Detection device and recovery system
By using a sampling and pressure regulation module detection device in the battery recycling process, the problems of complex structure and insufficient real-time accuracy of existing equipment are solved, realizing efficient ion concentration detection with a simplified structure, and achieving real-time and accurate detection results.
Patent Information
- Application Number
- CN202423266128.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-27
- Publication Date
- 2025-12-30
- Estimated Expiration
- 2034-12-27
AI Technical Summary
Existing ion concentration detection equipment has problems such as complex structure, which leads to high operation difficulty and high maintenance cost in the battery recycling process. At the same time, simplified equipment cannot guarantee the real-time and accuracy of monitoring.
A detection device is provided, including a sampling module, a detection module, and a pressure regulating module. The sampling liquid is obtained from the solution to be tested through a sampling pipeline, and the pressure regulating module controls the gas pressure value. The sample is delivered to the detection module at low pressure and returned to the solution at high pressure, which simplifies the structure and ensures real-time performance and accuracy.
It achieves real-time and accurate ion concentration detection, while simplifying the structure of the detection device and reducing the difficulty of operation and maintenance costs.
Smart Images
Figure CN223742382U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model belongs to the technical field of ion concentration detection, specifically, the utility model relates to a detection device and recovery system. BACKGROUND
[0002] In the field of ion concentration detection, especially in the process of battery recovery, the battery recovery liquid often contains various metal ions, and the extraction efficiency of metal ions is crucial.
[0003] The detection equipment in the related art has many problems, on the one hand, in order to realize high-precision online monitoring, the structure of the detection equipment is often complex, which increases the operation difficulty and maintenance cost, on the other hand, the detection equipment with simplified structure is difficult to guarantee the real-time performance and accuracy of monitoring. UTILITY MODEL CONTENTS
[0004] One object of the utility model is to provide a new technical scheme of a detection device and recovery system.
[0005] According to the first aspect of the utility model, a detection device is provided, which comprises:
[0006] A sampling module, the sampling module comprises a sampling pipeline;
[0007] A detection module, one end of the sampling pipeline is used to obtain a sampling liquid from a to-be-detected solution, the other end of the sampling pipeline is located in the detection module, and the detection module is used to detect the concentration of a set ion in the sampling liquid in real time;
[0008] A pressure regulating module, the pressure regulating module is connected to the sampling pipeline and is used to control the air pressure value in the sampling pipeline;
[0009] In the case that the air pressure value in the sampling pipeline is less than or equal to a first low pressure threshold, the sampling liquid is transported to the detection module through the sampling pipeline; in the case that the air pressure value in the sampling pipeline is greater than or equal to a first high pressure threshold, the sampling liquid in the sampling pipeline flows back to the to-be-detected solution.
[0010] Optionally, the detection module is an electrochemical detection module or an AAS detection module.
[0011] Optionally, the electrochemical detection module comprises a detection electrode, a detection main body and a detection container, one end of the detection electrode is connected to the detection main body, and the other end of the detection electrode is located in the detection container.
[0012] In the case that the air pressure value in the sampling pipeline is less than or equal to a first low pressure threshold, the sampling liquid is transported to the detection container through the sampling pipeline.
[0013] Optionally, the detection electrode comprises a detection electrode, a reference electrode and a counter electrode, and a metal organic framework layer is arranged on the surface of the detection electrode, and the metal organic framework layer is used for complexing with the set ions in the sampling liquid.
[0014] Optionally, the material of the metal organic framework layer is a material synthesized by at least one of nickel, cobalt and manganese and an organic ligand of benzoic acid, or the material of the metal organic framework layer is a material synthesized by at least one of nickel, cobalt and manganese and a derivative of the organic ligand of benzoic acid.
[0015] Optionally, the waste liquid container and the washing container are both connected to the detection container.
