A dynamic coordination dechlorination circulating system and method for desulfurization wastewater zirconium salt

Abstract

This invention discloses a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, comprising a zirconium salt acidification unit, a primary coordination unit, an extraction unit, a back-extraction unit, and a zirconium salt regeneration unit connected in sequence. The zirconium salt regeneration unit is connected to the zirconium salt acidification unit. The inlet of the extraction unit is also connected to the extractant acidification unit. A side loop is provided between the primary coordination unit and the extraction unit, on which a dynamic coordination activation circulation unit and an electrically controlled valve assembly are installed. A first online monitoring component is provided at the outlet of the primary coordination unit, and a second online monitoring component is provided at the end of the dynamic coordination activation circulation unit. Each online monitoring component, the dynamic coordination activation circulation unit, and the electrically controlled valve assembly are electrically connected to the same controller. This invention achieves enhanced solution coordination through the dynamic coordination activation circulation unit, and, combined with dual-stage online monitoring and intelligent circulation control, significantly improves the zirconium chloride coordination saturation and dechlorination efficiency.

Description

Technical Field

[0001] This invention relates to the field of advanced treatment technology for desulfurization wastewater, and in particular to a dynamic coordination dechlorination circulation system and method for desulfurization wastewater containing zirconium salts. Background Technology

[0002] Desulfurization wastewater generated during wet desulfurization processes in coal-fired power plants contains high concentrations of chloride ions. Direct discharge of this wastewater causes severe environmental pollution and exacerbates equipment corrosion. Existing desulfurization wastewater treatment technologies, such as sedimentation, coagulation, and biological treatment, have limited effectiveness in removing chloride ions. In recent years, zirconium salt coordination dechlorination technology has attracted attention due to its high selectivity and efficiency. However, in existing technologies, the coordination reaction between chloride and zirconium ions is often incomplete, leading to low dechlorination efficiency and reagent waste. Furthermore, existing systems lack intelligent monitoring and dynamic adjustment capabilities for the coordination process, making it difficult to effectively recycle and regenerate the extractant and zirconium salt, resulting in high operating costs. Summary of the Invention

[0003] The present invention aims to at least partially solve one of the technical problems in the related art.

[0004] To achieve the above objectives, the present invention proposes a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, comprising a zirconium salt acidification unit, a primary coordination unit, an extraction unit, a back-extraction unit, and a zirconium salt regeneration unit connected in sequence, wherein the zirconium salt regeneration unit is connected to the zirconium salt acidification unit. The feed inlet of the extraction unit is also connected to the extractant acidification unit; A side loop is provided on the pipeline connecting the primary coordination unit and the extraction unit. A dynamic coordination activation circulation unit is provided on the side loop. An electrically controlled valve assembly for controlling the on / off state of the side loop is provided on the side loop. The discharge port of the primary coordination unit is connected to a first online monitoring component; the end of the dynamic coordination activation unit is provided with a second online monitoring component; The first online monitoring component, the dynamic coordination activation circulation unit, and the electronically controlled valve component are all electrically or communicatively connected to the same controller.

[0005] This invention introduces a dynamic coordination activation cycle unit, which can significantly improve the coordination saturation of chloride ions and zirconium ions. At the same time, it sets up a dual-stage online detection and cyclic activation mechanism to completely solve the problem of incomplete primary coordination and significantly improve dechlorination efficiency.

[0006] Optionally, the first online monitoring component includes a first total chlorine online detector, a first free chlorine online detector, and a first total zirconium online detector arranged sequentially along the material flow direction; The total chlorine concentration in the outlet solution of the primary coordination unit was measured separately. Free chlorine concentration is Total zirconium concentration is ; The test results are transmitted to the controller via electrical or communication connections.

[0007] Furthermore, the dynamic coordination activation cycle unit includes an ultrasonic activator, a pulse activator, and a microwave activator connected in sequence; the inlet of the ultrasonic activator is connected to the inlet pipe of the side circuit; and the outlet of the microwave activator is connected to the outlet pipe of the side circuit. The ultrasonic activator is equipped with a first intermediate water pump at its outlet; the pulse activator is equipped with a second intermediate water pump at its outlet; and the microwave activator is equipped with a third intermediate water pump at its outlet. The second online monitoring component is installed on the outlet pipe of the microwave activator. The second online monitoring component includes a second total chlorine online detector, a second free chlorine online detector, and a second total zirconium online detector; it respectively detects the total chlorine concentration of the coordination solution after activation. Free chlorine concentration is Total zirconium concentration is .

[0008] Furthermore, the bypass circuit has a return pipe between the outlet pipe and the inlet pipe; The electrically controlled valve assembly includes a first electrically controlled valve disposed at the inlet of the bypass loop, a second electrically controlled valve disposed on the connecting pipe between the primary coordination unit and the extraction unit, a third electrically controlled valve disposed on the reflux pipe, and a fourth electrically controlled valve disposed at the outlet of the bypass loop. The third electrically controlled valve is located upstream of the fourth electrically controlled valve and downstream of the first electrically controlled valve; The second electrically controlled valve is located between the inlet connection and the outlet connection of the bypass circuit.

