Novel vanadium battery electrolyte continuous production line

Abstract

The novel vanadium battery electrolyte continuous production line comprises an electrochemical reaction device, a positive electrode liquid storage tank, a negative electrode liquid storage tank, a reducing agent preparation feeding tank group, a reducing agent temporary storage tank, a reaction liquid storage tank, a solution preparation feeding tank group, an adjusting liquid storage tank, a solution adjusting feeding tank group, a finished product liquid storage tank and a finished product filling and weighing device. On the basis of a technical route for preparing the electrolyte by a reduction method, the raw materials can be high-purity V2O5 powder, high-purity NH4VO3 powder, VO2SO4 crystals and the like, and can also be a vanadium electrolyte solution of which the valence state is higher than 3.5, so that the method has the characteristics of high raw material adaptability and wide application range; the reducing agent of the production line is only the low-valence vanadium electrolyte, other elements are not introduced, the purity of the vanadium electrolyte is guaranteed, the reducing agent is produced by the production line, and the reducing agent does not need to be additionally supplemented except one-time adding of the reducing agent in the initial starting stage; the production line also has the characteristics of high production speed, good production stability, stable product quality, continuous production, easiness in operation and manpower and material resource saving.

Description

Technical Field

[0001] This invention belongs to the field of energy storage flow battery electrolyte production technology, and in particular relates to a novel continuous production line for vanadium battery electrolyte. Background Technology

[0002] Vanadium redox flow batteries (VRBs) are characterized by intrinsic safety, long charge-discharge cycle life, recyclable electrolyte, good life-cycle economics, and environmental friendliness. They are considered one of the best choices for high-power, high-capacity, and long-term energy storage technologies in the industry. The electrolyte is the core component of a vanadium battery and also serves as its energy storage medium.

[0003] Currently, the main production methods for vanadium battery electrolytes include the following: ① Reduction Method for Electrolyte Preparation: In the reduction method for preparing vanadium battery electrolytes, vanadium pentoxide (V₂O₅) or ammonium metavanadate (NH₄VO₃) are typically used as raw materials. Since both have poor solubility in sulfuric acid solution, a reducing agent (such as inorganic reagents like oxalic acid, ethanol, tartaric acid, formic acid, acetic acid, or inorganic gases like H₂S, SO₂, H₂, CO) needs to be added, along with heating treatment. This utilizes a redox reaction to dissolve vanadium ions and prepare the electrolyte. The electrolyte prepared using this method is usually in a tetravalent state, requiring an electrolytic cell stack to reduce the valence state to 3.5. Although this technology for preparing vanadium battery electrolytes is relatively mature, the added reducing agent can easily leave residues, thus affecting the quality of the finished electrolyte.

[0004] ② Electrolytic preparation of electrolyte: In an electrolytic cell, a suspension of vanadium pentoxide (V₂O₅) or ammonium metavanadate (NH₄VO₃) with sulfuric acid is used as the negative electrode reaction solution, and the sulfuric acid solution is used as the positive electrode reaction solution. Direct current is passed through, causing vanadium ions to undergo a redox reaction on the electrode surface, resulting in electrolysis at the negative electrode and the production of a 3.5-valent vanadium electrolyte. However, this method suffers from drawbacks such as large side reactions, low electrolysis efficiency, and high energy consumption.