[0016] When the air pressure value in the detection container is greater than or equal to a second high pressure threshold value, the sampling liquid in the detection container can be output to the waste liquid container; when the air pressure value in the detection container is less than or equal to a second low pressure threshold value, the washing liquid in the washing container can be input to the detection container.
[0017] Optionally, the pressure adjusting module comprises a vacuum component and a pressurizing component, the vacuum component is connected to the sampling pipeline and can make the air pressure value in the sampling pipeline less than or equal to a first low pressure threshold value.
[0018] The pressurizing component is connected to the sampling pipeline and can make the air pressure value in the sampling pipeline greater than or equal to a first high pressure threshold value.
[0019] Optionally, the pressure adjusting module comprises a piston driving component, and the piston driving component is connected to the sampling pipeline.
[0020] According to the second aspect of the utility model, a recycling system is provided, the recycling system comprises infusion pipeline and the detection device of first aspect, and the detection device is arranged on the infusion pipeline.
[0021] The infusion pipeline is used for conveying a solution to be detected, and the sampling pipeline is connected to the infusion pipeline.
[0022] Optionally, the recycling system comprises an acid immersion device, a first filtering device, a first pH adjusting device and a second filtering device connected in sequence.
[0023] The acid immersion device is used for acid treatment of recycled materials, and the second filtering device is connected to the input end of the infusion pipeline.
[0024] Optionally, the recycling system comprises a second pH adjusting device, a centrifugal extraction device and a crystallization device connected in sequence.
[0025] The second pH adjusting device is connected to an output end of the infusion pipeline and is used for adjusting the pH value of the solution to be detected, and the centrifugal extraction device and the crystallization device are used for obtaining at least part of metal ions in the solution to be detected.
[0026] One technical effect of the utility model lies in:
[0027] The detection device provided by the embodiment of the application comprises a sampling module, the sampling module comprises a sampling pipeline, a detection module, one end of the sampling pipeline is used for obtaining sampling liquid from a solution to be detected, the other end of the sampling pipeline is located at the detection module, and the detection module is used for detecting the concentration of set ions in the sampling liquid in real time, and a pressure adjusting module, the pressure adjusting module is connected to the sampling pipeline and is used for controlling the air pressure value in the sampling pipeline, the sampling liquid is transported to the detection module through the sampling pipeline in the case that the air pressure value in the sampling pipeline is less than or equal to a first low pressure threshold value, and the sampling liquid in the sampling pipeline flows back to the solution to be detected in the case that the air pressure value in the sampling pipeline is greater than or equal to a first high pressure threshold value, so that the structure of the detection device is simplified, and the real-time performance and the accuracy of the detection device when monitoring the concentration of set ions are ensured.
[0028] Other features and advantages of the utility model will become clear from the following detailed description of exemplary embodiments of the utility model with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS
[0029] The accompanying drawings incorporated in and forming a part of the specification illustrate embodiments of the utility model and, together with the description, serve to explain the principles of the utility model.
[0030] Figure 1 A schematic view of a detection device provided for one embodiment of the utility model;
[0031] Figure 2 A schematic view of a recovery system provided for one embodiment of the utility model.
[0032] Wherein:
[0033] 100, detection device; 1, sampling module; 11, sampling pipeline; 2, detection module; 21, detection electrode; 22, detection main body; 23, detection container; 3, pressure adjusting module; 4, control module; 5, electrical module; 6, waste liquid container; 7, washing container;
[0034] 200, infusion pipeline; 300, acid immersion device; 400, first filter device; 500, first pH adjusting device; 600, second filter device; 700, second pH adjusting device; 800, centrifugal extraction device; 900, crystallization device. DETAILED DESCRIPTION
[0035] Various exemplary embodiments of the present application will now be described in detail with reference to the accompanying drawings. It should be noted that the relative arrangement of the components and steps set forth in the examples, the numerical expressions, and the numerical values set forth in the examples are not limiting to the scope of the present application unless specifically stated otherwise.
