the external outlet tank. This invention injects bromine-containing high-salt wastewater into an electrolytic cell and adjusts the pH of the wastewater to a suitable value, thereby facilitating subsequent efficient electrolytic oxidation. Electro-oxidation is used to efficiently oxidize bromide ions in the bromine-containing high-salt wastewater to bromate ions. This invention then mixes the oxidized solution converted to bromate ions with the bromine-containing high-salt wastewater again in a proportional ratio, allowing bromate ions and bromide ions to undergo a disproportionation reaction, efficiently obtaining a bromine-containing feed solution containing bromine water. Adjusting the pH of the mixture again is to further enhance the disproportionation reaction, resulting in a bromine-containing feed solution with a higher concentration of bromine water. This invention uses the principle of alkaline membrane absorption to absorb bromine-containing... The feed solution is introduced into the tube side of the membrane absorption tube assembly, while the alkaline absorbent is introduced into the shell side. At this time, the bromine in the bromine-containing feed solution diffuses through the membrane into the alkaline absorbent, ultimately obtaining a bromine-enriched solution, which is a high-purity bromine water. After the bromide ions in the bromine-containing high-salt wastewater are removed, it becomes debromine-removed permeate that can be reused. The entire bromine extraction process is highly efficient and effective. The resulting bromine-enriched solution can realize the recovery and reuse of bromine resources without any safety hazards or environmental pollution risks. The final permeate in the tube side after bromine removal is directly used for industrial production, thereby achieving the ultimate goal of highly efficient bromine extraction.

[0015] Preferably, the bromide ion content in the bromine-containing high-salinity wastewater is 100 mg / L to 20000 mg / L. More preferably, the bromide ion content in the bromine-containing high-salinity wastewater is 500 mg / L to 15000 mg / L. More preferably, the bromide ion content in the bromine-containing high-salinity wastewater is 1000 mg / L to 10000 mg / L. More preferably, the bromide ion content in the bromine-containing high-salinity wastewater is 2000 mg / L to 8000 mg / L. More preferably, the bromide ion content in the bromine-containing high-salinity wastewater is 4000 mg / L to 6000 mg / L. This limitation on the bromide ion content in the bromine-containing high-salinity wastewater allows for a more accurate determination of the bromide ion content to be treated, thereby enabling more precise control of the electrolysis pressure, current density, and electrolysis time. It also provides an expectation of the bromate content in the final oxidized solution, making subsequent addition of the bromine-containing high-salinity wastewater in proportion more accurate.

[0016] Preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 1000 mg / L to 100000 mg / L. More preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 2000 mg / L to 80000 mg / L. More preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 4000 mg / L to 60000 mg / L. More preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 6000 mg / L to 40000 mg / L. More preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 8000 mg / L to 20000 mg / L. More preferably, the chloride ion content in the bromine-containing high-salinity wastewater is 10000 mg / L to 15000 mg / L.

[0017] Preferably, in step (S01), the pH of the bromine-containing high-salt wastewater is adjusted to 8-11. More preferably, in step (S01), the pH of the bromine-containing high-salt wastewater is adjusted to 8.5-10.5. Even more preferably, in step (S01), the pH of the bromine-containing high-salt wastewater is adjusted to 9-10. Adjusting the pH to a defined range here makes the bromine-containing high-salt wastewater generally alkaline, thereby facilitating more efficient subsequent electrolytic oxidation.

[0018] Preferably, the solution used to adjust the pH in step (S01) is a sodium hydroxide solution. Sodium hydroxide solution can more quickly and accurately adjust the pH of bromine-containing, high-salt wastewater to a suitable range.

[0019] Preferably, the current density of the electro-oxidation in step (S02) is 10 A / m. 2 ~300A / m 2 More preferably, the current density of the electro-oxidation in step (S02) is 20 A / m. 2 ~250A / m 2 More preferably, the current density of the electro-oxidation in step (S02) is 50 A / m. 2 ~200A / m 2 More preferably, the current density of the electro-oxidation in step (S02) is 80 A / m. 2 ~180A / m 2 More preferably, the current density of the electro-oxidation in step (S02) is 100 A / m. 2 ~150A / m 2 The specific current density limit here is to more accurately control the overall electro-oxidation rate, so that bromide ions in the bromine-containing high-salt wastewater can be efficiently oxidized at the anode to form bromate ions.

[0020] Preferably, the voltage for electro-oxidation in step (S02) is 10V to 50V. More preferably, the voltage for electro-oxidation in step (S02) is 12V to 45V. More preferably, the voltage for electro-oxidation in step (S02) is 16.5V to 40V. More preferably, the voltage for electro-oxidation in step (S02) is 20V to 35V. More preferably, the voltage for electro-oxidation in step (S02) is 25V to 30V. The specific voltage limits here are to more accurately control the overall electro-oxidation rate, ensuring that bromide ions in the high-salt bromide wastewater can efficiently undergo an oxidation reaction at the anode to generate bromate ions.

[0021] Preferably, the electro-oxidation time in step (S02) is 30 min to 300 min. More preferably, the electro-oxidation time in step (S02) is 40 min to 250 min. More preferably, the electro-oxidation time in step (S02) is 50 min to 200 min. More preferably, the electro-oxidation time in step (S02) is 80 min to 180 min. More preferably, the electro-oxidation time in step (S02) is 100 min to 150 min. More preferably, the electro-oxidation time in step (S02) is 120 min to 140 min. The specific limitation on the electro-oxidation time here is to ensure the complete electro-oxidation reaction while also considering timeliness.

[0022] Preferably, the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:3 to 8. More preferably, the volume ratio is 1:4 to 7. Even more preferably, the volume ratio is 1:5 to 6. This limitation on the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater is to ensure a more complete and efficient disproportionation reaction between bromate and bromide ions, resulting in a bromine-containing feed solution containing bromine water.

[0023] Preferably, the reaction vessel in step (S03) is a discharge tank. The discharge tank provides a safe and suitable reaction environment for the disproportionation reaction of bromate and bromide ions.

[0024] Preferably, in step (S04), the pH of the mixture is adjusted to 2-4. More preferably, in step (S04), the pH of the mixture is adjusted to 2.5-3.5. Even more preferably, in step (S04), the pH of the mixture is adjusted to 3. This specific limitation on the pH of the mixture is to facilitate a more efficient disproportionation reaction and obtain a bromine-containing solution with a higher concentration of bromine in the water.

[0025] Preferably, the solution used to adjust the pH of the mixture in step (S04) is hydrochloric acid. Hydrochloric acid can adjust the pH of the mixture to a suitable range more quickly and accurately.

[0026] Preferably, the reaction time in step (S04) is 20 min to 60 min. More preferably, the reaction time in step (S04) is 25 min to 55 min. Even more preferably, the reaction time in step (S04) is 30 min to 50 min. Even more preferably, the reaction time in step (S04) is 35 min to 45 min. This specific limitation on the reaction time is to ensure the entire neutralization reaction is complete while also considering timeliness.

[0027] Preferably, the membrane material in the membrane absorption tube assembly is polytetrafluoroethylene (PTFE). PTFE has good acid and alkali resistance and corrosion resistance, and as the membrane material in the membrane absorption tube assembly, it will have a longer service life.

[0028] Preferably, the membrane absorption temperature in step (S05) is 45°C to 55°C. More preferably, the membrane absorption temperature in step (S05) is 48°C to 52°C. Even more preferably, the membrane absorption temperature in step (S05) is 50°C. This specific limitation on the membrane absorption temperature is to allow bromine in the bromine-containing feed solution in the tube side to diffuse more efficiently through the membrane into the alkali absorbent in the shell side.

[0029] Preferably, in step (S05), the flow rate of the bromine-containing solution in the tubular section is 4 L / h to 20 L / h. More preferably, the flow rate of the bromine-containing solution in the tubular section is 6 L / h to 18 L / h. More preferably, the flow rate of the bromine-containing solution in the tubular section is 8 L / h to 15 L / h. More preferably, the flow rate of the bromine-containing solution in the tubular section is 10 L / h to 11.5 L / h. This specific limitation on the flow rate of the bromine-containing solution in the tubular section is to ensure a certain bromine extraction rate.

[0030] Preferably, in step (S05), the flow rate of the alkali absorbent in the shell side is 10 L / h to 100 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 15 L / h to 90 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 20 L / h to 80 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 25 L / h to 70 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 30 L / h to 60 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 33.1 L / h to 50 L / h. More preferably, the flow rate of the alkali absorbent in the shell side is 40 L / h to 45 L / h. The specific limit on the flow rate of the alkali absorbent in the shell side is to ensure that the bromine in the bromine feed solution in the tube side is absorbed as fully as possible.

[0031] Preferably, the absorption time in step (S05) is 1 hour to 10 hours. More preferably, the absorption time in step (S05) is 2 hours to 8 hours. Even more preferably, the absorption time in step (S05) is 3 hours to 6 hours. Even more preferably, the absorption time in step (S05) is 4 hours to 5 hours. This specific limitation on the absorption time is to ensure that the alkaline absorbent can absorb the bromine in the bromine feed solution in the tube as fully as possible, while also considering timeliness.

[0032] Preferably, the alkali absorbent in step (S05) is a sodium hydroxide solution. Sodium hydroxide solution, as an alkali absorbent, has a good absorption effect on bromine in the bromine feed solution.

[0033] Preferably, the pH of the sodium hydroxide solution is 11-15. More preferably, the pH of the sodium hydroxide solution is 11.5-14.5. More preferably, the pH of the sodium hydroxide solution is 12-14. More preferably, the pH of the sodium hydroxide solution is 12.5-13.5. More preferably, the pH of the sodium hydroxide solution is 13. Sodium hydroxide solutions with specific pH values ​​exhibit better absorption of bromine in bromine feed solutions.

[0034] Preferably, the bromine storage container is a bromine storage tank assembly. Bromine storage tank assemblies can store bromine-enriched solutions more stably.