[0005] ③ Extraction method for preparing electrolyte: This method utilizes a vanadium-containing solution to prepare vanadium electrolyte in a short process. A specific extractant is added to the vanadium-containing solution, causing vanadium ions to selectively transfer to the extract phase. After back-extraction and other operations, the vanadium ions are transferred to the back-extraction solution. Further processing yields the vanadium electrolyte, which is then electrolyzed to obtain a 3.5-valent vanadium electrolyte. However, this method results in a low vanadium concentration in the vanadium-containing solution, which also contains significant amounts of metallic impurities such as iron, manganese, aluminum, copper, calcium, and potassium, as well as non-metallic impurities such as silicon. Complete removal of these impurities is difficult, and extractant residues are unavoidable during the extraction and back-extraction processes. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a novel continuous production line for vanadium battery electrolytes. Based on a reduction method for electrolyte preparation, the raw materials can be high-purity V₂O₅ powder, high-purity NH₄VO₃ powder, VO₂SO₄ crystals, etc., or vanadium electrolyte solutions with a valence state higher than 3.5, exhibiting high raw material adaptability and a wide range of applications. The reducing agent in this production line is only a low-valence vanadium electrolyte, without introducing other elements, ensuring the purity of the vanadium electrolyte. The reducing agent is produced by the production line and requires no additional replenishment except for a single addition during the initial start-up phase. This production line also features high production speed, good production stability, stable product quality, continuous production, easy operation, and savings in manpower and resources.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: a novel continuous production line for vanadium battery electrolyte, comprising a reducing agent preparation area, a reducing agent temporary storage area, a solution preparation area, a solution conditioning area, and a finished product filling area; the reducing agent preparation area is equipped with an electrochemical reaction device, a positive electrode storage tank, a negative electrode storage tank, and a reducing agent preparation feeding tank group; the reducing agent temporary storage area is equipped with a reducing agent temporary storage tank; the solution preparation area is equipped with a reaction storage tank and a solution preparation feeding tank group; the solution conditioning area is equipped with a conditioning storage tank and a solution conditioning feeding tank group; the finished product filling area is equipped with a finished product storage tank and a finished product filling weighing device; the positive electrode storage tank is connected to the positive electrode of the electrochemical reaction device through a circulation pipeline; the negative electrode storage tank is connected to the negative electrode of the electrochemical reaction device through a circulation pipeline; the positive electrode storage tank and... The filling port of the negative electrode storage tank is connected to the reducing agent preparation feeding tank group via pipeline; the drain port of the negative electrode storage tank is connected to the inlet of the reducing agent temporary storage tank via pipeline; the drain port of the reducing agent temporary storage tank has two outputs, one connected to the inlet of the reaction storage tank via pipeline, and the other connected to the solution conditioning feeding tank group via pipeline; the filling port of the reaction storage tank is connected to the solution preparation feeding tank group via pipeline, and the drain port of the reaction storage tank has two outputs, one connected to the inlet of the conditioning storage tank via pipeline, and the other connected to the reducing agent replenishment port of the negative electrode storage tank via pipeline; the filling port of the conditioning storage tank is connected to the solution conditioning feeding tank group via pipeline, and the drain port of the conditioning storage tank is connected to the inlet of the finished product storage tank via pipeline; the drain port of the finished product storage tank is connected to the finished product filling and weighing device.

[0008] The new vanadium battery electrolyte continuous production line adopts a PLC automated control system.

[0009] The electrochemical reaction device uses an electrolytic stack powered by DC power; the finished product filling and weighing device adopts a bucket-type structure or a tank-type structure; when the finished product filling and weighing device is a tank-type structure, it adopts a steel-lined storage tank structure or a fiberglass spiral wound storage tank structure; the weighing modes of the finished product filling and weighing device include weight mode and volume mode.

[0010] The novel vanadium battery electrolyte continuous production line also includes a gas recovery zone, in which a gas recovery device is installed; the exhaust ports of the positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank are all connected to the gas recovery device through pipelines; the exhaust ports of the positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank adopt natural exhaust or low-pressure suction exhaust.

[0011] The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank are all equipped with cooling devices; the cooling devices are water-cooled heat exchangers or air-cooled heat exchangers.

[0012] Liquid pumps, filters, control valves, and detection instruments are installed on the circulation pipeline between the positive electrode storage tank and the positive electrode of the electrochemical reaction device, the circulation pipeline between the negative electrode storage tank and the negative electrode of the electrochemical reaction device, the pipeline between the drain port of the negative electrode storage tank and the inlet of the reducing agent temporary storage tank, the pipeline between the drain port of the reducing agent temporary storage tank and the inlet of the reaction storage tank, the pipeline between the drain port of the reaction storage tank and the inlet of the regulating storage tank, the pipeline between the drain port of the regulating storage tank and the inlet of the finished product storage tank, and the pipeline between the drain port of the finished product storage tank and the finished product filling and weighing device. The liquid pumps are magnetic pumps; the filters are single-stage or multi-stage filters; and the detection instruments include flow meters, thermometers, and pressure gauges.