[0009] Furthermore, the controller is configured with a calculation model and compliance judgment conditions for the first online monitoring component; The calculation model is as follows: Let the coordination index of the primary coordination unit solution be denoted as . ,but, ; The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first and fourth solenoid valves and opens the second solenoid valve to deliver the solution of the primary zirconium chloride coordination unit to the extractor for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard in terms of zirconium chloride coordination, the controller closes the second solenoid valve and opens the first solenoid valve to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

[0010] Furthermore, the controller is configured with a calculation model and compliance judgment conditions for the second online monitoring component; The calculation model is as follows: the coordination index of the primary coordination unit solution is... ,but, ; The criteria for determining compliance include: when When the system is determined to have reached the required level of zirconium chloride coordination, the controller closes the third solenoid valve and opens the fourth solenoid valve to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller will close the fourth solenoid valve and open the third solenoid valve to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

[0011] Furthermore, the zirconium salt acidification unit includes a zirconium salt acidification tank, the inlet of which is connected to a zirconium salt dosing device and a sulfuric acid dosing device, and the outlet of which is connected to a leveling feed pump. The primary coordination unit includes a primary ligand, the inlet of which is connected to the outlet of the coordination feed pump, and the inlet of the primary ligand is also connected to a desulfurization wastewater source; the outlet of the primary coordination unit is connected to an extraction feed pump. The extractant acidification unit includes an extractant acidification tank, the inlet of which is connected to the sulfuric acid dosing device, and the inlet of which is also connected to the extractant dosing device; the outlet of the extractant is connected to an acidified extractant feed pump. The extraction unit includes an extractor, the inlet of which is connected to the outlet of the acidifying extractant feed pump and the outlet of the extraction feed pump; the extractor is also provided with a product water outlet, which is connected to a product water recovery system. The back-extraction unit includes a back-extractor, the inlet of which is connected to the outlet of the extractor, and the inlet of which is also connected to a back-extractant dosing device; the organic phase outlet of the back-extractor is connected to the extractant dosing device; the solid phase outlet of the back-extractor is connected to a zirconium salt delivery pump; and the aqueous phase outlet of the back-extractor is connected to a solution recovery system. The zirconium salt regeneration unit includes a zirconium salt regeneration tank, the inlet of which is connected to the outlet of the zirconium salt conveying pump and the sulfuric acid dosing device; the outlet of the zirconium salt regeneration pipe is connected to the zirconium salt dosing device.

[0012] This invention also provides a method for using a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, comprising the following steps: S1. Sulfuric acid is added to the zirconium salt acidification tank by the sulfuric acid dosing device, and zirconium salt is added to the zirconium salt acidification tank by the zirconium salt dosing device to perform acidification pretreatment on the zirconium salt. The acidified zirconium salt is then mixed with the effluent from the desulfurization wastewater triple tank in a primary coordination reaction to produce a zirconium chloride coordination reaction, forming a zirconium chloride complex, and outputting a zirconium chloride coordination solution. S2. The components of the zirconium chloride coordination solution after primary coordination are analyzed, and the monitoring results are fed back to the controller. The controller calculates the coordination index of the primary coordination unit solution based on the detection results according to the preset calculation model. ,Will Input the criteria for compliance judgment to obtain the next transportation action instruction; when Once the standard is met, the zirconium chloride complex solution is sent to the extraction unit for extraction. when If the standard is not met, the zirconium chloride coordination solution is sent to the dynamic coordination activation cycle unit for enhanced coordination. At the end of the dynamic coordination activation unit, the solution composition is detected again, and the controller calculates the coordination index of the enhanced coordination solution. ; when If the target is met, the enhanced zirconium chloride coordination solution will be sent to the extraction unit. when If the standard is not met, the solution is sent back to the dynamic coordination activation cycle unit for coordination enhancement, and this instruction is repeated until... Meets the standards; S3. Sulfuric acid is added to the extractant acidification unit by the sulfuric acid dosing device to acidify the extractant. After acidification, the extractant is sent to the extraction unit. The acidified extractant reacts with the zirconium chloride complex solution that meets the coordination standard to form zirconium chloride extract. S4, zirconium chloride extract is transported with the solution to the back-extraction unit. The back-extractor uses sodium hydroxide as the back-extraction agent. The sodium chloride solution generated by back-extraction is recovered and reused by the solution recovery device. The generated regenerated extractant is transported from the organic phase outlet to the extractant addition device for reuse. The generated zirconium hydroxide is transported from the solid phase outlet to the zirconium salt regeneration unit via the zirconium salt transfer pump. S5. Sulfuric acid is added to the zirconium salt regeneration unit by the sulfuric acid dosing device to convert zirconium hydroxide into zirconium sulfate, and the generated zirconium sulfate is transported to the zirconium salt dosing device for reuse.