[0035] The second technical solution of the present invention: a bromine extraction device for high-salinity bromine-containing wastewater, comprising a metal support frame, wherein the metal support frame is provided with a first placement area, a second placement area, and a third placement area; the first placement area is provided with a discharge tank control device, an electrolytic cell control device, and a membrane absorption tube control device; the second placement area is provided with a fixing frame, on which an electrolytic cell is installed, and the electrolytic cell is electrically connected to the electrolytic cell control device; the metal support frame is provided with a discharge area, and the discharge area is provided with a discharge tank, and the discharge tank is connected to a discharge tank control device. The equipment is electrically connected, with the discharge tank connected to the drain port of the electrolytic cell via a first feed pipe; a membrane absorption tube assembly is provided in the third placement area, which is electrically connected to the membrane absorption tube control equipment, and is connected to the discharge tank via a second feed pipe; an alkali tank is provided in the discharge area, which is connected to the membrane absorption tube assembly via an alkali pipe; an external placement area is provided outside the metal support, and a bromine storage tank group is provided in the external placement area, which is connected to the membrane absorption tube assembly via a third feed pipe.The metal support of this invention is divided into a first placement area, a second placement area, a third placement area, a discharge area, and an external placement area, providing installation positions for different equipment components. All equipment components are concentrated in the metal support, resulting in a high degree of integration for the entire bromine extraction equipment. The discharge tank control device in this invention can accurately control the inflow, outflow, and reaction at the discharge tank, mixing the oxidized liquid converted to bromate and the bromine-containing high-salt wastewater in a predetermined ratio, causing the bromate and bromide ions to undergo a disproportionation reaction, efficiently obtaining bromine-containing water. The electrolytic cell control equipment accurately controls the inlet, outlet, and reaction conditions at the electrolytic cell, enabling efficient oxidation of bromide ions in the bromine-containing, high-salt wastewater to bromate ions. The membrane absorber control equipment accurately controls the flow rate of the bromine-containing feed solution into the tube side of the membrane absorber assembly and the input rate of the alkaline absorbent into the shell side, allowing bromine in the bromine-containing feed solution to diffuse more efficiently through the membrane into the alkaline absorbent. The mounting bracket in this invention provides a stable installation position for the electrolytic cell. The electrolytic cell efficiently treats bromine-containing, high-salt wastewater. The bromide ions in the electrolyte are efficiently electro-oxidized to bromate ions; bromate ions and bromide ions in the discharge tank undergo a disproportionation reaction, efficiently yielding a bromine-containing liquid containing bromine water; the first feed pipe stably delivers the oxidizing liquid from the electrolytic cell into the discharge tank; the membrane absorption tube assembly in this invention efficiently achieves the absorption of bromine from the bromine liquid by the alkali absorption liquid; the second feed pipe stably delivers the bromine-containing liquid from the discharge tank into the tube side of the membrane absorption tube assembly; the alkali tank in this invention is used for the safe storage of the alkali absorption liquid; the alkali tube stably delivers the alkali absorption liquid into the membrane absorption tube assembly. The shell side of the receiving tube assembly provides a stable placement location for the bromine storage tank group; the bromine storage tank group can stably and safely store the obtained bromine-containing enriched solution; the third feed pipe can stably deliver the bromine-containing enriched solution in the shell side of the membrane absorption tube assembly into the bromine storage tank group; the invention as a whole has high integration and intelligence, and has a good bromine extraction effect and high bromine extraction efficiency in bromine-containing high-salt wastewater. The obtained bromine-containing enriched solution can realize the recycling and reuse of bromine resources, and there are no safety hazards or environmental re-pollution risks.

[0036] Preferably, the discharge tank control device includes a first housing, a first controller is provided inside the first housing, and a pressure monitoring display, a control switch group and a material feeding status display are provided on the first housing. The pressure monitoring display, the control switch group and the material feeding status display are all electrically connected to the first controller.

[0037] The electrolytic cell control device includes a second housing, a second controller is provided inside the second housing, and an upper and lower hydraulic control switch, an electrode control knob, an electrolyte feed control knob and an electrolytic cell status display screen are provided on the second housing. The upper and lower hydraulic control switch, the electrode control knob, the electrolyte feed control knob and the electrolytic cell status display screen are all electrically connected to the second controller.

[0038] The membrane absorption tube control device includes a third housing, within which a third controller is provided. The third housing is equipped with a membrane absorption tube pressure display, a bromine extraction tube control button, and a membrane absorption tube status display screen, all of which are electrically connected to the third controller.The present invention includes a pressure sensor installed inside the discharge tank for real-time monitoring of the pressure inside the tank. An electromagnetic pressure relief valve is also installed on the discharge tank; when the pressure inside the tank is too high, the electromagnetic pressure relief valve opens to release pressure, ensuring the safety of the reaction inside the tank. Both the pressure sensor and the electromagnetic pressure relief valve are electrically connected to a first controller, and the entire system is controlled by the first controller. A control switch group is used to control the opening and closing of the electromagnetic valves at the inlet and outlet of the discharge tank, rationally controlling the injection volume of the oxidizing liquid and bromine-containing high-salt wastewater into the discharge tank, ensuring the efficient conduct of the bromate and bromide ion neutralization reaction. A first feed pump is installed on the first feed pipe, and the first feed pump is electrically connected to the first controller; the start and stop of the first feed pump are also controlled by the control switch group. A first pH sensor is installed inside the discharge tank, and is electrically connected to a first controller to accurately monitor the pH of the mixed solution in the discharge tank, ensuring it remains within a reasonable range and guaranteeing the efficient reaction of bromate and bromide ions. A flow meter is installed on the first feed pipe, and a level gauge is installed inside the discharge tank. Both the flow meter and the level gauge are electrically connected to the first controller, thereby accurately controlling the injection volume of the oxidizing liquid and bromine-containing high-salt wastewater into the discharge tank. The feed status display screen can show the injection status and the liquid level in the discharge tank in real time. A hydraulic pump is installed on the liquid input pipeline of the electrolytic cell of this invention, and a flow meter is installed on the input pipeline. Both the hydraulic pump and the flow meter are electrically connected to a second controller. By controlling the hydraulic pump, the amount of bromine-containing high-salt wastewater entering the electrolytic cell can be controlled. The hydraulic pressure of the saline wastewater is adjusted to ensure that the high-salt, bromine-containing wastewater to be electrolyzed in the electrolytic cell is at a suitable level. The upper and lower hydraulic control switches accurately adjust the injection pressure of the hydraulic pump. The electrode control knob accurately controls the electrolysis voltage and current density of the electrolytic cell, thus accurately controlling the overall electro-oxidation rate. The electrolyte feed control knob accurately controls the opening of the solenoid valve for the high-salt, bromine-containing wastewater entering the electrolytic cell, ensuring the wastewater level is at a suitable height. A level gauge and a second pH sensor are installed in the electrolytic cell, both electrically connected to a second controller for real-time monitoring of the liquid level and pH. The electrolytic cell status display screen shows the electrolysis pressure, current density, and... The invention includes parameters such as electrolysis time, liquid level, and pH. A second feed pump is installed at the second feed pipe, and an alkali delivery pump is installed at the alkali pipe. Both the second feed pump and the alkali delivery pump are electrically connected to a third controller. The membrane absorption tube pressure display can show the delivery pressure of the second feed pump and the alkali delivery pump in real time, thereby accurately controlling the amount of material entering the membrane absorption tube assembly. The bromine extraction tube control button can control the solenoid valves for the liquid entering and exiting the membrane absorption tube assembly, thereby controlling the entire bromine extraction progress. A temperature sensor is installed inside the membrane absorption tube assembly and is electrically connected to the second controller. The membrane absorption tube status display can show parameters such as liquid flow rate, absorption temperature, and absorption time in the entire membrane absorption tube assembly in real time.

[0039] Preferably, the electrolytic cell is provided with a partition that divides the interior of the electrolytic cell into a first electrolytic cell and a second electrolytic cell; both the first and second electrolytic cells are equipped with plug-in plates, and the outer edge of each plug-in plate has multiple plug-in slots; the plug-in plates are respectively provided with a first electrode plate and a second electrode plate, both of which are electrically connected to a second controller; the first electrode plate is provided with a plurality of anode electrode blocks, and the second electrode plate is provided with a plurality of cathode electrode blocks, both of which are adjusted and positioned within their respective plug-in slots. A partition divides the entire electrolytic cell into a first electrolytic cell and a second electrolytic cell. The first and second electrolytic cells are relatively independent and can be used simultaneously or individually, providing a degree of selectivity. A connecting plate is used to adjust the first and second electrode plates relative to the electrolytic cell. By adjusting the contact area between the anode and cathode electrode blocks and the bromine-containing high-salt wastewater to be electrolyzed, the entire electrolysis process is controlled. A connecting slot cooperates with the anode and cathode electrode blocks to prevent the first and second electrode plates from moving left and right on the connecting plate, ensuring the stability of the electrolysis process. The first and second electrode plates provide installation positions and power conduction for the anode and cathode electrode blocks, respectively. Bromine ions in the bromine-containing high-salt wastewater undergo an oxidation reaction at the anode electrode block to generate bromate, transforming the bromine-containing wastewater in the electrolytic cell into an oxidized solution containing bromate.

[0040] Preferably, both the first and second electrolytic cells are provided with toothed grooves. A displacement rod is provided on the plug-in plate, and a first motor is mounted on the displacement rod. The drive end of the first motor has a displacement gear that meshes with the toothed grooves. The first motor is electrically connected to a second controller. The toothed grooves and displacement gear move under the driving force of the first motor, controlling the position of the plug-in plate within the electrolytic cell. This controls the contact area between the anode and cathode electrode blocks and the bromine-containing high-salt wastewater to be electrolyzed, thus controlling the entire electrolysis process. The end of the displacement rod extends to the outside of the electrolytic cell, limiting the insertion depth of the plug-in plate within the cell. This prevents the anode and cathode electrode blocks from moving indefinitely and colliding with the bottom of the electrolytic cell, causing damage. It also facilitates manual removal of the plug-in plate for inspection of the first and second electrode plates.

[0041] Preferably, both the first and second electrolytic cells are provided with a liquid discharge port at the bottom, and an electromagnetic liquid discharge valve is provided at the liquid discharge port. The electromagnetic liquid discharge valve is electrically connected to a second controller. The liquid discharge port is used to discharge the oxidizing liquid into a discharge tank; the electromagnetic liquid discharge valve can regulate the discharge rate of the oxidizing liquid.