[0013] The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, regulating storage tank, and finished product storage tank are all equipped with a stirring device and a liquid level sensor; the stirring device is a motor-driven paddle mixer; the liquid level sensor is a contact liquid level sensor or a non-contact liquid level sensor.

[0014] The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, regulating storage tank and finished product storage tank all adopt steel-lined storage tank structure or fiberglass spiral wound storage tank structure. All tanks are equipped with waste discharge ports at the bottom and corrosion-resistant layers on the inner wall surface of the tank.

[0015] Both the negative electrode storage tank and the regulating storage tank are equipped with valence state monitoring devices, which include a potentiometric titration measurement system and a spectrophotometric measurement system. The regulating storage tank is also equipped with a concentration monitoring device. The reaction storage tank is also equipped with a heating device, which adopts an internal electric heating wire device or an external electric heating jacket device.

[0016] The solution preparation feeding tank group includes a solid feeding tank and a liquid feeding tank. The filling port of the reaction storage tank is connected to the discharge ports of the solid feeding tank and the liquid feeding tank. The reaction mode in the reaction storage tank is a solid-liquid reaction or a liquid-liquid reaction.

[0017] The beneficial effects of this invention are: This invention discloses a novel continuous production line for vanadium battery electrolytes. Based on a reduction method for electrolyte preparation, the raw materials can be high-purity V₂O₅ powder, high-purity NH₄VO₃ powder, VO₂SO₄ crystals, etc., or vanadium electrolyte solutions with a valence higher than 3.5. This design features high raw material adaptability and a wide range of applications. The reducing agent in this production line is only a low-valence vanadium electrolyte, without introducing other elements, ensuring the purity of the vanadium electrolyte. The reducing agent is produced by the production line and requires no additional replenishment except for a single addition during the initial start-up phase. This production line also features high production speed, good production stability, stable product quality, continuous production, easy operation, and savings in manpower and resources. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the structural principle of a novel continuous production line for vanadium battery electrolyte according to the present invention; In the diagram, 1—electrochemical reaction device, 2—positive electrode storage tank, 3—negative electrode storage tank, 4—reducing agent preparation and feeding tank group, 5—reducing agent temporary storage tank, 6—reaction storage tank, 7—solution preparation and feeding tank group, 8—adjustment storage tank, 9—solution adjustment and feeding tank group, 10—finished product storage tank, 11—finished product filling and weighing device, 12—gas recovery device. Detailed Implementation

[0019] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0020] like Figure 1As shown, a novel continuous production line for vanadium battery electrolyte includes a reducing agent preparation area, a reducing agent temporary storage area, a solution preparation area, a solution conditioning area, and a finished product filling area. The reducing agent preparation area is equipped with an electrochemical reaction device 1, a positive electrode storage tank 2, a negative electrode storage tank 3, and a reducing agent preparation feeding tank group 4. The reducing agent temporary storage area is equipped with a reducing agent temporary storage tank 5. The solution preparation area is equipped with a reaction storage tank 6 and a solution preparation feeding tank group 7. The solution conditioning area is equipped with a conditioning storage tank 8 and a solution conditioning feeding tank group 9. The finished product filling area is equipped with a finished product storage tank 10 and a finished product filling weighing device 11. The positive electrode storage tank 2 is connected to the positive electrode of the electrochemical reaction device 1 via a circulation pipeline. The negative electrode storage tank 3 is connected to the negative electrode of the electrochemical reaction device 1 via a circulation pipeline. The feeding ports of both the positive electrode storage tank 2 and the negative electrode storage tank 3 are... The reducing agent preparation feeding tank group 4 is connected via a pipeline; the drain port of the negative electrode storage tank 3 is connected to the inlet of the reducing agent temporary storage tank 5 via a pipeline; the drain port of the reducing agent temporary storage tank 5 has two outputs, one connected to the inlet of the reaction storage tank 6 via a pipeline, and the other connected to the solution conditioning feeding tank group 9 via a pipeline; the filling port of the reaction storage tank 6 is connected to the solution preparation feeding tank group 7 via a pipeline, and the drain port of the reaction storage tank 6 has two outputs, one connected to the inlet of the conditioning storage tank 8 via a pipeline, and the other connected to the reducing agent replenishment port of the negative electrode storage tank 3 via a pipeline; the filling port of the conditioning storage tank 8 is connected to the solution conditioning feeding tank group 9 via a pipeline, and the drain port of the conditioning storage tank 8 is connected to the inlet of the finished product storage tank 10 via a pipeline; the drain port of the finished product storage tank 10 is connected to the finished product filling and weighing device 11.

