Method and device for recycling bromine triions based on irradiation coupling electric control ion exchange and application

Abstract

The invention relates to the technical field of water treatment, and discloses a method and a device for recycling bromine triions based on irradiation coupling electronic control ion exchange and application, the method comprises the following steps: placing a bromine-containing stock solution in an electronic control ion exchange device which is a single-chamber device, irradiating the bromine-containing stock solution by using gamma rays, bromine ions in the bromine-containing stock solution are oxidized and react to form bromine triions; and then switching on a circuit and applying an oxidation potential to the working electrode to drive the bromine triions to directionally move towards the membrane and adsorb the bromine triions, and selectively recovering the bromine triions. The device comprises a single-chamber reactor, a liquid path system, a gamma-ray irradiation source for the single-chamber reactor, an electrochemical driving system, a two-electrode system with electrodes immersed in a bromine-containing stock solution, and a potential control system.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, specifically a method, apparatus and application for recovering bromide triions based on irradiation-coupled electro-controlled ion exchange. Background Technology

[0002] Electro-controlled ion exchange, as a novel ion recovery technology, has been widely used in the recovery of various anions and cations due to its selective separation and recovery of target ions. It is applied in the recovery of seawater, radioactive wastewater, and other raw material liquids. Driven by an external electric field, it achieves reversible ion insertion and release by applying oxidation or reduction potentials to an electroactive membrane. This technology produces no secondary pollution, the membrane material is regenerable, and it can selectively target ions. Therefore, it has become a key research focus in ion recovery in recent years.

[0003] However, in electro-controlled ion exchange technology, the electric field is the only driving force for ion and electron migration. The oxidation process of bromide ions to bromide triions and the migration process of bromide triions both require electrical energy. That is, the system not only needs to provide the driving force for ion migration, but also needs to provide additional electrical energy for the electrochemical oxidation process of ions. The overall energy consumption is higher, which limits its application range. Therefore, reducing the electrical energy consumption in the electro-controlled ion exchange process has become the focus of research. Summary of the Invention

[0004] To address the problem that in current electro-controlled ion exchange processes, where the electric field is the sole driving force for ion and electron migration, resulting in high energy consumption in the oxidation step and necessitating control of electrical energy consumption, this invention provides a method, apparatus, and application for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange.

[0005] This invention is achieved using the following techniques: This invention provides a method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange, comprising the following steps: a. Irradiation oxidation The bromine-containing stock solution was placed in an electro-controlled ion exchange device with a bromide ion concentration of 0.001–1 M and a volume of 10–30 mL. The electro-controlled ion exchange device was a single-chamber device. The bromine-containing stock solution was irradiated with gamma rays, which were produced by radioactive nuclides. 60 Provided by Co, with an irradiation dose of 3.0 kGy·h -1 The irradiation time is 5~30min, and the bromide ions in the bromine-containing stock solution are oxidized and react to form bromide triions.

[0006] Gamma rays can irradiate water molecules in a solution, causing the water molecules to decompose and generate highly reactive particles, namely hydroxyl radicals. The hydroxyl radicals act on other ions in the solution. By regulating the generation of highly reactive particles, bromide ions are oxidized to elemental bromide, which then combines with bromide ions to form bromide triions.

[0007] b. Migration and Recycling In the electro-controlled ion exchange device, the circuit is turned on and an oxidation potential is applied to the working electrode. The working electrode is loaded with a bromide triion selective adsorption membrane. The oxidation potential is 0~1.0V, which causes the membrane material to lose electrons. In order to maintain the electroneutrality of the membrane electrode, the oxidation potential drives the bromide triion to move directionally to the membrane and be adsorbed. The adsorption time is 1~6h, and bromide triion is selectively recovered.

[0008] Specifically, the working electrode includes a conductive substrate on which a bromide triion selective adsorption membrane is deposited. The bromide triion selective adsorption membrane is made of an electroactive material with an ion-imprinted structure, selected from either bromide triion-imprinted polypyrrole or bismuth oxybromide.

[0009] This invention achieves directional migration of ions by applying a small oxidation potential to the membrane electrode material to drive ion movement. The oxidation of ions and the formation of tribromide ions are achieved by irradiation oxidation in step a. This effectively utilizes the energy of γ-ray radiation in irradiation technology, reducing the electrical energy required for the oxidation of bromide ions. At the same time, compared with the electro-controlled ion exchange technology for bromine recovery, the irradiation-coupled electro-controlled ion exchange technology effectively improves the adsorption capacity of bromide ions.