[0042] Preferably, the anode electrode block is a titanium metal electrode block with a surface coated with an alloy composed of ruthenium, iridium, and platinum; the cathode electrode block is also a titanium metal electrode block. The titanium metal electrode block with the surface coated with the alloy composed of ruthenium, iridium, and platinum, as the anode electrode block, works well with the titanium metal cathode electrode block, exhibiting high electrolysis efficiency for bromine-containing, high-salt wastewater, as well as high corrosion resistance and acid / alkali resistance, and a long service life.

[0043] Preferably, both the first and second electrolytic cells are made of PP material. Electrolytic cell bodies made of PP material are corrosion-resistant and insulating, ensuring the safe operation of the entire electrolysis process.

[0044] Preferably, the pH of the reaction solution in the electrolytic cell is 8–11. More preferably, the pH of the reaction solution in the electrolytic cell is 8.5–10.5. Even more preferably, the pH of the reaction solution in the electrolytic cell is 9–10. Adjusting the pH to this defined range makes the bromine-containing, high-salt wastewater generally alkaline, thereby facilitating more efficient subsequent electrolytic oxidation.

[0045] Preferably, both the first and second electrolytic cells are equipped with feeding pipes, each containing an electromagnetic feeding valve electrically connected to a second controller. The feeding pipes are used to add bromine-containing high-salt wastewater and sodium hydroxide solution to the electrolytic cells; the opening of the electromagnetic feeding valve can accurately control the amount of bromine-containing high-salt wastewater and sodium hydroxide solution added to the electrolytic cells.

[0046] Preferably, the bottom of the first electrolytic cell and the second electrolytic cell are respectively provided with a first outlet tank and a second outlet tank, and the bottom of the first outlet tank and the second outlet tank are respectively provided with a first outlet port and a second outlet port. Each of the first outlet port and the second outlet port is connected to an outlet pipe, which is connected to a first conveying pipe. The first outlet tank and the second outlet tank are used to collect the oxidized liquid after electrolysis in the first electrolytic cell and the second electrolytic cell, respectively, to ensure that the oxidized liquid fed into the discharge tank is a fully electrolyzed bromate solution. The first outlet port and the second outlet port are used to discharge the collected oxidized liquid in the first outlet tank and the second outlet tank into the discharge tank, respectively. The outlet pipe is used to smoothly feed the collected oxidized liquid in the first outlet tank and the second outlet tank into the first conveying pipe.

[0047] Preferably, a first electromagnetic discharge valve is provided at the first discharge port, and a second electromagnetic discharge valve is provided at the second discharge port. Both the first and second electromagnetic discharge valves are electrically connected to the second controller. The first and second electromagnetic discharge valves are used to control the discharge volume in the first and second discharge tanks, respectively.

[0048] Preferably, both the first and second outlet tanks are equipped with level sensors, which are electrically connected to the second controller. The level sensors are used to monitor the liquid level of the oxidized liquid accumulation in both the first and second outlet tanks in real time.

[0049] Preferably, the discharge tank is equipped with a first pH sensor, which is electrically connected to a first controller. The first pH sensor can accurately monitor the pH of the mixture in the discharge tank to ensure it remains within a reasonable range, thus guaranteeing the efficient conduct of the bromate and bromide ion disproportionation reaction.

[0050] Preferably, the discharge tank includes a tank body located within the discharge area. The tank body is equipped with an inlet pipe, an outlet pipe, and a liquid injection port. The inlet pipe is connected to the outlet pipe via a first conveying pipe, and the outlet pipe is connected to the membrane absorption tube assembly via a second conveying pipe. The inlet pipe is used to smoothly deliver bromine-containing high-salt wastewater and oxidizing liquid into the tank body for mixing and reaction; the outlet pipe is used to smoothly deliver the bromine-containing liquid after the neutralization reaction is completed into the tube side of the membrane absorption tube assembly; the liquid injection port is used to add hydrochloric acid solution into the tank body for pH adjustment.

[0051] Preferably, the can body has a first sealing layer at the can opening, and a first sealing ring is provided on the first sealing layer; the can body has a sealing cap at the can opening, one side of the sealing cap is rotatably connected to the can body by a sealing pin, a second sealing ring is provided inside the sealing cap, and a locking mechanism is provided on the can body. The first sealing layer, the first sealing ring, and the second sealing ring are all made of rubber, and are all for the purpose of achieving a good seal between the sealing cap and the can body, ensuring the airtightness of the reaction inside the can; the sealing cap is rotatably set relative to the top of the can body by the sealing pin, which facilitates the opening and sealing of the can opening at the top of the can body; the locking mechanism is used to achieve a good seal and lock the sealing cap at the can opening.

[0052] Preferably, the locking mechanism includes a frame mounted on the tank body, and a magnetic locking block is provided on the frame. A second locking block is provided on the side of the sealing cap away from the sealing pin, and the second locking block has an electromagnet slot corresponding to the magnetic locking block. The electromagnet slot is electrically connected to a first controller. This electromagnetic locking and unlocking mechanism, using the magnetic locking block and electromagnet slot in conjunction, features strong locking force and quick unlocking. Both locking and unlocking are electromagnetically controlled, making both processes relatively fast.

[0053] Preferably, the frame contains a first threaded rod, the end of which is rotatably mounted on the inner wall of the frame. A movable block is threadedly connected to the first threaded rod, a movable rod is mounted on the movable block, and a first locking block is mounted on the movable rod. A magnetic locking block is mounted on the first locking block. A first bevel gear is located on the first threaded rod away from the first locking block, and a second bevel gear meshes with the first bevel gear. A connecting rod is mounted on the second bevel gear. A second motor is mounted on the frame, the drive end of which is connected to the connecting rod, and the second motor is electrically connected to a first controller. The first threaded rod receives the driving force of the second motor, enabling the movable block to move up and down. Under the up and down force of the movable block, the movable rod drives the magnetic locking block to move up and down. When the magnetic locking block engages with the electromagnet slot, the movable block moves downward, achieving a good seal at the can opening. The first locking block provides an installation position for the magnetic locking block. The first and second bevel gears cooperate to convert the driving force of the horizontally placed second motor into a vertical rotational force on the first threaded rod.

[0054] Preferably, a third motor is provided at the top of the tank, and a stirring rod is provided at the drive end of the third motor. The stirring rod penetrates through the top of the tank and enters the interior of the tank. The stirring rod is provided with multiple sets of stirring blades. The third motor is electrically connected to the first controller. The third motor provides driving force for the rotation of the stirring rod; the stirring rod drives the stirring blades to rotate, so that bromate and bromide ions in the tank can fully undergo a neutralization reaction.

[0055] Preferably, the membrane absorption tube assembly includes several membrane absorption tubes, one end of each membrane absorption tube is provided with a feed inlet, which is connected to an alkali solution tube and a second feed tube respectively. A feed solenoid valve is provided at the feed inlet and is electrically connected to a third controller. The other end of the membrane absorption tube is connected to a control chamber, which is equipped with a hot and cold compression pump and is electrically connected to the third controller. Several bromine extraction tube assemblies are connected to the membrane absorption tube. The membrane absorber tube is used for the flow of alkaline absorbent in the shell side and bromine-containing feed solution in the tube side, thereby achieving efficient absorption of bromine from the bromine feed solution by the alkaline absorbent. The feed inlet is used for the inflow of alkaline absorbent and bromine-containing feed solution. The feed solenoid valve is used to control the feed rate of alkaline absorbent and bromine feed solution. The temperature control chamber is used to regulate the temperature of the membrane absorber tube throughout the absorption process. The hot and cold compressor pump is used to provide power for temperature regulation in the temperature control chamber. The bromine extraction tube assembly is used to stably deliver the bromine-enriched solution after absorption in the shell side to the bromine storage tank group, and to deliver the feed solution after bromine absorption in the tube side to the storage tank. Finally, the product water in the storage tank is used for industrial production.

[0056] Preferably, the membrane absorption tube is a serpentine tube. The serpentine shape of the membrane absorption tube allows for a larger absorption process, ensuring that the alkaline absorption solution fully absorbs and extracts bromine from the bromine-containing feed solution.

[0057] Preferably, the bromine extraction tube assembly is located at the bend of the membrane absorption tube, allowing the bromine-enriched solution and the final permeate to be discharged to appropriate locations respectively.

[0058] Preferably, the bromine extraction pipe assembly includes a third liquid outlet pipe, a first liquid outlet pipe, and a second liquid outlet pipe; the bromine storage tank group includes several bromine storage tanks, and adjacent bromine storage tanks are connected by a first gas transmission pipe; the third liquid outlet pipe is connected to an external liquid storage tank through a fourth feed pipe; the first liquid outlet pipe and the second liquid outlet pipe are both connected to the bromine storage tank through the third feed pipe. The third liquid outlet pipe is used to deliver the bromine-absorbed liquid in the tube side to the storage tank, which can be directly used for industrial applications. The fourth feed pipe is equipped with a fourth feed pump and a flow meter, both of which are electrically connected to the third controller. The first and second liquid outlet pipes are used to stably deliver the bromine-enriched liquid in the shell side after absorption to the bromine storage tank group through the third feed pipe. The third feed pipe is equipped with a third feed pump and a flow meter, both of which are electrically connected to the third controller. The first gas supply pipe connects adjacent bromine storage tanks together, allowing the bromine vapor in the storage tanks to circulate with each other, thereby ensuring the stability of the gas pressure in the entire bromine storage tank. The bromine storage tank is equipped with an electromagnetic pressure relief valve, which is electrically connected to the third controller.

[0059] Preferably, several bromine storage tanks are arranged in parallel.

[0060] Preferably, the membrane absorption tube includes a tube body, inside which a permeable membrane tube is disposed. The interior of the permeable membrane tube forms the tube side, and the space between the permeable membrane tube and the tube body forms the shell side. One end of the shell side of the membrane absorption tube is connected to the alkali solution tube, and the other end of the shell side is connected to the first and second outlet pipes. One end of the tube side is connected to the second feed pipe, and the other end of the tube side is connected to the third outlet pipe. The permeable membrane tube enables stable transport of the bromine-containing liquid while effectively allowing the bromine in the liquid to be absorbed by the alkali absorbent. The tube side is used for stable transport of the bromine-containing liquid, and the shell side is used for stable transport of the alkali absorbent. The entire membrane absorption tube has a simple and ingenious structure, provides good absorption of bromine from the bromine-containing liquid by the alkali absorbent, and eliminates the problem of additional environmental pollution.