[0021] The new vanadium battery electrolyte continuous production line adopts a PLC automated control system.

[0022] The electrochemical reaction device 1 is an electrolytic stack powered by DC power; the finished product filling and weighing device 11 adopts a bucket-type structure or a tank-type structure; when the finished product filling and weighing device 11 is a tank-type structure, it adopts a steel-lined storage tank structure or a fiberglass wound storage tank structure; the weighing modes of the finished product filling and weighing device 11 include weight mode and volume mode.

[0023] Specifically, the recommended voltage range for the electrochemical reaction device 1 is 50V to 800V, the recommended current range is 50A to 1500A, and the recommended reaction time is 1h to 8h. Preferably, the voltage range is 100V to 400V, the preferred current range is 200A to 800A, and the preferred reaction time is 2h to 6h. The recommended weighing accuracy for the finished product filling and weighing device 11 is 0.05kg to 5.0kg, and the preferred weighing accuracy is 0.1kg to 1.0kg. The positive electrode solution of the electrochemical reaction device 1 is an aqueous sulfuric acid solution with a concentration range of 3mol / L to 8mol / L. The negative electrode solution of the electrochemical reaction device 1 is a vanadium electrolyte with a valence state range of 2 to 5 and a vanadium ion concentration range of 0.8mol / L to 2.2mol / L.

[0024] The novel vanadium battery electrolyte continuous production line also includes a gas recovery zone, in which a gas recovery device 12 is installed; the exhaust ports of the positive electrode storage tank 2, negative electrode storage tank 3, reducing agent temporary storage tank 5, reaction storage tank 6, and regulating storage tank 8 are all connected to the gas recovery device 12 through pipelines; the exhaust ports of the positive electrode storage tank 2, negative electrode storage tank 3, reducing agent temporary storage tank 5, reaction storage tank 6, and regulating storage tank 8 adopt natural exhaust or low-pressure suction exhaust.

[0025] The positive electrode storage tank 2, negative electrode storage tank 3, reducing agent temporary storage tank 5, reaction storage tank 6, and regulating storage tank 8 are all equipped with cooling devices; the cooling devices are water-cooled heat exchangers or air-cooled heat exchangers.

[0026] Liquid pumps, filters, control valves, and detection instruments are installed on the circulation pipeline between the positive electrode storage tank 2 and the positive electrode of the electrochemical reaction device 1; on the circulation pipeline between the negative electrode storage tank 3 and the negative electrode of the electrochemical reaction device 1; on the pipeline between the drain port of the negative electrode storage tank 3 and the inlet of the reducing agent temporary storage tank 5; on the pipeline between the drain port of the reducing agent temporary storage tank 5 and the inlet of the reaction storage tank 6; on the pipeline between the drain port of the reaction storage tank 6 and the inlet of the regulating storage tank 8; on the pipeline between the drain port of the regulating storage tank 8 and the inlet of the finished product storage tank 10; and on the pipeline between the drain port of the finished product storage tank 10 and the finished product filling and weighing device 11. The liquid pumps are magnetic pumps; the filters are single-stage or multi-stage filters; and the detection instruments include flow meters, thermometers, and pressure gauges.

[0027] Specifically, the magnetic pump used is a magnetic pump lined with PTFE or PP material, and the recommended flow rate is 10m³ / h. 3 / h~50m 3 / h, with a preferred flow rate range of 20m³ / h. 3 / h~40m3 / h; The filter is preferably a two-stage filter. The recommended filtration accuracy of the first stage filter is 0.2μm to 1.0μm, and the recommended filtration accuracy of the second stage filter is 0.01μm to 0.2μm. The preferred filtration accuracy of the first stage filter is 0.3μm to 0.6μm, and the preferred filtration accuracy of the second stage filter is 0.05μm to 0.1μm.