[0013] Furthermore, in S2, the controller internally targets... The calculation model and judgment conditions include: The calculation model is as follows: ; The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first and fourth solenoid valves and opens the second solenoid valve to deliver the solution of the primary zirconium chloride coordination unit to the extractor for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard in terms of zirconium chloride coordination, the controller closes the second solenoid valve and opens the first solenoid valve to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

[0014] Furthermore, in S2, the controller internally targets... The calculation model and judgment conditions include: The calculation model is as follows: ; The criteria for determining compliance include: when When the system is determined to have reached the required level of zirconium chloride coordination, the controller closes the third solenoid valve and opens the fourth solenoid valve to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller will close the fourth solenoid valve and open the third solenoid valve to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

[0015] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

[0016] Beneficial effects of this invention: 1. Improve the coordination efficiency of chloride and zirconium: By introducing a dynamic coordination activation cycle unit and utilizing the multi-field coupling of ultrasound-pulse-microwave, the coordination saturation of chloride ions and zirconium ions can be significantly improved. At the same time, a dual-segment online detection and cycle activation mechanism is set up to completely solve the problem of incomplete primary coordination and significantly improve the dechlorination efficiency.

[0017] 2. Intelligent energy-saving operation: based on coordination index , The system features online intelligent judgment, automatic switching of process flow and cyclic activation mode. It only starts the high-energy-consuming activation unit when the coordination is not up to standard, and immediately switches to the low-energy-consuming extraction process after the standard is met, thus achieving energy-saving and intelligent control. Attached Figure Description

[0018] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments taken in conjunction with the accompanying drawings, wherein: Figure 1 This is a schematic diagram of a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater according to the present invention.

[0019] Explanation of reference numerals in the attached figures: 1. Sulfuric acid dosing device; 2. Zirconium salt acidification tank; 3. Zirconium salt dosing device; 4. Coordination feed pump; 5. Primary coordinate unit; 6. Desulfurization wastewater source; 7. Extraction feed pump; 8. Extractant dosing device; 9. Extractant acidification tank; 10. Acidification extractant feed pump; 11. Dynamic coordination circulation activation unit; 12. Ultrasonic activator; 13. First intermediate water pump; 14. Pulse activator; 15. Second intermediate water pump; 16. Microwave activator; 17. Third intermediate water pump; 18. Extractor; 19. 20. Product water recovery system; 21. Back-extraction agent dosing device; 22. Back-extractor; 23. Solution recovery device; 24. Zirconium salt transfer pump; 25. Zirconium salt regeneration tank; 26. First online total chlorine detector; 27. First online free chlorine detector; 28. First online total zirconium detector; 29. ​​First electric control valve; 30. Second online total chlorine detector; 31. Second online free chlorine detector; 32. Second online total zirconium detector; 33. Third electric control valve; 34. Fourth electric control valve. Detailed Implementation

[0020] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0021] This invention proposes a dynamic coordination dechlorination circulation system for zirconium salts in desulfurization wastewater, as described below. Figure 1 Please provide a detailed explanation.

[0022] A zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater includes a zirconium salt acidification unit, a primary coordination unit, an extraction unit, a back-extraction unit, and a zirconium salt regeneration unit connected in sequence, wherein the zirconium salt regeneration unit is connected to the zirconium salt acidification unit. The feed inlet of the extraction unit is also connected to the extractant acidification unit; A side loop is provided on the pipeline connecting the primary coordination unit and the extraction unit. A dynamic coordination activation circulation unit is provided on the side loop. An electrically controlled valve assembly for controlling the opening and closing of the side loop is provided on the side loop. The discharge port of the primary coordination unit is connected to a first online monitoring component; a second online monitoring component is installed at the end of the dynamic coordination activation unit. The first online monitoring component, the dynamic coordination activation circulation unit, and the electric control valve component are all electrically or communicatively connected to the same controller, which is a PLC controller.

[0023] This invention introduces a dynamic coordination activation cycle unit, which can significantly improve the coordination saturation of chloride ions and zirconium ions. At the same time, it sets up a dual-stage online detection and cyclic activation mechanism to completely solve the problem of incomplete primary coordination and significantly improve dechlorination efficiency.

[0024] In some embodiments, the first online monitoring component includes a first total chlorine online detector 25, a first free chlorine online detector 26, and a first total zirconium online detector 27 arranged sequentially along the material flow direction; The total chlorine concentration in the outlet solution of the primary coordination unit was measured separately. Free chlorine concentration is Total zirconium concentration is ; The test results are transmitted to the controller via electrical or communication connections.