[0061] Preferably, the outer wall of the tube is provided with a heating layer and an insulation layer from the inside out. A first temperature sensor is installed in the heating layer and is electrically connected to a third controller. The heating layer is connected to a hot and cold compression pump to control the temperature of bromine absorption inside the tube; the insulation layer prevents heat loss and saves energy; the first temperature sensor can monitor the temperature of bromine absorption in real time to ensure better absorption of bromine.

[0062] Preferably, the filtration membrane tube is made of polytetrafluoroethylene (PTFE). PTFE filtration membrane tubes have good acid and alkali resistance and corrosion resistance, and as the membrane material in the membrane absorption tube assembly, they will have a longer service life.

[0063] Preferably, the concentration of the alkali solution in the alkali solution tank is 0.002 mol / L to 1 mol / L. More preferably, the concentration of the alkali solution in the alkali solution tank is 0.005 mol / L to 0.8 mol / L. More preferably, the concentration of the alkali solution in the alkali solution tank is 0.01 mol / L to 0.5 mol / L. More preferably, the concentration of the alkali solution in the alkali solution tank is 0.05 mol / L to 0.3 mol / L. More preferably, the concentration of the alkali solution in the alkali solution tank is 0.08 mol / L to 0.1 mol / L. Alkali solutions of specific concentrations can more effectively absorb bromine from bromine-containing feed solutions.

[0064] The present invention has the following beneficial effects:

[0065] (1) By injecting bromine-containing high-salt wastewater into an electrolytic cell, the pH of the bromine-containing high-salt wastewater is adjusted to a suitable value, which facilitates subsequent efficient electrolytic oxidation; by using electro-oxidation, the bromide ions in the bromine-containing high-salt wastewater are efficiently oxidized to bromate ions;

[0066] (2) The oxidizing solution converted to bromate and the high-salt bromine-containing wastewater are mixed again in proportion to allow bromate and bromide ions to undergo a disproportionation reaction, so as to efficiently obtain a bromine-containing liquid containing bromine water; the pH of the mixture is adjusted again to allow the disproportionation reaction to occur more efficiently, so as to obtain a bromine-containing liquid with a higher concentration of bromine water.

[0067] (3) Using the principle of alkaline membrane absorption, the bromine-containing liquid is passed into the tube side of the membrane absorption tube assembly, and the alkaline absorbent is introduced into the shell side of the membrane absorption tube assembly. At this time, the bromine in the bromine-containing liquid will diffuse through the membrane into the alkaline absorbent, and finally a bromine-rich solution is obtained, which is a high-purity bromine water. After the bromine ions in the bromine-containing high-salt wastewater are removed, it will become debromine-removed product water that can be reused. The whole bromine extraction process is highly efficient and effective. The obtained bromine-rich solution can realize the recycling and reuse of bromine resources, and there are no safety hazards or environmental pollution risks. The final product water after debromine removal can also be directly used for industrial production, thereby achieving the final goal of high-efficiency bromine extraction.

[0068] (4) The metal bracket is divided into a first placement area, a second placement area, a third placement area, a discharge area and an outer placement area, providing installation positions for different equipment components. All equipment components are concentrated in the metal bracket, making the entire bromine extraction equipment highly integrated.

[0069] (5) The discharge tank control equipment can accurately control the liquid inlet, liquid outlet and reaction at the discharge tank, and mix the oxidized liquid converted to bromate and the bromine-containing high-salt wastewater in a certain proportion, so that bromate and bromide ions undergo a neutralization reaction, and efficiently obtain bromine-containing liquid containing bromine water; the electrolytic cell control equipment can accurately control the liquid inlet, liquid outlet and reaction at the electrolytic cell, so that bromide ions in the bromine-containing high-salt wastewater in the electrolytic cell can be efficiently oxidized to bromate; the membrane absorption tube control equipment can accurately control the amount of bromine-containing liquid entering the tube side of the membrane absorption tube assembly and the amount of alkaline absorbent entering the shell side of the membrane absorption tube assembly, so that the bromine in the bromine-containing liquid can diffuse into the alkaline absorbent more efficiently after passing through the membrane;

[0070] (6) The fixed frame provides a stable installation position for the electrolytic cell; the electrolytic cell can efficiently electro-oxidize bromide ions in bromine-containing high-salt wastewater into bromate ions; the bromate ions and bromide ions in the discharge tank undergo a neutralization reaction, which can efficiently obtain bromine-containing liquid containing bromine water; the first conveying pipe can stably send the oxidized liquid in the electrolytic cell into the discharge tank;

[0071] (7) The membrane absorption tube assembly can efficiently realize the absorption of bromine in the bromine feed liquid by the alkaline absorption liquid; the second feed pipe can stably deliver the bromine-containing feed liquid in the discharge tank into the tube side of the membrane absorption tube assembly.

[0072] (8) The alkali tank is used to safely store the alkali absorbent; the alkali pipe can stably deliver the alkali absorbent into the shell side of the membrane absorber assembly; the external placement area provides a stable placement position for the bromine storage tank group; the bromine storage tank group can stably and safely store the obtained bromine-containing enriched liquid; the third feed pipe can stably deliver the bromine-containing enriched liquid in the shell side of the membrane absorber assembly into the bromine storage tank group.

[0073] (9) It has high integration and intelligence, and has a good bromine extraction effect and high bromine extraction efficiency in bromine-containing high-salt wastewater. The obtained bromine-containing enriched liquid can realize the recycling and reuse of bromine resources, and there are no safety hazards or environmental pollution risks. Attached Figure Description

[0074] Figure 1 This is a first structural schematic diagram of the main body of the bromine extraction equipment in this invention;

[0075] Figure 2 This is a second structural schematic diagram of the main body of the bromine extraction equipment in this invention;

[0076] Figure 3 This is a schematic diagram of the first structure of the electrolytic cell in this invention;

[0077] Figure 4 This is a schematic diagram of the second structure of the electrolytic cell in this invention;

[0078] Figure 5This is a schematic diagram of the third structure of the electrolytic cell in this invention;

[0079] Figure 6 This is a schematic diagram of the fourth structure of the electrolytic cell in this invention;

[0080] Figure 7 This is a schematic diagram of the structure at the tooth groove in this invention;

[0081] Figure 8 This is a schematic diagram of the membrane absorption tube in this invention;

[0082] Figure 9 This is a schematic diagram of the structure of the bromine extraction tube assembly in this invention;

[0083] Figure 10 This is a schematic diagram of the first structure of the material discharge tank in this invention;

[0084] Figure 11 This is a schematic diagram of the second structure of the material discharge tank in this invention;

[0085] Figure 12 This is a schematic diagram of the structure of the filter membrane tube in this invention;

[0086] Figure 13 This is a photograph of bromine extracted from high-salt wastewater containing bromine in this invention.

[0087] Figure 14 This is a photograph of the raw bromine-containing, high-salt wastewater used in this invention;

[0088] Figure 15 This is a photograph of the oxidized liquid obtained after electrolysis of bromine-containing high-salt wastewater in this invention.

[0089] The markings in the attached diagram are as follows: 100-Metal support; 1001-Discharge area; 101-First placement area; 1011-Discharge tank control equipment; 10111-Gas pressure monitoring display; 10112-Control switch group; 10113-Feed status display screen; 10114-First housing; 1012-Electrolytic cell control equipment; 10121-Electrolytic cell status display screen; 10122-Upper and lower hydraulic control switches; 10123-Electrode control knob; 10124-Electrolyte feed control knob; 10125-Second housing; 1013-Membrane absorber tube control equipment; 10131-Membrane absorber tube pressure display; 10133-Bromine extraction tube control button; 101 34-Membrane absorber tube status display screen; 10135-Third housing; 102-Second placement area; 1021-Fixing frame; 103-Third placement area; 104-External placement area; 200-Electrolytic cell; 201-First electrolytic cell; 20112-Displacement rod; 20113-First motor; 20114-Displacement gear; 2012-Second electrode plate; 20121-Anode electrode block; 2013-Groove; 2014-Feeding pipe; 2016-Liquid outlet; 2017-First liquid outlet tank; 20171-First liquid outlet; 20172-Liquid outlet pipe; 202-Second electrolytic cell; 2022-First electrode plate; 20221-Cathode electrode block; 2024 - Second liquid outlet tank; 20241- Second liquid outlet; 203- Partition plate; 204- Insertion plate; 2041- Insertion groove; 300- Discharge tank; 3001- Tank body; 301- Inlet pipe; 302- Discharge pipe; 303- First sealing layer; 3031- First sealing ring; 304- Sealing cover; 3041- Second sealing ring; 305- Sealing pin; 306- Third motor; 3061- Stirring rod; 3062- Stirring blade; 400- Locking mechanism; 401- Frame; 402- First threaded rod; 4021- First bevel gear; 403- Moving block; 4031- Moving rod; 4032- First locking block; 4033- Magnetic locking block; 404- Second clamping block; 405-Second bevel gear; 4051-Connecting rod; 406-Second motor; 500-Membrane absorption tube assembly; 501-Membrane absorption tube; 5011-Inlet; 502-Controlled temperature chamber; 503-Bromine extraction tube assembly; 5031-Third liquid outlet pipe; 5032-First liquid outlet pipe; 5033-Second liquid outlet pipe; 504-Pipe body; 5041-Heating layer; 5042-Insulation layer; 505-Filter membrane tube; 506-Tube side; 507-Shell side; 600-Bromine storage tank assembly; 601-Bromine storage tank; 701-First feed pipe; 702-Second feed pipe; 703-Third feed pipe; 704-Fourth feed pipe; 705-First gas supply pipe. Detailed Implementation

[0090] The present invention will be further described below with reference to the accompanying drawings and embodiments, but this should not be construed as limiting the present invention.

[0091] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0092] (S01) Take an appropriate amount as follows Figure 14 The bromine-containing high-salt wastewater shown is injected into the electrolytic cell to adjust its pH. The bromide content in the bromine-containing high-salt wastewater is 100 mg / L to 20000 mg / L, and the chloride content is 1000 mg / L to 100000 mg / L. In step (S01), the pH of the bromine-containing high-salt wastewater is adjusted to 8 to 11.