[0036] The embodiments of the present application will be described in detail below with reference to the accompanying drawings. The embodiments described below are exemplary only, and are used to explain the present application, and should not be understood as limiting the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.
[0037] The terms "first", "second" in the specification and claims of the present application can explicitly or implicitly include one or more features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise specified. In addition, "and / or" in the specification and claims means at least one of the connected objects, and the character " / ", generally indicates that the front and rear associated objects are in an "or" relationship.
[0038] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.
[0039] In the description of the present application, it should be noted that unless otherwise specifically stated and limited, the terms "mounting", "connecting", "connecting" should be broadly understood, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium, or it can be connected inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.
[0040] It should be noted that similar reference numerals and letters refer to similar items in the following drawings, and therefore, once an item is defined in one drawing, it need not be further discussed in subsequent drawings.
[0041] Reference Figure 1The embodiment of the present application provides a detection device for detecting the ion concentration in a solution, which comprises:
[0042] A sampling module 1, the sampling module 1 comprising a sampling pipeline 11;
[0043] A detection module 2, one end of the sampling pipeline 11 being used for obtaining sampling liquid from the solution to be detected, and the other end of the sampling pipeline 11 being located at the detection module 2, and the detection module 2 being used for detecting the concentration of the set ions in the sampling liquid in real time;
[0044] A pressure regulating module 3, the pressure regulating module 3 being connected to the sampling pipeline 11 and being used for controlling the air pressure value in the sampling pipeline 11;
[0045] In the case that the air pressure value in the sampling pipeline 11 is less than or equal to a first low pressure threshold value, the sampling liquid is transported to the detection module 2 through the sampling pipeline 11; in the case that the air pressure value in the sampling pipeline 11 is greater than or equal to a first high pressure threshold value, the sampling liquid in the sampling pipeline 11 flows back to the solution to be detected.
[0046] In this embodiment, the sampling module 1 is used for obtaining the sampling liquid from the solution to be detected, and the solution to be detected can be a recovery solution at different process stages in the battery recovery process or other solutions to be detected, such as directly sampling the solution in the lithium iron phosphate battery wet recovery line through the sampling pipeline 11 of the sampling module 1, so as to quickly obtain the sampling liquid in the battery recovery solution and provide convenience for subsequent analysis and detection of the sampling liquid.
[0047] For example, when the detection module 2 detects that the concentration of the set ions in the sampling liquid is high, it represents that the concentration of the set ions in the solution to be detected is also high, which indicates that the recovery efficiency of the set ions in the solution to be detected is low, and the set ions in the solution to be detected can be continuously recovered; if the detection module 2 detects that the concentration of the set ions in the sampling liquid is low, such as the concentration of the set ions in the sampling liquid has been lower than the standard of recovery, it represents that the concentration of the set ions in the solution to be detected is also low, which indicates that the recovery efficiency of the set ions in the solution to be detected is high, and the solution to be detected can be treated as waste liquid.
[0048] In this embodiment, when the detection device is used for detecting the concentration of the set ions in the recovery liquid in the battery recovery process, the set ions can be lithium ions, copper ions, iron ions, nickel ions, cobalt ions or manganese ions, the above-mentioned ions can be recovered separately through different process lines or recovered uniformly through the same process line, and the embodiment of the present application does not make any limitation in this aspect.
[0049] In this embodiment, the detection module 2 can monitor the residual concentration of the ions in the solution to be detected in real time, which can effectively control the ion residues in the solution to be detected while ensuring the purity of the recovered ions, avoid the waste of the ions in the solution to be detected, and ensure the ion recovery efficiency.
[0050] In the above embodiment, the pressure regulating module 3 can be a motor or a pump body, and the pressure regulating module 3 is connected to the sampling pipeline 11 and used to control the air pressure value in the sampling pipeline 11. For example, the pressure regulating module 3 can extract the gas in the sampling pipeline 11 to form a certain vacuum degree in the sampling pipeline 11; or the pressure regulating module 3 can deliver inert gas to the sampling pipeline 11 to form a gas pressure greater than the atmospheric pressure in the sampling pipeline 11.