[0025] It should be noted that by setting up the first online total chlorine detector 25, the first online free chlorine detector 26, and the first online total zirconium detector 27, the concentration data of total chlorine, free chlorine, and total zirconium in the primary coordination solution can be acquired in real time and synchronously, providing an accurate online analytical basis for the controller to accurately calculate the coordination index. The joint monitoring of these three parameters can fully reflect the degree of completion of chlorine-zirconium coordination in the system; the difference between total chlorine and free chlorine reflects the amount of coordinated chlorine, while the total zirconium concentration determines the theoretical coordination capacity, thus providing a clear and quantitative basis for determining whether to activate the dynamic coordination activation cycle unit.

[0026] In some embodiments, the dynamic coordination activation cycle unit includes an ultrasonic activator 12, a pulse activator 14, and a microwave activator 16 connected in sequence; the inlet of the ultrasonic activator 12 is connected to the inlet pipe of the side circuit; and the outlet of the microwave activator 16 is connected to the outlet pipe of the side circuit. The ultrasonic activator 12 is equipped with a first intermediate water pump 13 at its outlet; the pulse activator 14 is equipped with a second intermediate water pump 15 at its outlet; and the microwave activator 16 is equipped with a third intermediate water pump 17 at its outlet. The second online monitoring component is installed on the outlet pipe of the microwave activator 16. The second online monitoring component includes a second total chlorine online detector 30, a second free chlorine online detector 31, and a second total zirconium online detector 32; these respectively detect the total chlorine concentration of the activated coordination solution. Free chlorine concentration is Total zirconium concentration is .

[0027] It should be noted that the ultrasonic activator 12 (12), the pulse activator 14 (14), and the microwave activator 16 (16) are connected in series to form an ultrasonic-pulse-microwave multi-field coupled enhanced activation system. Under the synergistic effect of the ultrasonic field, the pulse electric field, and the microwave field, the hydration layer structure wrapped on the surface of zirconium ions can be effectively destroyed at the molecular level, and various low-activity and unstable coordination structures such as low-coordination zirconium chloride complexes, hydroxyzirconium chloride, polymeric zirconium, and basic zirconium salts that already exist in the system can be broken down. This promotes the rapid migration, rearrangement, and saturation coordination of the remaining free chloride ions in the water to the zirconium ion coordination center, thereby significantly improving the coordination saturation. An intermediate water pump is set between each activator to ensure stable delivery and sufficient residence time of the material in the multi-field coupling region; a second online monitoring component is set at the outlet to perform secondary monitoring of the activated coordination liquid and provide closed-loop feedback data for whether the circulation meets the standards.

[0028] In some embodiments, a return pipe is provided between the outlet pipe and the inlet pipe in the bypass circuit; The electronically controlled valve assembly includes a first electronically controlled valve 28 located at the inlet of the bypass circuit, a second electronically controlled valve 29 located on the connecting pipe between the primary coordination unit and the extraction unit, a third electronically controlled valve 33 located on the reflux pipe, and a fourth electronically controlled valve 34 located at the outlet of the bypass circuit. The third solenoid valve 33 is located upstream of the fourth solenoid valve 34 and downstream of the first solenoid valve 28; The second electrically controlled valve 29 is located between the inlet connection and the outlet connection of the bypass circuit.

[0029] Understandably, by setting up reflux pipes and corresponding electrically controlled valve components, a process flow that can be repeatedly activated and enhanced in coordination can be constructed.

[0030] When the second online monitoring component at the outlet of the dynamic coordination activation circulation unit determines that the coordination is still not up to standard, the controller can close the fourth solenoid valve 34 and open the third solenoid valve 33, allowing the material to return to the inlet of the side loop via the reflux pipe and re-enter the dynamic coordination activation circulation unit for secondary or even multiple enhancement treatments until the coordination index meets the requirements. This loop design avoids substandard material directly entering the extraction unit and affecting the extraction efficiency, while also eliminating the need for additional buffer equipment and resulting in a compact structure.

[0031] In some embodiments, the controller is configured with a calculation model and compliance judgment conditions for the first online monitoring component; The calculation model is as follows: Let the coordination index of the primary coordination unit solution be denoted as . ,but, ; The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first solenoid valve 28 and the fourth solenoid valve 34, opens the second solenoid valve 29, and delivers the solution of the primary zirconium chloride coordination unit to the extractor 18 for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard due to insufficient zirconium chloride coordination, the controller closes the second solenoid valve 29 and opens the first solenoid valve 28 to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

[0032] It should be noted that the controller uses the coordination index to perform online quantitative evaluation of the primary coordination results. The obtained value directly reflects the proportion of effectively coordinated chloride ions to the theoretical maximum coordination capacity. When When the primary coordination has reached a high degree of completion, fully meeting the requirements for subsequent extraction, the controller closes the first solenoid valve 28 and the fourth solenoid valve 34, cutting off the path to the dynamic coordination activation cycle unit. Simultaneously, the second solenoid valve 29 is opened to directly feed the material to the extractor 18 and the activation unit is closed, and the system operates in the lowest energy consumption mode. When the primary coordination reaction is incomplete, a large number of free chloride ions are not effectively coordinated. The controller automatically switches the path and introduces the material into the dynamic coordination activation cycle unit for enhanced treatment to ensure sufficient coordination and avoid waste of reagents and failure to meet dechlorination standards.