[0093] (S02) After the pH is adjusted in step (S01), perform electro-oxidation. The result after completion is as follows: Figure 15 The oxidation solution shown; the current density for electro-oxidation in step (S02) is 10 A / m. 2 ~300A / m 2 The electro-oxidation time in step (S02) is 30 min to 300 min.

[0094] (S03) The oxidizing liquid from step (S02) is fed into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:3 to 8; the reaction vessel in step (S03) is a discharge tank;

[0095] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 2-4; in step (S04), the reaction time is 20 min-60 min.

[0096] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 45℃~55℃. The flow rate of the bromine-containing solution in the tube side in step (S05) is 4L / h~20L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 10L / h~100L / h. The absorption time in step (S05) is 1h~10h. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 11~15.

[0097] (S06) The bromine-enriched solution in the shell side of step (S05) is transferred to the bromine storage container, and the feed solution in the tube side of step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank group. The debromine-removed solution is as follows: Figure 13The final product water shown can be used directly for industrial production.

[0098] like Figure 1 and Figure 2 The bromine extraction equipment for high-salt bromine-containing wastewater shown includes a metal support 100, inside which are a first placement area 101, a second placement area 102, and a third placement area 103; the first placement area is equipped with a discharge tank control device 1011, an electrolytic cell control device 1012, and a membrane absorption tube control device 1013; the second placement area is equipped with a fixing frame 1021, on which are mounted... Figure 3 , Figure 4 , Figure 5 and Figure 6 The electrolytic cell 200 shown is electrically connected to the electrolytic cell control equipment; a feeding area 1001 is provided inside the metal support, and the feeding area is equipped with... Figure 10 and Figure 11 The discharge tank 300 shown is electrically connected to the discharge tank control equipment and is connected to the drain port of the electrolytic cell through the first conveying pipe 701. A membrane absorption tube assembly 500 is provided in the third placement area. The membrane absorption tube assembly is electrically connected to the membrane absorption tube control equipment and is connected to the discharge tank through the second conveying pipe 702. An alkali tank is provided in the discharge area and is connected to the membrane absorption tube assembly through an alkali pipe. An outer placement area 104 is provided outside the metal support. A bromine storage tank group is provided in the outer placement area and is connected to the membrane absorption tube assembly through the third conveying pipe 703.

[0099] The discharge tank control device includes a first housing 10114, within which a first controller is housed. The first housing is equipped with a pressure monitoring display 10111, a control switch group 10112, and a feed status display 10113. The pressure monitoring display, control switch group, and feed status display are all electrically connected to the first controller. The electrolytic cell control device includes a second housing 10125, within which a second controller is housed. The second housing is equipped with an up / down hydraulic control switch 10122, an electrode control knob 10123, and an electrolyte feed control knob 10114. The electrolytic cell status display screen 10121, the upper and lower hydraulic control switches, the electrode control knob, the electrolyte feed control knob, and the electrolytic cell status display screen are all electrically connected to the second controller; the membrane absorption tube control device includes a third housing 10135, a third controller is installed inside the third housing, and a membrane absorption tube pressure display screen 10131, a bromine extraction tube control button 10133, and a membrane absorption tube status display screen 10134 are installed on the third housing, and the membrane absorption tube pressure display screen, the bromine extraction tube control button, and the membrane absorption tube status display screen are all electrically connected to the third controller.

[0100] An electrolytic cell is equipped with a partition 203, which divides the interior of the electrolytic cell into a first electrolytic cell 201 and a second electrolytic cell 202. Both the first and second electrolytic cells are equipped with adjustable plug-in plates 204, each with multiple plug-in slots 2041 along its outer edge. The plug-in plates are respectively equipped with a first electrode plate 2022 and a second electrode plate 2012, both of which are electrically connected to a second controller. The first electrode plate has several anode electrode blocks 20121, and the second electrode plate has several cathode electrode blocks 20221, all of which are adjusted and positioned within their respective plug-in slots. Both the first and second electrolytic cells are equipped with... Figure 7The toothed groove 2013 shown has a displacement rod 20112 on the plug-in plate, a first motor 20113 on the displacement rod, and a displacement gear 20114 on the drive end of the first motor. The displacement gear meshes with the toothed groove, and the first motor is electrically connected to the second controller. Both the first and second electrolytic cells have a liquid outlet 2016 at the bottom, with an electromagnetic liquid outlet valve electrically connected to the second controller. The anode electrode block is a titanium metal electrode block coated with an alloy composed of ruthenium, iridium, and platinum; the cathode electrode block is also a titanium metal electrode block. Both the first and second electrolytic cells are made of PP material. The pH of the reaction solution in the electrolytic cell is 8–11. Both the first and second electrolytic cells are equipped with a feed pipe 2014, with an electromagnetic feed valve inside, electrically connected to the second controller. The bottom of the first electrolytic cell and the second electrolytic cell are respectively provided with a first outlet tank 2017 and a second outlet tank 2024. The bottom of the first outlet tank and the second outlet tank are respectively provided with a first outlet port 20171 and a second outlet port 20241. Both the first outlet port and the second outlet port are connected to outlet pipes 20172, which are connected to the first feed pipe. A first electromagnetic outlet valve is provided at the first outlet port, and a second electromagnetic outlet valve is provided at the second outlet port. Both the first electromagnetic outlet valve and the second electromagnetic outlet valve are electrically connected to a second controller. Liquid level sensors are provided in both the first outlet tank and the second outlet tank, and the liquid level sensors are electrically connected to the second controller. A first pH sensor is provided in the discharge tank, and the first pH sensor is electrically connected to the first controller. The discharge tank includes a tank body 3001, which is located in the discharge area. The tank body is provided with an inlet pipe 301, an outlet pipe 302, and a liquid injection port. The inlet pipe is connected to the outlet pipe through the first feed pipe, and the outlet pipe is connected to the membrane absorption tube assembly through the second feed pipe. The can body has a first sealing layer 303 at the can opening, and a first sealing ring 3031 on the first sealing layer; a sealing cover 304 is provided at the can opening, one side of which is rotatably connected to the can body via a sealing pin 305, and a second sealing ring 3041 is provided inside the sealing cover; a locking mechanism 400 is provided on the can body. The locking mechanism includes a frame 401, which is set on the can body, and a magnetic snap-fit ​​block 4033 is provided on the frame; a second snap-fit ​​block 404 is provided on the side of the sealing cover away from the sealing pin, and an electromagnet slot is provided on the second snap-fit ​​block, which corresponds to the magnetic snap-fit ​​block and is electrically connected to the first controller. The frame contains a first threaded rod 402, the end of which is rotatably mounted on the inner wall of the frame. A moving block 403 is threadedly connected to the first threaded rod, a moving rod 4031 is mounted on the moving block, and a first locking block 4032 is mounted on the moving rod. A magnetic locking block is mounted on the first locking block. A first bevel gear 4021 is located on the first threaded rod away from the first locking block. A second bevel gear 405 meshes with the first bevel gear, and a connecting rod 4051 is mounted on the second bevel gear. A second motor 406 is mounted on the frame, the drive end of which is connected to the connecting rod, and the second motor is electrically connected to the first controller.The top of the tank is equipped with a third motor 306, and the drive end of the third motor is equipped with a stirring rod 3061. The stirring rod passes through the top of the tank and enters the interior of the tank. The stirring rod is equipped with multiple sets of stirring blades 3062. The third motor is electrically connected to the first controller.

[0101] The membrane absorber assembly includes several such Figure 8 The membrane absorption tube 501 shown has an inlet 5011 at one end, which is connected to the alkali solution pipe and the second feed pipe. An inlet solenoid valve is installed at the inlet and is electrically connected to a third controller. The other end of the membrane absorption tube is connected to a control chamber 502, which contains a hot and cold compression pump, also electrically connected to the third controller. Several [unclear - possibly referring to a series of devices] are connected to the membrane absorption tube. Figure 9 The bromine extraction tube assembly 503 is shown. The membrane absorption tube is a serpentine tube. The bromine extraction tube assembly is located at the bend of the membrane absorption tube.

[0102] The bromine extraction pipe assembly includes a third liquid outlet pipe 5031, a first liquid outlet pipe 5032, and a second liquid outlet pipe 5033; the bromine storage tank group 600 includes several bromine storage tanks 601, with adjacent bromine storage tanks connected by a first gas transmission pipe 705; the third liquid outlet pipe is connected to an external liquid storage tank via a fourth feed pipe 704, and both the first and second liquid outlet pipes are connected to the bromine storage tanks via the third feed pipe. Several bromine storage tanks are arranged side-by-side.

[0103] The membrane absorption tube includes a tube body 504, and the interior of the tube body is provided with, for example, Figure 12 The filter membrane tube 505 shown has an internal tube side 506 and a shell side 507 between it and the tube body. One shell side interface of the membrane absorption tube is connected to the alkali solution tube, and the other shell side interface is connected to the first and second outlet pipes. One tube side interface of the membrane absorption tube is connected to the second feed pipe, and the other tube side interface is connected to the third outlet pipe. The outer wall of the tube body has a heating layer 5041 and an insulation layer 5042 arranged sequentially from the inside out. A first temperature sensor is located at the heating layer and is electrically connected to a third controller. The filter membrane tube is made of polytetrafluoroethylene (PTFE), and the alkali concentration in the alkali solution tank is 0.002 mol / L to 1 mol / L.

[0104] Example 1:

[0105] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0106] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater; in step (S01), adjust the pH of the bromine-containing high-salt wastewater to 8;

[0107] (S02) After the pH is adjusted in step (S01), electro-oxidation is performed, and an oxidized solution is obtained after completion; the current density of electro-oxidation in step (S02) is 10 A / m 2 The electro-oxidation time in step (S02) is 30 min.

[0108] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:3; the reaction vessel in step (S03) is a discharge tank;

[0109] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 2; in step (S04), the reaction time is 20 min;

[0110] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 45°C. The flow rate of the bromine-containing solution in the tube side in step (S05) is 4 L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 10 L / h. The absorption time in step (S05) is 1 h. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 11.