[0051] When the air pressure value in the sampling pipeline 11 is less than or equal to the first low pressure threshold, for example, a certain vacuum degree is formed in the sampling pipeline 11 by the pressure regulating module 3, so that the sampling liquid can be delivered to the detection module 2 through the sampling pipeline 11 under the action of the pressure difference, thereby ensuring the timely detection of the detection module 2 on the concentration of the set ions in the sampling liquid.
[0052] When the air pressure value in the sampling pipeline 11 is greater than or equal to the first high pressure threshold, for example, a certain pressure of high pressure gas is formed in the sampling pipeline 11 by the pressure regulating module 3, so that the sampling liquid in the sampling pipeline 11 can flow back to the solution to be measured under the action of the pressure difference, thereby avoiding the influence of the residual sampling liquid in the sampling pipeline 11 on the subsequent sampling.
[0053] The detection device provided in the embodiment of the present application directly samples from the solution to be measured to the detection module 2 for detection through the sampling pipeline 11, so that the detection device integrates sampling, pressure regulation and detection in one, thereby simplifying the structure of the detection device while ensuring the detection efficiency and stability.
[0054] The detection device provided in the embodiment of the present application includes a sampling module 1, the sampling module 1 includes a sampling pipeline 11; a detection module 2, one end of the sampling pipeline 11 is used to obtain sampling liquid from the solution to be measured, and the other end of the sampling pipeline 11 is located in the detection module 2, and the detection module 2 is used to detect the concentration of the set ions in the sampling liquid in real time; a pressure regulating module 3, the pressure regulating module 3 is connected to the sampling pipeline 11 and used to control the air pressure value in the sampling pipeline 11; when the air pressure value in the sampling pipeline 11 is less than or equal to the first low pressure threshold, the sampling liquid is delivered to the detection module 2 through the sampling pipeline 11; when the air pressure value in the sampling pipeline 11 is greater than or equal to the first high pressure threshold, the sampling liquid in the sampling pipeline 11 flows back to the solution to be measured, thereby simplifying the structure of the detection device and ensuring the real-time performance and accuracy of the detection device when monitoring the concentration of the set ions.
[0055] In one embodiment, the detection module 2 is an electrochemical detection module or an AAS detection module.
[0056] In this embodiment, the detection module 2 is configured as an electrochemical detection module or an AAS (Atomic Absorption Spectroscopy) detection module, so as to timely monitor the concentration of the set ions in the sampling liquid through real-time detection on the basis of ensuring the accuracy of the detection of the set ion concentration in the sampling liquid, so as to facilitate the timely processing of the solution to be measured.
[0057] In some embodiments, referring to Figure 1 , the electrochemical detection module comprises a detection electrode 21, a detection main body 22 and a detection container 23, one end of the detection electrode 21 is connected to the detection main body 22, and the other end of the detection electrode 21 is located in the detection container 23.
[0058] In the case that the air pressure value in the sampling pipeline 11 is less than or equal to the first low pressure threshold value, the sampling liquid is transported to the detection container 23 through the sampling pipeline 11.
[0059] In this embodiment, the detection container 23 can be a sealed detection pool, the sealing cover of the sealed detection pool is a polytetrafluoroethylene sealing cover, and the volume of the detection container 23 is 30-50 mL, so as to avoid the waste of the sampling liquid and ensure the accuracy of the detection.
[0060] The sampling liquid is transported to the detection container 23 through the sampling pipeline 11 under the pressure difference between the air pressure value of the solution to be measured and the air pressure value in the sampling pipeline 11. The detection module 2 provided in the embodiment can directly insert the detection electrode 21 into the sampling liquid in the detection container 23 to perform real-time detection on the concentration of the set ions in the sampling liquid. The detection main body 22 can realize rapid and in-situ detection of the set ion concentration, so as to ensure the efficiency of the detection.