[0033] In some embodiments, the controller is configured with a calculation model and compliance judgment conditions for the second online monitoring component; The calculation model is as follows: the coordination index of the primary coordination unit solution is... ,but, ; The criteria for determining compliance include: when When the system is determined to have reached the required level of zirconium chloride coordination, the controller closes the third solenoid valve 33 and opens the fourth solenoid valve 34 to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller closes the fourth solenoid valve 34 and opens the third solenoid valve 33 to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

[0034] It should be noted that the controller calculates the activated coordination index based on real-time data from the second online monitoring component, which serves as the criterion for determining the enhanced coordination effect. When When the multi-field coupling activation has been completed, the controller opens the fourth electronic control valve 34 to send the qualified complex solution into the extractor 18 to ensure the quality of the extraction feed. when If the target coordination degree is not reached even after one activation, the controller automatically closes the fourth solenoid valve 34 and opens the third solenoid valve 33, and uses the return pipeline to send the material back to the dynamic coordination activation cycle unit for circulation processing, forming a closed-loop control of cycle detection and judgment, until the coordination meets the standard before it is allowed to enter the extraction process.

[0035] This mechanism ensures that the complexing solution entering the extraction unit always meets the requirement of high complexing saturation under various water quality fluctuations, while repeated activation is only required when necessary, thus balancing treatment reliability and energy efficiency.

[0036] In some embodiments, the zirconium acidification unit includes a zirconium acidification tank 2, the inlet of the zirconium acidification tank 2 is connected to a zirconium salt addition device 3 and a sulfuric acid addition device 1, and the outlet of the zirconium acidification tank 2 is connected to a proportioning feed pump 4. The primary coordination unit includes a primary coordination device 5. The inlet of the primary coordination device 5 is connected to the outlet of the coordination feed pump 4. The inlet of the primary coordination device 5 is also connected to a desulfurization wastewater source 6. The desulfurization wastewater source 6 uses the effluent from the desulfurization wastewater triple tank. The outlet of the primary coordination unit is connected to an extraction feed pump 7. The extractant acidification unit includes an extractant acidification tank 9, the inlet of which is connected to the sulfuric acid dosing device 1, and the inlet of the extractant acidification tank 9 is also connected to the extractant dosing device 8; the outlet of the extractant is connected to the acidified extractant feed pump 10. The extraction unit includes an extractor 18, the inlet of which is connected to the outlet of the acidifying extractant feed pump 10 and the outlet of the extraction feed pump 7; the extractor 18 is also provided with a product water outlet, which is connected to a product water recovery system 19. The back-extraction unit includes a back-extractor 21, the inlet of which is connected to the outlet of the extractor 18. The inlet of the back-extractor 21 is also connected to a back-extractant dosing device 20. The organic phase outlet of the back-extractor 21 is connected to the extractant dosing device 8. The solid phase outlet of the back-extractor 21 is connected to a zirconium salt transfer pump 23. The aqueous phase outlet of the back-extractor 21 is connected to a solution recovery system. The stripping agent in the stripping agent dosing device 20 is sodium hydroxide; The zirconium salt regeneration unit includes a zirconium salt regeneration tank 24, the inlet of which is connected to the outlet of the zirconium salt conveying pump and the sulfuric acid dosing device 1; the outlet of the zirconium salt regeneration pipe is connected to the zirconium salt dosing device 3.

[0037] By connecting the aforementioned functional devices, a complete process interface is constructed, sequentially completing zirconium salt acidification, primary coordination, intelligent enhanced coordination, extraction, back-extraction, and zirconium salt regeneration. The zirconium salt acidification tank 2 performs acidification pretreatment on the zirconium salt, ensuring it enters the primary coordinater 5 in a highly active ionic form, thus increasing the initial coordination reaction rate. The extractant acidification tank 9 simultaneously completes the acidification and activation of the extractant, ensuring efficient contact with the qualified coordination solution in the extractor 18. The back-extractor 21 uses sodium hydroxide for back-extraction, decomposing the zirconium chloride extractant in the organic phase and recovering the regenerated extractant, sodium chloride solution, and zirconium hydroxide solid phase. The regenerated extractant is returned to the extractant dosing device 8, and the regenerated zirconium sulfate solution is transported to the zirconium salt dosing device 3, achieving a closed-loop recycling of the extractant and zirconium salt throughout the entire process, with no waste reagent discharge, significantly reducing operating costs.

[0038] In some embodiments, a stirring mechanism is provided in the zirconium salt acidification tank 2, the primary ligand 5, the extractant acidification tank 9, the extractor 18, the back-extractor 21, and the zirconium salt regeneration tank 24.