[0111] (S06) The bromine-enriched solution from the shell side in step (S05) is transferred to a bromine storage container, and the feed solution from the tube side in step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank assembly. 50 ml of the final permeate after bromine removal is taken for testing, and the testing technical indicators are as follows:

[0112] 1 Chlorine content (mg / L) 67273.81 70458.20 2 Bromine content (mg / L) 13722.14 832.19 3 Iodine content (mg / L) 69.31 80.11

[0113] Example 2:

[0114] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0115] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater; in step (S01), adjust the pH of the bromine-containing high-salt wastewater to 11;

[0116] (S02) After the pH is adjusted in step (S01), electro-oxidation is performed, and an oxidized solution is obtained after completion; the current density of electro-oxidation in step (S02) is 300 A / m 2 The electro-oxidation time in step (S02) is 300 min.

[0117] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:8; the reaction vessel in step (S03) is a discharge tank;

[0118] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 4; in step (S04), the reaction time is 60 min.

[0119] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 55°C. The flow rate of the bromine-containing solution in the tube side in step (S05) is 20 L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 100 L / h. The absorption time in step (S05) is 10 h. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 15.

[0120] (S06) The bromine-enriched solution from the shell side in step (S05) is transferred to a bromine storage container, and the feed solution from the tube side in step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank assembly. 50 ml of the final permeate after bromine removal is taken for testing, and the testing technical indicators are as follows:

[0121] 1 Chlorine content (mg / L) 67273.81 72843.76 2 Bromine content (mg / L) 13722.14 397.62 3 Iodine content (mg / L) 69.31 82.29

[0122] Example 3:

[0123] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0124] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater; in step (S01), adjust the pH of the bromine-containing high-salt wastewater to 10;

[0125] (S02) After the pH is adjusted in step (S01), electro-oxidation is performed, and an oxidized solution is obtained after completion; the current density of electro-oxidation in step (S02) is 100 A / m 2 The electro-oxidation time in step (S02) is 100 min.

[0126] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:6; the reaction vessel in step (S03) is a discharge tank;

[0127] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 3; in step (S04), the reaction time is 40 min.

[0128] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 50°C. The flow rate of the bromine-containing solution in the tube side in step (S05) is 10 L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 50 L / h. The absorption time in step (S05) is 5 h. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 13.

[0129] (S06) The bromine-enriched solution from the shell side in step (S05) is transferred to a bromine storage container, and the feed solution from the tube side in step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank assembly. 50 ml of the final permeate after bromine removal is taken for testing, and the testing technical indicators are as follows:

[0130] 1 Chlorine content (mg / L) 67273.81 98597.01 2 Bromine content (mg / L) 13722.14 446.81 3 Iodine content (mg / L) 69.31 76.19

[0131] Example 4:

[0132] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0133] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater; in step (S01), adjust the pH of the bromine-containing high-salt wastewater to 8.64;

[0134] (S02) After the pH is adjusted in step (S01), electro-oxidation is performed, and an oxidized solution is obtained after completion; the current density of electro-oxidation in step (S02) is 12.6 A / m 2 The electrolysis voltage is 16.5V; the electro-oxidation time in step (S02) is 40min;

[0135] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:5; the reaction vessel in step (S03) is a discharge tank;

[0136] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 3; in step (S04), the reaction time is 30 min;

[0137] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 50°C. The flow rate of the bromine-containing solution in the tube side in step (S05) is 11.5 L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 33.1 L / h. The absorption time in step (S05) is 3 h. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 13.5.

[0138] (S06) The bromine-enriched solution from the shell side in step (S05) is transferred to a bromine storage container, and the feed solution from the tube side in step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank assembly. 50 ml of the final permeate after bromine removal is taken for testing, and the testing technical indicators are as follows:

[0139] 1 Chlorine content (mg / L) 67273.81 69773.30 2 Bromine content (mg / L) 13722.14 447.03 3 Iodine content (mg / L) 69.31 72.36

[0140] Example 5:

[0141] A method for extracting bromine from high-salt, bromine-containing wastewater includes the following steps:

[0142] (S01) Take an appropriate amount of bromine-containing high-salt wastewater and inject it into the electrolytic cell to adjust the pH of the bromine-containing high-salt wastewater; in step (S01), adjust the pH of the bromine-containing high-salt wastewater to 8.64;

[0143] (S02) After the pH is adjusted in step (S01), electro-oxidation is performed, and an oxidized solution is obtained after completion; the current density of electro-oxidation in step (S02) is 12.6 A / m 2 The electrolysis voltage is 16.5V; the electro-oxidation time in step (S02) is 40min;

[0144] (S03) The oxidizing liquid from step (S02) is sent into the reaction vessel, and an appropriate amount of bromine-containing high-salt wastewater is injected into the reaction vessel again and mixed; the volume ratio of the oxidizing liquid to the bromine-containing high-salt wastewater in step (S03) is 1:5; the reaction vessel in step (S03) is a discharge tank;

[0145] (S04) Adjust the pH of the mixture in step (S03) and stir to obtain a bromine-containing solution; in step (S04), adjust the pH of the mixture to 3; in step (S04), the reaction time is 30 min;

[0146] (S05) The bromine-containing solution from step (S04) is fed into the tube side of the membrane absorption tube assembly, while an alkaline absorbent is simultaneously introduced into the shell side of the membrane absorption tube assembly. After absorption is completed, a bromine-rich solution is obtained. The membrane material in the membrane absorption tube assembly is polytetrafluoroethylene. The membrane absorption temperature in step (S05) is 50°C. The flow rate of the bromine-containing solution in the tube side in step (S05) is 8.68 L / h. The flow rate of the alkaline absorbent in the shell side in step (S05) is 33.1 L / h. The absorption time in step (S05) is 3 hours. The alkaline absorbent in step (S05) is a sodium hydroxide solution. The pH of the sodium hydroxide solution is 13.5.

[0147] (S06) The bromine-enriched solution from the shell side in step (S05) is transferred to a bromine storage container, and the feed solution from the tube side in step (S05) is transferred to an external storage tank; the bromine storage container is a bromine storage tank assembly. 50 ml of the final permeate after bromine removal is taken for testing, and the testing technical indicators are as follows:

[0148] 1 Chlorine content (mg / L) 67273.81 68523.72 2 Bromine content (mg / L) 13722.14 330.48 3 Iodine content (mg / L) 69.31 66.83

[0149] The working process of this invention is as follows:

[0150] Bromine-containing, high-salt wastewater is fed into the first electrolytic cell 201 and the second electrolytic cell 202. The second controller controls the first motor 20113 to adjust the position of the plug-in plate 204 within the electrolytic cell 200, ensuring that the anode electrode block 20121 and the cathode electrode block 20221 achieve a suitable contact area with the wastewater. Electrolytic oxidation is then performed. After electrolytic oxidation, the bromine-containing, high-salt wastewater in the first and second electrolytic cells becomes an oxidized solution containing bromate. The second controller opens the electromagnetic discharge valve, and the oxidized solution from the first and second electrolytic cells enters the first outlet tank 2017 and the second outlet tank 202, respectively. Inside the second outlet tank 2024; the second controller opens the corresponding electromagnetic outlet valve, and the oxidizing liquid is sent into the discharge tank 300. Simultaneously, high-salt bromine-containing wastewater is again added to the discharge tank in proportion, and acid is added and stirred until the pH of the liquid in the discharge tank reaches 3, undergoing a neutralization reaction. After the neutralization reaction is complete, the bromine-containing liquid in the discharge tank is sent to the tube side 506 of the membrane absorption tube 501 through the second feed pipe 702. Simultaneously, sodium hydroxide solution is sent to the shell side 507 of the membrane absorption tube through the alkali pipe. The bromine in the bromine-containing liquid is continuously absorbed by the sodium hydroxide solution, and finally, the sodium hydroxide solution becomes a bromine-rich solution. The bromine-absorbed liquid is sent to an external storage tank through the third outlet pipe 5031 for industrial reuse. The bromine-enriched liquid is sent to a bromine storage tank 601 through the first outlet pipe 5032 and the second outlet pipe 5033 for storage. The electro-oxidation process converts bromide ions in bromine-containing high-salt wastewater into bromate ions. The high-valence bromine in the bromate ions reacts with the low-valence bromine in the bromide ions in a disproportionation reaction, rapidly consuming the bromine in the wastewater and extracting elemental bromine. This process is effective in treating bromide ions in bromine-containing high-salt wastewater and achieves ideal bromine extraction. During electrolytic oxidation... When the process is too fast, the second controller changes the position of the plug plate in the electrolytic cell, reducing the contact area between the anode and cathode electrode blocks and the bromine-containing high-salt wastewater, thus slowing down the electrolysis rate. When the electrolytic oxidation process is too slow, the second controller changes the position of the plug plate in the electrolytic cell, increasing the contact area between the anode and cathode electrode blocks and the bromine-containing high-salt wastewater, thus accelerating the electrolysis rate and increasing the controllability of the electro-oxidation process. The bromine in bromate has a +5 oxidation state, and the bromine in bromide ions has a -1 oxidation state, ensuring that all bromine elements entering the discharge tank for the disproportionation reaction can complete the disproportionation reaction to form elemental bromine.

[0151] The metal support 100 is divided into a first placement area 101, a second placement area 102, a third placement area 103, a discharge area 1001, and an outer placement area 104, providing installation positions for different equipment components. All equipment components are concentrated at the metal support, giving the entire bromine extraction equipment a high degree of integration. The discharge tank control device 1011 can accurately control the inlet, outlet, and reaction conditions at the discharge tank 300, mixing the oxidized liquid converted to bromate and the high-salt bromine-containing wastewater in a predetermined ratio, causing the bromate and bromide ions to undergo a disproportionation reaction, efficiently obtaining bromine-containing wastewater. The electrolytic cell control device 1012 accurately controls the inlet, outlet, and reaction conditions at the electrolytic cell 200, enabling efficient oxidation of bromide ions in the bromide-containing high-salt wastewater to bromate ions. The membrane absorber control device 1013 accurately controls the flow rate of the bromide-containing solution in the tube side 506 of the membrane absorber assembly 500 and the input rate of the alkaline absorbent in the shell side 507, allowing bromine in the bromide-containing solution to diffuse more efficiently through the membrane into the alkaline absorbent. The mounting bracket 1021 provides a stable installation position for the electrolytic cell. The electrolytic cell efficiently electro-oxidizes bromide ions in high-salt wastewater containing bromine to bromate ions. In the discharge tank 300, bromate ions and bromide ions undergo a disproportionation reaction, efficiently producing a bromine-containing solution. The first feed pipe 701 stably delivers the oxidizing solution from the electrolytic cell into the discharge tank 300. The membrane absorption tube assembly efficiently absorbs bromine from the bromine solution using the alkali absorbent. The second feed pipe 702 stably delivers the bromine-containing solution from the discharge tank into the tube side of the membrane absorption tube assembly. The alkali tank is used for the safe storage of the alkali absorbent. The alkali pipe stably delivers the alkali... The absorbent is fed into the shell side of the membrane absorption tube assembly; the external placement area provides a stable placement location for the bromine storage tank group 600; the bromine storage tank group can stably and safely store the obtained bromine-containing enriched liquid; the third feed pipe 703 can stably deliver the bromine-containing enriched liquid in the shell side of the membrane absorption tube assembly into the bromine storage tank group; the whole system has high integration and intelligence, and has a good bromine extraction effect and high bromine extraction efficiency in bromine-containing high-salt wastewater. The obtained bromine-containing enriched liquid can realize the recycling and reuse of bromine resources, and there are no safety hazards or environmental re-pollution risks.