[0010] The present invention also provides an apparatus for implementing the above-described method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, comprising: A single-chamber reactor is used to contain bromine-containing stock solution; the oxidation reaction of bromide ions, the formation of tribromide ions, and the placement of tribromide ions into the membrane are all completed within it. The liquid circuit system is used to input and output bromine-containing stock solution to the single-chamber reactor; A gamma-ray irradiation source is positioned above the single-chamber reactor to provide gamma-ray irradiation into the single-chamber reactor. An electrochemically driven system includes a two-electrode system in which the electrodes are immersed in a bromine-containing stock solution. The two-electrode system is electrically connected and controlled by a potential control system. The two-electrode system includes a working electrode and a counter electrode. The working electrode includes a conductive substrate, which is selected from carbon paper, carbon cloth, and conductive glass. A bromide triion selective adsorption membrane is deposited on the conductive substrate. The bromide triion selective adsorption membrane is an electroactive material with an ion-imprinted structure, selected from either bromide triion imprinted polypyrrole or bismuth oxybromide. The counter electrode is selected from either a platinum sheet or a graphite rod.

[0011] This invention also provides an application for the recovery of bromide triions based on irradiation-coupled electro-controlled ion exchange, which can be used to recover bromide ions from seawater, radioactive wastewater and raw material liquid.

[0012] Compared with the prior art, the present invention has the following beneficial effects: This application provides a method, apparatus, and application for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange. By coupling irradiation technology and electro-controlled ion exchange technology, the oxidation of bromide ions to tribromide ions is completed using free radicals generated by gamma-ray irradiation. The oxidation of ions is entirely provided by irradiation, and the irradiation energy is adjustable and does not consume electrical energy. The electric field in the system is only used for the directional migration and adsorption of tribromide ions. Compared with traditional electro-controlled ion exchange, which relies on electrical energy to drive both oxidation and migration, the electric field in this invention only provides the driving force required for ion migration, resulting in a small electric field input, which effectively reduces the electrical energy consumed in the oxidation process. The external electric field potential is controllable, and the application range is wide. In the field of water treatment, no external chemical reagents are involved, fundamentally avoiding the problems of residues and secondary pollution caused by the use of chemicals. The process is clean and pollution-free, in line with the concepts of green chemistry and sustainable development.

[0013] The essence of the bromide ion recovery in this invention is the recovery of bromide ions by converting them into bromide triions. Compared with the recovery of bromide ions alone, this invention effectively improves the adsorption capacity of ions, has a high conversion rate, achieves efficient enrichment, and effectively improves the recovery efficiency.

[0014] In summary, this invention overcomes the limitations of single technologies and achieves a "1+1>2" effect through system integration. It demonstrates significant advantages in energy saving, consumption reduction, and environmentally friendly processes, and has important prospects for industrial application. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the device of the present invention.

[0016] Figure 2 The diagram illustrates the principle of recovering bromide triions from bismuth oxybromide removed in situ.

[0017] Figure 3 This is a schematic diagram illustrating the principle of recovering bromide triions from polypyrrole, which is removed in situ. Detailed Implementation

[0018] The specific embodiments of the present invention will be described in detail below. Example 1

[0019] A method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, such as Figure 1 , 2 As shown: Includes the following steps: a. Irradiation oxidation A 1M bromine-containing stock solution was placed in an electro-controlled ion exchange device with a volume of 20 mL. A bismuth oxybromine membrane imprinted with bromide triion was assembled in the radiation-coupled electro-controlled ion exchange device. The irradiation system was turned on, and the bromine-containing stock solution was pre-oxidized by irradiating it with gamma rays for 30 min. The gamma rays were emitted by a radionuclide. 60 Provided by Co, with an irradiation dose of 3.0 kGy·h -1 The process involves irradiating the liquid with gamma rays, causing the bromide ions in the bromine-containing stock solution to be oxidized and react to form bromide triions. The oxidation rate of bromide ions in the bromine-containing stock solution can reach 66.2%~68.5%, and the corresponding bromide triion formation yield is stable at 61.0%~63.8%.

[0020] b. Migration and Recycling In the electrically controlled ion exchange device, the circuit is turned on, and an oxidation potential of 1.0V is applied to the working electrode of the bromide triion selective adsorption membrane. This drives the bromide triions to move directionally towards the membrane and be adsorbed. The adsorption time is 6 hours, completing the adsorption and recovery of bromide triions. The saturated adsorption capacity of the bromide triion-imprinted bismuth oxybromide membrane for bromide triions can reach 128.6~135.2 mg / g. Example 2

[0021] A method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, such as Figure 1 , 2 As shown: Includes the following steps: In step a, the concentration of the bromine stock solution was 0.001 M, and the pre-oxidation treatment time was 10 min. In step b, the oxidation potential was 0.6 V, and the rest were the same as in Example 1. The saturated adsorption capacity of the tribromide-imprinted bismuth oxybromine membrane for tribromide ions reached 60.3~62.2 mg / g. Example 3