[0039] The stirring mechanism ensures uniform mixing of materials in each reactor, avoiding side reactions or incomplete reactions caused by local concentration differences. In particular, in the primary ligand 5 and extractor 18, sufficient stirring can enhance the mass transfer process between zirconium ions and chloride ions, and between the extract and the organic phase, thereby improving the reaction rate and conversion efficiency. In the back-extractor 21, appropriate stirring helps the back-extraction reaction to proceed fully and promotes the separation of the three phases.

[0040] This invention also provides a method for using a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, comprising the following steps: S1. Sulfuric acid is added to zirconium salt acidification tank 2 by sulfuric acid dosing device 1, and zirconium salt is added to zirconium salt acidification tank 2 by zirconium salt dosing device 3. The zirconium salt is pretreated by acidification, and the acidified zirconium salt is mixed with the effluent from the desulfurization wastewater triple tank for primary coordination mixing, resulting in chlorine-zirconium coordination reaction, forming chlorine-zirconium complex, and outputting chlorine-zirconium coordination solution. S2. The components of the zirconium chloride coordination solution after primary coordination are analyzed, and the monitoring results are fed back to the controller. The controller calculates the coordination index of the primary coordination unit solution based on the detection results according to the preset calculation model. ,Will Input the criteria for compliance judgment to obtain the next transportation action instruction; when Once the standard is met, the zirconium chloride complex solution is sent to the extraction unit for extraction. when If the standard is not met, the zirconium chloride coordination solution is sent to the dynamic coordination activation cycle unit for enhanced coordination. At the end of the dynamic coordination activation unit, the solution composition is detected again, and the controller calculates the coordination index of the enhanced coordination solution. ; when If the target is met, the enhanced zirconium chloride coordination solution will be sent to the extraction unit. when If the standard is not met, the solution is sent back to the dynamic coordination activation cycle unit for coordination enhancement, and this instruction is repeated until... Meets the standards; S3. Sulfuric acid is added to the extractant acidification unit by the sulfuric acid dosing device 1 to acidify the extractant. After acidification, the extractant is sent to the extraction unit. The acidified extractant reacts with the zirconium chloride complex solution that meets the coordination standard to form zirconium chloride extract. S4. The zirconium chloride extract is transported to the back-extraction unit along with the solution. The back-extractor 21 uses sodium hydroxide as the back-extraction agent. The sodium chloride solution generated by back-extraction is recovered and reused by the solution recovery device 22. The generated regenerated extractant is transported from the organic phase outlet to the extractant addition device 8 for reuse. The generated zirconium hydroxide is transported from the solid phase outlet to the zirconium salt regeneration unit via the zirconium salt transfer pump 23. S5. Sulfuric acid is added to the zirconium salt regeneration unit by the sulfuric acid dosing device 1 to convert zirconium hydroxide into zirconium sulfate, and the generated zirconium sulfate is transported to the zirconium salt dosing device 3 for reuse.

[0041] In some embodiments, S2, the controller is configured to... The calculation model and judgment conditions include: The calculation model is as follows: ; The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first solenoid valve 28 and the fourth solenoid valve 34, opens the second solenoid valve 29, and delivers the solution of the primary zirconium chloride coordination unit to the extractor 18 for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard due to insufficient zirconium chloride coordination, the controller closes the second solenoid valve 29 and opens the first solenoid valve 28 to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

[0042] By incorporating a coordination index calculation model and compliance criteria into the controller, the system can monitor the completion quality of primary coordination in real time and automatically determine the material flow direction. When this occurs, it indicates that most of the free chlorine has been coordinated and directly enters the extraction process. Simultaneously, the energy-intensive dynamic coordination activation circulation unit is shut down to minimize energy consumption. If the signal is insufficient, the activation and enhancement pathway is immediately initiated to ensure that the material entering the extraction process is always in a state of high coordination saturation. This avoids waste of extractant and substandard dechlorination caused by insufficient coordination. This intelligent switching mechanism enables the system to dynamically optimize operating energy consumption while ensuring processing effectiveness.

[0043] In some embodiments, S2, the controller is configured to... The calculation model and judgment conditions include: The calculation model is as follows: ; The criteria for determining compliance include: when When the system is determined to be in the correct zirconium chloride coordination, the controller closes the third solenoid valve 33 and opens the fourth solenoid valve 34 to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller closes the fourth solenoid valve 34 and opens the third solenoid valve 33 to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

[0044] The introduction of a second online monitoring component creates a closed-loop feedback mechanism for the activation effect. Based on the enhanced coordination index, the controller automatically determines whether another activation cycle is needed. At that time, the high coordination requirements have been met, and the material directly enters the extraction process; when If necessary, the system utilizes a return pipeline to circulate back to the dynamic coordination activation circulation unit, continuing multi-field coupling enhancement until the target is met. This closed-loop control strategy of cyclic detection and judgment ensures that regardless of fluctuations in the influent water quality, the coordination index of the coordination solution ultimately entering the extractor 18 remains constant. This provides a reliable guarantee for subsequent efficient extraction and dechlorination; at the same time, by limiting the number of cycles and condition triggering, unnecessary continuous cycles are avoided, thus balancing treatment effect and system energy efficiency.