[0152] A pressure sensor is installed inside the discharge tank 300 to monitor the pressure inside the tank in real time. An electromagnetic pressure relief valve is installed on the discharge tank; when the pressure inside the tank is too high, the electromagnetic pressure relief valve opens to release pressure, ensuring the safety of the reaction inside the tank. Both the pressure sensor and the electromagnetic pressure relief valve are electrically connected to the first controller, and the entire system is controlled by the first controller. The control switch group 10112 is used to control the opening and closing of the electromagnetic valves at the liquid inlet and outlet of the discharge tank, rationally controlling the injection volume of oxidizing liquid and bromine-containing high-salt wastewater into the discharge tank, ensuring the efficient conduct of the bromate and bromide ion neutralization reaction. A first feed pump is installed on the first feed pipe 701, and the first feed pump is electrically connected to the first controller; the start and stop of the first feed pump are also controlled by the control switch group. Control: A first pH sensor is installed in the discharge tank, electrically connected to a first controller, to accurately monitor the pH of the mixed solution in the discharge tank and ensure that it remains within a reasonable range, guaranteeing the efficient conduct of the bromate and bromide ion neutralization reaction; a flow meter is installed on the first feed pipe, and a level gauge is installed in the discharge tank. Both the flow meter and the level gauge are electrically connected to the first controller, thereby accurately controlling the injection volume of the oxidizing liquid and bromine-containing high-salt wastewater into the discharge tank. The feed status display screen 10113 can display the injection status and the liquid level in the discharge tank in real time; a hydraulic pump is installed on the liquid input pipeline of the electrolytic cell 200 of this invention, and a flow meter is installed on the input pipeline. Both the hydraulic pump and the flow meter are electrically connected to a second controller, and the hydraulic pump can be controlled to maintain the pH of the mixed solution within the reasonable range, ensuring the efficient conduction of the bromate and bromide ion neutralization reaction; a flow meter is installed on the first feed pipe, and both the flow meter and the second controller are electrically connected to the second controller, thereby controlling the pH of the mixed solution within the discharge tank; a flow meter is installed on the first feed pipe, electrically connected to a first controller, to ensure the efficient conduction of the mixed solution within the discharge tank. The hydraulic pressure of the high-salt, bromine-containing wastewater entering the electrolytic cell is controlled to ensure that the wastewater is at a suitable level. The upper and lower hydraulic control switch 10122 accurately adjusts the injection pressure of the hydraulic pump. The electrode control knob 10123 accurately controls the electrolysis voltage and current density of the electrolytic cell, thus accurately controlling the overall electro-oxidation rate. The electrolyte feed control knob 10124 accurately controls the opening of the solenoid valve for the high-salt, bromine-containing wastewater entering the electrolytic cell, ensuring that the wastewater level is at a suitable height. A level gauge and a second pH sensor are installed in the electrolytic cell, both electrically connected to the second controller for real-time monitoring of the liquid level and pH in the cell. The electrolysis tank status display screen 10121 is used to display parameters such as electrolysis pressure, current density, electrolysis time, liquid level, and pH in real time. A second feed pump is installed at the second feed pipe 702, and an alkali delivery pump is installed at the alkali pipe. Both the second feed pump and the alkali delivery pump are electrically connected to the third controller. The membrane absorption tube pressure display screen 10131 can display the delivery pressure of the second feed pump and the alkali delivery pump in real time, thereby accurately controlling the amount of material entering the membrane absorption tube assembly 500. The bromine extraction tube control button 10133 can control the solenoid valve for liquid entering the membrane absorption tube assembly and the solenoid valve for liquid exiting the membrane absorption tube assembly, thereby controlling the entire bromine extraction progress. A temperature sensor is installed inside the membrane absorption tube assembly, and the temperature sensor is electrically connected to the second controller.The membrane absorption tube status display screen 10134 can display parameters such as liquid flow rate, absorption temperature, and absorption time in the entire membrane absorption tube assembly in real time.

[0153] The partition 203 divides the entire electrolytic cell 200 into a first electrolytic cell 201 and a second electrolytic cell 202. The first and second electrolytic cells are relatively independent and can be used simultaneously or individually, providing a certain degree of selectivity. The plug-in plate 204 is used to adjust the first electrode plate 2022 and the second electrode plate 2012 relative to the electrolytic cell. By adjusting the contact area between the anode electrode block 20121 and the cathode electrode block 20221 and the bromine-containing high-salt wastewater to be electrolyzed, the entire electrolysis process is controlled. The plug-in slot 2041 cooperates with the anode electrode block and the cathode electrode block to prevent the first and second electrode plates from moving left and right on the plug-in plate, ensuring the stability of the electrolysis process. The first and second electrode plates provide installation positions for the anode electrode block and the cathode electrode block, respectively, and provide power conduction. The bromide ions in the bromine-containing high-salt wastewater undergo an oxidation reaction at the anode electrode block to generate bromate, and the bromine-containing wastewater in the electrolytic cell becomes an oxidized liquid containing bromate. The toothed groove 2013 engages with the displacement gear 20114, moving under the driving force of the first motor 20113 to control the position of the plug-in plate within the electrolytic cell. This controls the contact area between the anode and cathode electrode blocks and the bromine-containing high-salt wastewater to be electrolyzed, thus controlling the entire electrolysis process. The end of the displacement rod 20112 extends to the outside of the electrolytic cell, limiting the insertion depth of the plug-in plate within the cell. This prevents the anode and cathode electrode blocks from moving indefinitely downwards and colliding with the bottom of the electrolytic cell, causing damage. It also facilitates manual removal of the plug-in plate for inspection of the first and second electrode plates. The liquid outlet 2016 discharges the oxidizing liquid into the discharge tank 300; the electromagnetic liquid outlet valve regulates the discharge rate of the oxidizing liquid. The titanium metal electrode block, coated with an alloy of ruthenium, iridium, and platinum, serves as the anode electrode block. It works well with the titanium metal cathode electrode block, exhibiting high electrolysis efficiency for bromine-containing high-salt wastewater, as well as high corrosion resistance and acid / alkali resistance, resulting in a long service life. The electrolytic cell body, made of PP material, is corrosion-resistant and insulating, ensuring the safe operation of the entire electrolysis process. Feed pipe 2014 is used to add bromine-containing high-salt wastewater and sodium hydroxide solution to the electrolytic cell; the opening adjustment of the electromagnetic feed valve can accurately control the amount of bromine-containing high-salt wastewater and sodium hydroxide solution added to the electrolytic cell; the feed liquid after bromine absorption in the membrane absorption tube assembly 500 tube side 506 is sent to the external storage tank through the third liquid outlet pipe 5031, and can finally be directly used for industrial production; the first liquid outlet tank 2017 and the second liquid outlet tank 2024 are respectively used to collect the oxidized liquid after electrolysis in the first electrolytic cell and the second electrolytic cell, to ensure that the oxidized liquid sent into the discharge tank is a bromate solution after complete electrolysis; the first liquid outlet 10171 and the second liquid outlet 20241 are respectively used to discharge the collected oxidized liquid in the first liquid outlet tank and the second liquid outlet tank into the discharge tank; the liquid outlet pipe 20172 is used to smoothly send the collected oxidized liquid in the first liquid outlet tank and the second liquid outlet tank into the first feed pipe 701.The first and second electromagnetic discharge valves are used to control the discharge volume in the first and second discharge tanks, respectively. A level sensor is used to monitor the liquid level of the oxidized liquid in the first and second discharge tanks in real time. A first pH sensor accurately monitors the pH of the mixed liquid in the discharge tank, ensuring it remains within a reasonable range and guaranteeing the efficient displacement reaction of bromate and bromide ions.

[0154] The feed pipe 301 is used to smoothly feed the bromine-containing high-salt wastewater and oxidizing liquid into the tank 3001 for mixing and reaction; the discharge pipe 302 is used to smoothly feed the bromine-containing liquid after the neutralization reaction into the tube side 506 of the membrane absorption tube assembly 500; the injection port is used to add hydrochloric acid solution into the tank for pH adjustment. The first sealing layer 303, the first sealing ring 3031, and the second sealing ring 3041 are all made of rubber, which are used to achieve a good seal between the sealing cap 304 and the tank, ensuring the airtightness of the neutralization reaction in the tank; the sealing cap is rotated relative to the top of the tank by the sealing pin 305, which facilitates the opening and sealing of the tank opening at the top of the tank; the locking mechanism 400 is used to achieve a good seal and lock the sealing cap at the tank opening. The electromagnetic locking and unlocking is achieved by using a magnetic snap-fit ​​block 4033 in conjunction with an electromagnet slot, which has the characteristics of strong locking force when locking and quick unlocking force. The entire locking and unlocking is electromagnetically controlled, and both locking and unlocking are relatively quick. The first threaded rod 402 receives the driving force from the second motor 406, enabling the moving block 403 to move up and down. The moving rod 4031, under the up-and-down force of the moving block, drives the magnetic locking block to move up and down. When the magnetic locking block engages with the electromagnet slot, the moving block moves downwards, achieving a good seal at the tank opening. The first locking block 4032 provides an installation position for the magnetic locking block. The first bevel gear 4021 and the second bevel gear 405 cooperate to convert the driving force of the horizontally placed second motor into a vertical rotational force on the first threaded rod. The third motor 306 provides the driving force for the rotation of the stirring rod 3061. The stirring rod drives the stirring blades 3062 to rotate, allowing bromate and bromide ions in the tank to undergo a complete neutralization reaction. The membrane absorption tube 501 is used for the flow of the alkaline absorbent in the shell side 507 and the bromine-containing feed solution in the tube side 506, thereby achieving efficient absorption of bromine from the bromine feed solution by the alkaline absorbent. The inlet is used for the inflow of both the alkaline absorbent and bromine-containing feed solutions. The feed solenoid valve is used to control the feed rate of both the alkaline absorbent and bromine feed solutions. The temperature control chamber 502 is used to regulate the temperature of the membrane absorption tube throughout the absorption process. The hot and cold compressor pump provides power for temperature regulation within the temperature control chamber. The bromine extraction tube assembly 503 is used to stably deliver the bromine-enriched solution after absorption in the shell side to the bromine storage tank group 600, and to deliver the feed solution after bromine absorption in the tube side to the storage tank, with the final product water discharged for industrial production. The serpentine shape of the membrane absorption tube 501 allows for a larger absorption process, ensuring the full absorption and extraction of bromine from the bromine-containing feed solution by the alkaline absorbent.