[0028] The positive electrode storage tank 2, negative electrode storage tank 3, reducing agent temporary storage tank 5, reaction storage tank 6, regulating storage tank 8, and finished product storage tank 10 are all equipped with stirring devices and liquid level sensors; the stirring device is a motor-driven paddle mixer; the liquid level sensor is a contact liquid level sensor or a non-contact liquid level sensor.

[0029] The positive electrode storage tank 2, negative electrode storage tank 3, reducing agent temporary storage tank 5, reaction storage tank 6, regulating storage tank 8, and finished product storage tank 10 all adopt steel-lined storage tank structure or fiberglass spiral wound storage tank structure. Each tank has a waste discharge port at the bottom and a corrosion-resistant layer on the inner wall surface.

[0030] Specifically, the tank body adopts a vertical cylindrical shape and is fixed by direct grounding or triangular support; the corrosion-resistant layer on the inner wall surface of the tank is made of PP, PE or PTFE.

[0031] Both the negative electrode storage tank 3 and the regulating storage tank 8 are equipped with valence state monitoring devices, which include a potentiometric titration measurement system and a spectrophotometric measurement system. The regulating storage tank 8 is also equipped with a concentration monitoring device. The reaction storage tank 6 is also equipped with a heating device, which adopts an internal electric heating wire device or an external electric heating jacket device.

[0032] The solution preparation feeding tank group 7 includes a solid feeding tank and a liquid feeding tank. The feeding port of the reaction storage tank 6 is connected to the discharge ports of the solid feeding tank and the liquid feeding tank. The reaction mode in the reaction storage tank 6 is a solid-liquid reaction or a liquid-liquid reaction.

[0033] Specifically, the pressure inside the reaction storage tank 6 is the normal pressure, the recommended feeding accuracy at the feeding port is 0.05kg to 5.0kg, the recommended reaction time is 1h to 8h, the recommended reaction temperature is 10℃ to 120℃, the preferred feeding accuracy is 0.1kg to 1.0kg, the preferred reaction time is 2h to 6h, and the preferred reaction temperature is 30℃ to 100℃.

[0034] The following description, in conjunction with the accompanying drawings, illustrates the usage of this invention: Example 1

[0035] In this embodiment, the reducing agent preparation feeding tank group 4 includes a sulfuric acid storage tank and a vanadium electrolyte storage tank. The sulfuric acid storage tank supplies a 5 mol / L sulfuric acid aqueous solution to the positive electrode of the electrochemical reaction device 1, and the vanadium electrolyte storage tank supplies a 2 mol / L high-valence vanadium electrolyte to the negative electrode of the electrochemical reaction device 1. After the electrochemical reaction device 1 is powered on and started, the high-valence vanadium electrolyte at the negative electrode of the electrochemical reaction device 1 is reduced to divalent vanadium electrolyte. Then, the divalent vanadium electrolyte is introduced from the negative electrode of the electrochemical reaction device 1 into the reducing agent temporary storage tank 5 for later use.

[0036] In this embodiment, the solution preparation feeding tank group 7 includes a solid raw material storage tank, a sulfuric acid storage tank, and a pure water storage tank. The solid raw material storage tank stores high-purity V2O5 powder. First, a portion of the divalent vanadium electrolyte in the reducing agent temporary storage tank 5 is introduced into the vanadium electrolyte storage tank of the solution conditioning feeding tank group 9 for subsequent solution conditioning. The other portion of the divalent vanadium electrolyte in the reducing agent temporary storage tank 5 is quantitatively introduced into the reaction storage tank 6. Then, high-purity V2O5 powder, sulfuric acid, and pure water are added to the reaction storage tank 6. At the same time, the stirring device and tank exhaust are started until a high-concentration 3.5-valent vanadium electrolyte is generated in the reaction storage tank 6. At this time, the vanadium ion concentration of the 3.5-valent vanadium electrolyte is about 2.0 mol / L, and the sulfuric acid concentration is about 2.5 mol / L.