[0022] A method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, such as Figure 1 , 3 As shown: Includes the following steps: A tribromide-imprinted polypyrrole membrane was assembled in the electro-controlled ion exchange device. In step a, the concentration of the bromine-containing stock solution was 0.5 M, and the pre-oxidation treatment time was 20 min. In step b, the oxidation potential was 0.8 V, and the rest were the same as in Example 1. The saturated adsorption capacity of the tribromide-imprinted bismuth oxybromide membrane for tribromide ions reached 88.5~91.7 mg / g. Example 4

[0023] A method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, such as Figure 1 , 3 As shown: Includes the following steps: In step a, the concentration of the bromine stock solution was 0.1 M, and the pre-oxidation treatment time was 30 min. In step b, the oxidation potential was 1.0 V, and the rest were the same as in Example 3. The saturated adsorption capacity of the tribromide-imprinted bismuth oxybromine membrane for tribromide ions reached 104.9~107.3 mg / g. Example 5

[0024] A method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange, such as Figure 1 , 3 As shown: Includes the following steps: In step a, the concentration of the bromine stock solution was 1M, and the pre-oxidation treatment time was 5 min. In step b, the oxidation potential was 0V, and the rest were the same as in Example 3. The saturated adsorption capacity of the tribromide-imprinted bismuth oxybromine membrane for tribromide ions reached 13.6~15.8 mg / g.

[0025] The scope of protection claimed by this invention is not limited to the specific embodiments described above. Moreover, for those skilled in the art, this invention can have various modifications and alterations. Any modifications, improvements, and equivalent substitutions made within the concept and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange, characterized in that, Includes the following steps: a. Irradiation oxidation The bromine-containing stock solution is placed in an electrically controlled ion exchange device, which is a single-chamber device. The bromine-containing stock solution is irradiated with γ-rays, and the bromide ions in the bromine-containing stock solution are oxidized and reacted to form bromide triions. b. Migration and Recycling In an electronically controlled ion exchanger, the circuit is switched on and an oxidation potential is applied to the working electrode, driving the tribromide ions to move directionally toward the membrane and be adsorbed, thus selectively recovering the tribromide ions.

2. The method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 1, characterized in that, In step a, the γ-rays are produced by a radioactive nuclide. 60 Provided by Co, with an irradiation dose of 3.0 kGy·h -1 The irradiation time is 5 to 30 minutes.

3. The method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 1, characterized in that, In step a, the concentration of bromide ions in the bromine-containing stock solution is 0.001~1M, and the volume is 10~30mL.

4. The method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 1, characterized in that, In step b, the oxidation potential is 0~1.0V and the adsorption time is 1~6h.

5. The method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 1, characterized in that, The working electrode is loaded with a bromide triion selective adsorption membrane.

6. The method for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 5, characterized in that, The working electrode includes a conductive substrate on which a bromide triion selective adsorption membrane is deposited. The bromide triion selective adsorption membrane is made of an electroactive material with an ion-imprinted structure, selected from either bromide triion-imprinted polypyrrole or bismuth oxybromide.

7. An apparatus for implementing the method for recovering tribromide ions based on irradiation-coupled electro-controlled ion exchange as described in any one of claims 1 to 6, characterized in that, include: A single-chamber reactor for containing bromine-containing stock solution; The liquid circuit system is used to input and output bromine-containing stock solution to the single-chamber reactor; A gamma-ray irradiation source is positioned above the single-chamber reactor to provide gamma-ray irradiation into the single-chamber reactor. An electrochemically driven system includes a two-electrode system in which the electrodes are immersed in a bromine-containing stock solution, the two-electrode system being electrically connected and controlled by a potential control system.

8. The apparatus for recovering tribromide ions based on radiation-coupled electro-controlled ion exchange according to claim 7, characterized in that, The two-electrode system includes a working electrode and a counter electrode. The working electrode includes a conductive substrate, which is selected from carbon paper, carbon cloth, and conductive glass. A bromide triion selective adsorption membrane is deposited on the conductive substrate. The bromide triion selective adsorption membrane is an electroactive material with an ion-imprinted structure, selected from polypyrrole or bismuth oxybromide imprinted with bromide triion. The counter electrode is selected from platinum sheet or graphite rod.

9. An application for the recovery of tribromide ions based on irradiation-coupled electro-controlled ion exchange, characterized in that, It is used for the recovery of bromide ions from seawater, radioactive wastewater, and raw material liquids.

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