[0155] The third liquid outlet pipe 5031 is used to send the bromine-absorbed liquid in the tube side 506 of the membrane absorption tube assembly 500 to an external storage tank, which is ultimately used directly for industrial production. A fourth feed pump and a flow meter are installed on the fourth feed pipe, and both the fourth feed pump and the flow meter are electrically connected to the third controller. The first liquid outlet pipe 5032 and the second liquid outlet pipe 5033 are used to stably send the bromine-containing enriched liquid after absorption in the shell side 507 to the bromine storage tank group 600 through the third feed pipe 703. A third feed pump and a flow meter are installed on the third feed pipe, and both the third feed pump and the flow meter are electrically connected to the third controller. The first gas supply pipe 705 connects adjacent bromine storage tanks together, so that the bromine vapor in the bromine storage tank 601 can be mutually ventilated, thereby ensuring the gas pressure stability in the entire bromine storage tank. An electromagnetic pressure relief valve is installed on the bromine storage tank, and the electromagnetic pressure relief valve is electrically connected to the third controller. The filtration membrane tube 505 enables stable delivery of the bromine-containing liquid while simultaneously facilitating the absorption of bromine by the alkaline absorbent. The tube side is used for stable delivery of the bromine-containing liquid, while the shell side is used for stable delivery of the alkaline absorbent. The entire membrane absorption tube 501 has a simple and ingenious design, resulting in good absorption of bromine from the bromine-containing liquid by the alkaline absorbent without causing additional environmental pollution. The heating layer 5041 is connected to a hot and cold compression pump to control the bromine absorption temperature within the tube 504. The insulation layer 5042 prevents heat loss and saves energy. The first temperature sensor monitors the bromine absorption temperature in real time, ensuring optimal bromine absorption.

Claims

1. A bromine extraction device for high-salt, bromine-containing wastewater, characterized by: The device includes a metal support (100), which has a first placement area (101), a second placement area (102), and a third placement area (103) inside. The first placement area includes a discharge tank control device (1011), an electrolytic cell control device (1012), and a membrane absorption tube control device (1013). The second placement area includes a fixing frame (1021) on which an electrolytic cell (200) is mounted, and the electrolytic cell is electrically connected to the electrolytic cell control device. The metal support also includes a discharge area (1001) containing a discharge tank (300). The discharge tank is electrically connected to the discharge tank control equipment, and the discharge tank is connected to the drain port of the electrolytic cell through the first conveying pipe (701); the third placement area is provided with a membrane absorption tube assembly (500), the membrane absorption tube assembly is electrically connected to the membrane absorption tube control equipment, and the membrane absorption tube assembly is connected to the discharge tank through the second conveying pipe (702); the discharge area is provided with an alkali tank, and the alkali tank is connected to the membrane absorption tube assembly through an alkali pipe; the metal support is provided with an external placement area (104), and the external placement area is provided with a bromine storage tank group, and the bromine storage tank group is connected to the membrane absorption tube assembly through the third conveying pipe (703); The discharge tank control device includes a first housing (10114), a first controller is provided inside the first housing, and a pressure monitoring display (10111), a control switch group (10112), and a feeding status display (10113) are provided on the first housing. The pressure monitoring display, the control switch group, and the feeding status display are all electrically connected to the first controller. The electrolytic cell control device includes a second housing (10125), a second controller is provided inside the second housing, and an upper and lower hydraulic control switch (10122), an electrode control knob (10123), an electrolyte feed control knob (10124), and an electrolytic cell status display screen (10121) are provided on the second housing. The upper and lower hydraulic control switch, the electrode control knob, the electrolyte feed control knob, and the electrolytic cell status display screen are all electrically connected to the second controller. The membrane absorption tube control device includes a third housing (10135), a third controller is provided inside the third housing, and a membrane absorption tube pressure display (10131), a bromine extraction tube control button (10133), and a membrane absorption tube status display (10134) are provided on the third housing. The membrane absorption tube pressure display, the bromine extraction tube control button, and the membrane absorption tube status display are all electrically connected to the third controller. The discharge tank includes a tank body (3001) located within the discharge area. The tank body is equipped with an inlet pipe (301), an outlet pipe (302), and a liquid injection port. The inlet pipe is connected to the outlet pipe via a first conveying pipe, and the outlet pipe is connected to the membrane absorption tube assembly via a second conveying pipe. A first sealing layer (303) is provided at the tank opening, and a first sealing ring (3031) is provided on the first sealing layer. A sealing cap (304) is provided at the tank opening, and one side of the sealing cap is sealed... The pin (305) is rotatably connected to the tank body. The sealing cover is provided with a second sealing ring (3041). The tank body is provided with a locking mechanism (400). The locking mechanism includes a frame (401), which is disposed on the tank body. The frame is provided with a magnetic snap block (4033). The sealing cover is provided with a second snap block (404) on the side away from the sealing pin. The second snap block is provided with an electromagnet slot, which corresponds to the magnetic snap block. The electromagnet slot is electrically connected to the first controller. The electrolytic cell is equipped with a partition (203) that divides the interior of the electrolytic cell into a first electrolytic cell (201) and a second electrolytic cell (202). Both the first and second electrolytic cells are equipped with adjustable plug-in plates (204), each with multiple plug-in slots (2041) along its outer edge. The plug-in plates are respectively equipped with a first electrode plate (2022) and a second electrode plate (2012). Both the first and second electrode plates are electrically connected to a second controller. The first electrode plate is equipped with several anode electrode blocks (20121), and the second electrode plate is equipped with several cathode electrode blocks (20221). The anode and cathode electrode blocks are adjusted and positioned within their respective plug-in slots. The anode electrode blocks are titanium metal electrode blocks coated with an alloy composed of ruthenium, iridium, and platinum. The cathode electrode blocks are also titanium metal electrode blocks. Both the first and second electrolytic cells are provided with toothed grooves (2013). The plug-in plate is provided with a displacement rod (20112). The displacement rod is provided with a first motor (20113). The drive end of the first motor is provided with a displacement gear (20114). The displacement gear meshes with the toothed groove. The first motor is electrically connected to the second controller.

2. The bromine extraction equipment for high-salt bromine-containing wastewater according to claim 1, characterized in that: The frame is provided with a first threaded rod (402), the end of which is rotatably mounted on the inner wall of the frame. A moving block (403) is threadedly connected to the first threaded rod. A moving rod (4031) is provided on the moving block. A first locking block (4032) is provided on the moving rod. A magnetic locking block is provided on the first locking block. A first bevel gear (4021) is provided on the first threaded rod away from the first locking block. A second bevel gear (405) meshes with the first bevel gear. A connecting rod (4051) is provided on the second bevel gear. A second motor (406) is provided on the frame. The driving end of the second motor is connected to the connecting rod. The second motor is electrically connected to the first controller. A third motor (306) is provided at the top of the tank. A stirring rod (3061) is provided at the driving end of the third motor. The stirring rod penetrates the top of the tank and enters the interior of the tank. Multiple sets of stirring blades (3062) are provided on the stirring rod. The third motor is electrically connected to the first controller.

3. The bromine extraction equipment for high-salt bromine-containing wastewater according to claim 1, characterized in that: The membrane absorption tube assembly includes several membrane absorption tubes (501), one end of which is provided with a feed inlet (5011), which is connected to an alkali solution tube and a second feed tube respectively. A feed solenoid valve is provided at the feed inlet, which is electrically connected to a third controller. The other end of the membrane absorption tube is connected to a control chamber (502), which is equipped with a hot and cold compression pump, which is electrically connected to the third controller. Several bromine extraction tube assemblies (503) are connected to the membrane absorption tube.

4. The bromine extraction equipment for high-salinity bromine-containing wastewater according to claim 3, characterized in that: The bromine extraction tube assembly includes a third liquid outlet pipe (5031), a first liquid outlet pipe (5032), and a second liquid outlet pipe (5033); the bromine storage tank group (600) includes several bromine storage tanks (601), and adjacent bromine storage tanks are connected by a first gas supply pipe (705); the third liquid outlet pipe is connected to a liquid storage tank through a fourth feed pipe (704), and the first and second liquid outlet pipes are both connected to the bromine storage tanks through the third feed pipe; the membrane absorption tube includes a tube body (504), and a filter membrane tube (505) is provided inside the tube body, and a tube is formed inside the filter membrane tube. The space between the filter membrane tube and the tube body forms a shell side (507); the shell side interface at one end of the membrane absorption tube is connected to the alkali solution tube, and the shell side interface at the other end of the membrane absorption tube is connected to the first liquid outlet pipe and the second liquid outlet pipe; the tube side interface at one end of the membrane absorption tube is connected to the second feed pipe, and the tube side interface at the other end of the membrane absorption tube is connected to the third liquid outlet pipe; the outer wall surface of the tube body is provided with a heating layer (5041) and a heat insulation layer (5042) from the inside to the outside, and a first temperature sensor is provided at the heating layer, and the first temperature sensor is electrically connected to the third controller.

Images