[0037] In this embodiment, the solution conditioning and feeding tank group 9 includes a vanadium electrolyte storage tank, a sulfuric acid storage tank, a pure water storage tank, and other trace element storage tanks. First, a portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the negative electrode of the electrochemical reaction device 1 to prepare a new divalent vanadium electrolyte. Another portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the conditioning storage tank 8. Then, divalent vanadium electrolyte, sulfuric acid, pure water, and other trace elements are added to the reaction storage tank 6 until the required vanadium electrolyte product is prepared in the conditioning storage tank 8.

[0038] Once the required vanadium electrolyte is prepared, the vanadium electrolyte in the regulating storage tank 8 is first transferred to the finished product storage tank 10, and then transferred from the finished product storage tank 10 to the finished product filling and weighing device 11 to complete the filling and storage. The entire production process generates no waste and does not add other elements, making the production line clean and environmentally friendly.

[0039] Example 2

[0040] In this embodiment, the reducing agent preparation feeding tank group 4 includes a sulfuric acid storage tank and a vanadium electrolyte storage tank. The sulfuric acid storage tank supplies a 6 mol / L sulfuric acid aqueous solution to the positive electrode of the electrochemical reaction device 1, and the vanadium electrolyte storage tank supplies a 2.2 mol / L high-valence vanadium electrolyte to the negative electrode of the electrochemical reaction device 1. After the electrochemical reaction device 1 is powered on and started, the high-valence vanadium electrolyte at the negative electrode of the electrochemical reaction device 1 is reduced to divalent vanadium electrolyte. Then, the divalent vanadium electrolyte is introduced from the negative electrode of the electrochemical reaction device 1 into the reducing agent temporary storage tank 5 for later use.

[0041] In this embodiment, the solution preparation feeding tank group 7 includes a solid raw material storage tank, a sulfuric acid storage tank, and a pure water storage tank. The solid raw material storage tank stores high-purity V2O5 powder. First, a portion of the divalent vanadium electrolyte in the reducing agent temporary storage tank 5 is introduced into the vanadium electrolyte storage tank of the solution conditioning feeding tank group 9 for subsequent solution conditioning. The other portion of the divalent vanadium electrolyte in the reducing agent temporary storage tank 5 is quantitatively introduced into the reaction storage tank 6. Then, high-purity NH4VO3 powder, sulfuric acid, and pure water are added to the reaction storage tank 6. At the same time, the stirring device and tank exhaust are started until a high-concentration 3.5-valent vanadium electrolyte is generated in the reaction storage tank 6. At this time, the vanadium ion concentration of the 3.5-valent vanadium electrolyte is about 2.0 mol / L, and the sulfuric acid concentration is about 2.5 mol / L.

[0042] In this embodiment, the solution conditioning and feeding tank group 9 includes a vanadium electrolyte storage tank, a sulfuric acid storage tank, a pure water storage tank, and other trace element storage tanks. First, a portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the negative electrode of the electrochemical reaction device 1 to prepare a new divalent vanadium electrolyte. Another portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the conditioning storage tank 8. Then, divalent vanadium electrolyte, sulfuric acid, pure water, and other trace elements are added to the reaction storage tank 6 until the required vanadium electrolyte product is prepared in the conditioning storage tank 8.

[0043] Once the required vanadium electrolyte is prepared, the vanadium electrolyte in the regulating storage tank 8 is first transferred to the finished product storage tank 10, and then transferred from the finished product storage tank 10 to the finished product filling and weighing device 11 to complete the filling and storage. The entire production process generates no waste and does not add other elements. Since the raw material is high-purity NH4VO3 powder, ammonia gas will be generated in the exhaust. The discharged ammonia gas can be directly processed in the gas recovery device 12 and can be used to produce ammonia by-products. Therefore, the production line is clean and environmentally friendly.

[0044] Example 3

[0045] In this embodiment, the reducing agent preparation feeding tank group 4 includes a sulfuric acid storage tank and a vanadium electrolyte storage tank. The sulfuric acid storage tank supplies a 4 mol / L sulfuric acid aqueous solution to the positive electrode of the electrochemical reaction device 1, and the vanadium electrolyte storage tank supplies a 1.75 mol / L high-valence vanadium electrolyte to the negative electrode of the electrochemical reaction device 1. After the electrochemical reaction device 1 is powered on and started, the high-valence vanadium electrolyte at the negative electrode of the electrochemical reaction device 1 is reduced to a low-valence vanadium electrolyte. The low-valence vanadium electrolyte can be of valence 2 to 3. Then, the low-valence vanadium electrolyte is introduced from the negative electrode of the electrochemical reaction device 1 into the reducing agent temporary storage tank 5 for later use.