[0045] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0046] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0047] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0048] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, "above," "over," and "on top" of the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.

[0049] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0050] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, characterized in that, It includes a zirconium salt acidification unit, a primary coordination unit, an extraction unit, a back-extraction unit, and a zirconium salt regeneration unit connected in sequence, wherein the zirconium salt regeneration unit is connected to the zirconium salt acidification unit; The feed inlet of the extraction unit is also connected to the extractant acidification unit; A side loop is provided on the pipeline connecting the primary coordination unit and the extraction unit. A dynamic coordination activation circulation unit is provided on the side loop. An electrically controlled valve assembly for controlling the on / off state of the side loop is provided on the side loop. The discharge port of the primary coordination unit is connected to a first online monitoring component; the end of the dynamic coordination activation unit is provided with a second online monitoring component; The first online monitoring component, the dynamic coordination activation circulation unit, and the electronically controlled valve component are all electrically or communicatively connected to the same controller.

2. The desulfurization wastewater zirconium salt dynamic coordination dechlorination circulation system as described in claim 1, characterized in that, The first online monitoring component includes a first total chlorine online detector, a first free chlorine online detector, and a first total zirconium online detector arranged sequentially along the material flow direction; The total chlorine concentration in the outlet solution of the primary coordination unit was measured separately. Free chlorine concentration is Total zirconium concentration is ; The test results are transmitted to the controller via electrical or communication connections.

3. The desulfurization wastewater zirconium salt dynamic coordination dechlorination circulation system as described in claim 2, characterized in that, The dynamic coordination activation cycle unit includes an ultrasonic activator, a pulse activator, and a microwave activator connected in sequence; the inlet of the ultrasonic activator is connected to the inlet pipe of the side circuit; and the outlet of the microwave activator is connected to the outlet pipe of the side circuit. The ultrasonic activator is equipped with a first intermediate water pump at its outlet; the pulse activator is equipped with a second intermediate water pump at its outlet; and the microwave activator is equipped with a third intermediate water pump at its outlet. The second online monitoring component is installed on the outlet pipe of the microwave activator. The second online monitoring component includes a second total chlorine online detector, a second free chlorine online detector, and a second total zirconium online detector; it respectively detects the total chlorine concentration of the coordination solution after activation. Free chlorine concentration is Total zirconium concentration is .

4. The desulfurization wastewater zirconium salt dynamic coordination dechlorination circulation system as described in claim 3, characterized in that, The bypass circuit has a return pipe between the outlet pipe and the inlet pipe; The electrically controlled valve assembly includes a first electrically controlled valve disposed at the inlet of the bypass loop, a second electrically controlled valve disposed on the connecting pipe between the primary coordination unit and the extraction unit, a third electrically controlled valve disposed on the reflux pipe, and a fourth electrically controlled valve disposed at the outlet of the bypass loop. The third electrically controlled valve is located upstream of the fourth electrically controlled valve and downstream of the first electrically controlled valve; The second electrically controlled valve is located between the inlet connection and the outlet connection of the bypass circuit.

5. The desulfurization wastewater zirconium salt dynamic coordination dechlorination circulation system as described in claim 4, characterized in that, The controller is configured with a calculation model and compliance judgment conditions for the first online monitoring component; The calculation model is as follows: Let the coordination index of the primary coordination unit solution be denoted as . ,but, ； The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first and fourth solenoid valves and opens the second solenoid valve to deliver the solution of the primary zirconium chloride coordination unit to the extractor for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard in terms of zirconium chloride coordination, the controller closes the second solenoid valve and opens the first solenoid valve to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

6. The desulfurization wastewater zirconium salt dynamic coordination dechlorination circulation system as described in claim 4, characterized in that, The controller is equipped with a calculation model and compliance judgment conditions for the second online monitoring component; The calculation model is as follows: the coordination index of the primary coordination unit solution is... ,but, ； The criteria for determining compliance include: when When the system is determined to have reached the required level of zirconium chloride coordination, the controller closes the third solenoid valve and opens the fourth solenoid valve to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller will close the fourth solenoid valve and open the third solenoid valve to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