[0046] In this embodiment, the solution preparation feeding tank group 7 only includes a liquid raw material storage tank, which stores a high-valence vanadium electrolyte with a valence higher than 3.5. First, a portion of the low-valence vanadium electrolyte in the reducing agent temporary storage tank 5 is introduced into the vanadium electrolyte storage tank of the solution conditioning feeding tank group 9 for subsequent solution conditioning. The other portion of the low-valence vanadium electrolyte in the reducing agent temporary storage tank 5 is quantitatively introduced into the reaction storage tank 6. Then, the high-valence vanadium electrolyte is added to the reaction storage tank 6, and at the same time, the stirring device and tank exhaust are started until a high concentration of 3.5-valence vanadium electrolyte is generated in the reaction storage tank 6.

[0047] In this embodiment, the solution conditioning and feeding tank group 9 includes a vanadium electrolyte storage tank, a sulfuric acid storage tank, a pure water storage tank, and other trace element storage tanks. First, a portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the negative electrode of the electrochemical reaction device 1 to prepare a new low-valent vanadium electrolyte. Another portion of the 3.5-valent vanadium electrolyte in the reaction storage tank 6 is introduced into the conditioning storage tank 8. Then, low-valent vanadium electrolyte, sulfuric acid, pure water, and other trace elements are added to the reaction storage tank 6 until the required vanadium electrolyte product is prepared in the conditioning storage tank 8.

[0048] Once the required vanadium electrolyte is prepared, the vanadium electrolyte in the regulating storage tank 8 is first transferred to the finished product storage tank 10, and then transferred from the finished product storage tank 10 to the finished product filling and weighing device 11 to complete the filling and storage. The entire production process generates no waste and does not add other elements, making the production line clean and environmentally friendly.

[0049] It should be noted that the 1.75 mol / L high-valence vanadium electrolyte supplied to the negative electrode of electrochemical reaction device 1 can be any valence state between 3.7 and 5. Before adding the high-valence and low-valence vanadium electrolytes to the reaction storage tank, relevant data such as valence state, concentration, and sulfate ion concentration need to be detected. Based on the detection results of valence state and concentration, the amount of high-valence and low-valence vanadium electrolytes to be added to the reaction storage tank should be determined.

[0050] The solutions in the embodiments are not intended to limit the scope of protection of the present invention. All equivalent implementations or modifications that do not depart from the present invention are included in the scope of protection of the present invention.

Claims

1. A novel continuous production line for vanadium battery electrolyte, characterized in that: The system includes a reducing agent preparation area, a reducing agent temporary storage area, a solution preparation area, a solution conditioning area, and a finished product filling area. The reducing agent preparation area is equipped with an electrochemical reaction device, a positive electrode storage tank, a negative electrode storage tank, and a reducing agent preparation feeding tank assembly. The reducing agent temporary storage area is equipped with a reducing agent temporary storage tank. The solution preparation area is equipped with a reaction storage tank and a solution preparation feeding tank assembly. The solution conditioning area is equipped with a conditioning storage tank and a solution conditioning feeding tank assembly. The finished product filling area is equipped with a finished product storage tank and a finished product filling weighing device. The positive electrode storage tank is connected to the positive electrode of the electrochemical reaction device via a circulation pipeline. The negative electrode storage tank is connected to the negative electrode of the electrochemical reaction device via a circulation pipeline. The feeding ports of both the positive and negative electrode storage tanks are connected to the reducing agent via pipelines. A feeding tank assembly is prepared. The drain port of the negative electrode storage tank is connected to the inlet of the reducing agent temporary storage tank via a pipeline. The drain port of the reducing agent temporary storage tank has two outputs: one connected to the inlet of the reaction storage tank via a pipeline, and the other connected to the solution conditioning feeding tank assembly via a pipeline. The filling port of the reaction storage tank is connected to the solution preparation feeding tank assembly via a pipeline. The drain port of the reaction storage tank has two outputs: one connected to the inlet of the conditioning storage tank via a pipeline, and the other connected to the reducing agent replenishment port of the negative electrode storage tank via a pipeline. The filling port of the conditioning storage tank is connected to the solution conditioning feeding tank assembly via a pipeline, and the drain port of the conditioning storage tank is connected to the inlet of the finished product storage tank via a pipeline. The drain port of the finished product storage tank is connected to the finished product filling and weighing device.

2. The novel vanadium battery electrolyte continuous production line according to claim 1, characterized in that: The new vanadium battery electrolyte continuous production line adopts a PLC automated control system.

3. The novel vanadium battery electrolyte continuous production line according to claim 1, characterized in that: The electrochemical reaction device uses an electrolytic stack powered by DC power; the finished product filling and weighing device adopts a bucket-type structure or a tank-type structure; when the finished product filling and weighing device is a tank-type structure, it adopts a steel-lined storage tank structure or a fiberglass spiral wound storage tank structure; the weighing modes of the finished product filling and weighing device include weight mode and volume mode.

4. The novel continuous production line for vanadium battery electrolyte according to claim 1, characterized in that: The novel vanadium battery electrolyte continuous production line also includes a gas recovery zone, in which a gas recovery device is installed; the exhaust ports of the positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank are all connected to the gas recovery device through pipelines; the exhaust ports of the positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank adopt natural exhaust or low-pressure suction exhaust.

5. A novel continuous production line for vanadium battery electrolyte according to claim 1, characterized in that: The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, and regulating storage tank are all equipped with cooling devices; the cooling devices are water-cooled heat exchangers or air-cooled heat exchangers.

6. The novel vanadium battery electrolyte continuous production line according to claim 1, characterized in that: Liquid pumps, filters, control valves, and detection instruments are installed on the circulation pipeline between the positive electrode storage tank and the positive electrode of the electrochemical reaction device, the circulation pipeline between the negative electrode storage tank and the negative electrode of the electrochemical reaction device, the pipeline between the drain port of the negative electrode storage tank and the inlet of the reducing agent temporary storage tank, the pipeline between the drain port of the reducing agent temporary storage tank and the inlet of the reaction storage tank, the pipeline between the drain port of the reaction storage tank and the inlet of the regulating storage tank, the pipeline between the drain port of the regulating storage tank and the inlet of the finished product storage tank, and the pipeline between the drain port of the finished product storage tank and the finished product filling and weighing device. The liquid pumps are magnetic pumps; the filters are single-stage or multi-stage filters; and the detection instruments include flow meters, thermometers, and pressure gauges.

7. The novel vanadium battery electrolyte continuous production line according to claim 1, characterized in that: The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, regulating storage tank, and finished product storage tank are all equipped with a stirring device and a liquid level sensor; the stirring device is a motor-driven paddle mixer; the liquid level sensor is a contact liquid level sensor or a non-contact liquid level sensor.

8. A novel continuous production line for vanadium battery electrolyte according to claim 1, characterized in that: The positive electrode storage tank, negative electrode storage tank, reducing agent temporary storage tank, reaction storage tank, regulating storage tank and finished product storage tank all adopt steel-lined storage tank structure or fiberglass spiral wound storage tank structure. All tanks are equipped with waste discharge ports at the bottom and corrosion-resistant layers on the inner wall surface of the tank.

9. A novel continuous production line for vanadium battery electrolyte according to claim 1, characterized in that: Both the negative electrode storage tank and the regulating storage tank are equipped with valence state monitoring devices, which include a potentiometric titration measurement system and a spectrophotometric measurement system. The regulating storage tank is also equipped with a concentration monitoring device. The reaction storage tank is also equipped with a heating device, which adopts an internal electric heating wire device or an external electric heating jacket device.

10. A novel continuous production line for vanadium battery electrolyte according to claim 1, characterized in that: The solution preparation feeding tank group includes a solid feeding tank and a liquid feeding tank. The filling port of the reaction storage tank is connected to the discharge ports of the solid feeding tank and the liquid feeding tank. The reaction mode in the reaction storage tank is a solid-liquid reaction or a liquid-liquid reaction.

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