7. A zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater as described in any one of claims 1-6, characterized in that, The zirconium salt acidification unit includes a zirconium salt acidification tank, the inlet of which is connected to a zirconium salt dosing device and a sulfuric acid dosing device, and the outlet of which is connected to a balancing feed pump. The primary coordination unit includes a primary ligand, the inlet of which is connected to the outlet of the coordination feed pump, and the inlet of the primary ligand is also connected to a desulfurization wastewater source; the outlet of the primary coordination unit is connected to an extraction feed pump. The extractant acidification unit includes an extractant acidification tank, the inlet of which is connected to the sulfuric acid dosing device, and the inlet of which is also connected to the extractant dosing device; the outlet of the extractant is connected to an acidified extractant feed pump. The extraction unit includes an extractor, the inlet of which is connected to the outlet of the acidifying extractant feed pump and the outlet of the extraction feed pump; the extractor is also provided with a product water outlet, which is connected to a product water recovery system. The back-extraction unit includes a back-extractor, the inlet of which is connected to the outlet of the extractor, and the inlet of which is also connected to a back-extractant dosing device; the organic phase outlet of the back-extractor is connected to the extractant dosing device; the solid phase outlet of the back-extractor is connected to a zirconium salt delivery pump; and the aqueous phase outlet of the back-extractor is connected to a solution recovery system. The zirconium salt regeneration unit includes a zirconium salt regeneration tank, the inlet of which is connected to the outlet of the zirconium salt conveying pump and the sulfuric acid dosing device; the outlet of the zirconium salt regeneration pipe is connected to the zirconium salt dosing device.

8. A method for using a zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater, characterized in that, Includes the following steps: S1. Sulfuric acid is added to the zirconium salt acidification tank by the sulfuric acid dosing device, and zirconium salt is added to the zirconium salt acidification tank by the zirconium salt dosing device to perform acidification pretreatment on the zirconium salt. The acidified zirconium salt is then mixed with the effluent from the desulfurization wastewater triple tank in a primary coordination reaction to produce a zirconium chloride coordination reaction, forming a zirconium chloride complex, and outputting a zirconium chloride coordination solution. S2. The components of the zirconium chloride coordination solution after primary coordination are analyzed, and the monitoring results are fed back to the controller. The controller calculates the coordination index of the primary coordination unit solution based on the detection results according to the preset calculation model. ,Will Input the criteria for compliance judgment to obtain the next transportation action instruction; when Once the standard is met, the zirconium chloride complex solution is sent to the extraction unit for extraction. when If the standard is not met, the zirconium chloride coordination solution is sent to the dynamic coordination activation cycle unit for enhanced coordination. At the end of the dynamic coordination activation unit, the solution composition is detected again, and the controller calculates the coordination index of the enhanced coordination solution. ; when If the target is met, the enhanced zirconium chloride coordination solution will be sent to the extraction unit. when If the standard is not met, the solution is sent back to the dynamic coordination activation cycle unit for coordination enhancement, and this instruction is repeated until... Meets the standards; S3. Sulfuric acid is added to the extractant acidification unit by the sulfuric acid dosing device to acidify the extractant. After acidification, the extractant is sent to the extraction unit. The acidified extractant reacts with the zirconium chloride complex solution that meets the coordination standard to form zirconium chloride extract. S4, zirconium chloride extract is transported with the solution to the back-extraction unit. The back-extractor uses sodium hydroxide as the back-extraction agent. The sodium chloride solution generated by back-extraction is recovered and reused by the solution recovery device. The generated regenerated extractant is transported from the organic phase outlet to the extractant addition device for reuse. The generated zirconium hydroxide is transported from the solid phase outlet to the zirconium salt regeneration unit via the zirconium salt transfer pump. S5. Sulfuric acid is added to the zirconium salt regeneration unit by the sulfuric acid dosing device to convert zirconium hydroxide into zirconium sulfate, and the generated zirconium sulfate is transported to the zirconium salt dosing device for reuse.

9. The method of using the zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater as described in claim 8, characterized in that, In S2, the controller internally targets... The calculation model and judgment conditions include: The calculation model is as follows: ； The criteria for determining compliance include: when When the system is determined to have met the zirconium chloride coordination standard, the controller closes the first and fourth solenoid valves and opens the second solenoid valve to deliver the solution of the primary zirconium chloride coordination unit to the extractor for extraction reaction, while simultaneously closing the dynamic coordination activation circulation unit. when If the primary coordination system is found to be substandard in terms of zirconium chloride coordination, the controller closes the second solenoid valve and opens the first solenoid valve to transport the solution from the primary zirconium chloride coordination unit to the dynamic coordination activation circulation unit.

10. The method of using the zirconium salt dynamic coordination dechlorination circulation system for desulfurization wastewater as described in claim 8, characterized in that, In S2, the controller internally targets... The calculation model and judgment conditions include: The calculation model is as follows: ； The criteria for determining compliance include: when When the system is determined to have reached the required level of zirconium chloride coordination, the controller closes the third solenoid valve and opens the fourth solenoid valve to deliver the enhanced coordination solution to the extraction unit for extraction reaction. when If the system is found to have insufficient zirconium chloride coordination, the controller will close the fourth solenoid valve and open the third solenoid valve to deliver the enhanced coordination solution to the dynamic coordination activation circulation unit for further enhanced coordination until the standard is met.

Images