[0061] In one embodiment, referring to Figure 1 , the detection device further comprises a control module 4 and an electrical module 5. The detection main body 22 can realize the detection of the ion concentration of copper ions, lithium ions and the like in the sampling liquid within 5 minutes, and transmit the detection data to the control module 4. The control module 4 can obtain the real-time ion concentration after processing, and can also control the ion detector and the like to change different modes to realize the ion concentration detection, baseline calibration and data processing and the like, and save and output the data detected by the detection main body 22. The electrical module 5 can control the pressure in the pressure adjusting module 3 and the detection container 23, so as to ensure the transportation and backflow of the sampling liquid in the sampling pipeline 11.
[0062] In one embodiment, referring to Figure 1 , the detection electrode 21 comprises a detection electrode, a reference electrode and a counter electrode, and the surface of the detection electrode is provided with a metal organic framework layer, which is used for complexing with the set ions in the sampling liquid.
[0063] In this embodiment, the detection electrode is used to detect the ion concentration of copper ions, lithium ions, etc.; the reference electrode plays a role of calibration and can prevent potential drift; and the counter electrode is used to form a current loop. The three electrodes of the detection electrode, the reference electrode and the counter electrode are all immersed in the sampling liquid during the detection process, and the three electrodes are connected to the detection main body 22 through wires to transmit signals such as current and potential to the detection main body 22, so as to realize ion detection.
[0064] In some embodiments, the material of the metal organic framework layer is a material synthesized by at least one of nickel, cobalt and manganese and a benzoic acid type organic ligand, or a material synthesized by at least one of nickel, cobalt and manganese and a benzoic acid type organic ligand derivative.
[0065] In one embodiment, the material of the metal organic framework layer is an existing MOFs material. The MOFs (Metal organic Framework, i.e. porous metal organic framework material) material is a kind of crystalline porous material with periodic network structure formed by self-assembly of inorganic metal center metal ions or metal clusters of nickel, cobalt, manganese, etc. and bridged benzoic acid type organic ligands, i.e. the above-mentioned material synthesized by at least one of nickel, cobalt and manganese and a benzoic acid type organic ligand; or the MOFs material is a material synthesized by at least one of nickel, cobalt and manganese and a benzoic acid type organic ligand derivative through self-assembly of inorganic metal center metal ions or metal clusters of nickel, cobalt, manganese, etc. and bridged benzoic acid type organic ligand derivatives. The MOFs material has both the rigidity of inorganic materials and the flexibility of organic materials.
[0066] When the detection electrode 21 detects the set ion concentration, the pores of the metal organic framework layer match the set ions, and the pore walls of the pores in the metal organic framework layer have chemical functional groups that can chemically interact with the set ions, so that the set ions can be accurately identified and stably complexed with the set ions. After complexation, the detection main body 22 can detect the reduction current of the set ions or the potential of the electrode surface. Since the complexation reaction is reversible, when the concentration of the set ions is high, more set ions enter the pores to complex, and when the concentration of the set ions is low, fewer set ions enter the pores to complex. The reduction current value or the electrode surface potential will be different according to the amount of complexed set ions, that is, the high and low of the current or potential value can establish a linear relationship with the set ions, so as to achieve selective detection of the set ions.
[0067] In one embodiment, the detection electrode 21 modified with the metal organic framework material can selectively detect copper ions in the sampling liquid.
[0068] In a specific embodiment, the detection device is used for detecting copper ions in lithium ion battery recycling liquid. After mechanical crushing, black powder is separated from the lithium ion battery. The black powder can be converted into solution ions by acid leaching. Due to the mechanical crushing process, part of the copper foil is ground into powder by mechanical force. Therefore, the solution after acid leaching contains a large amount of copper ions, but there is no interference of other ions such as nickel, cobalt and manganese. The detection electrode 21 modified with the metal-organic framework material can realize selective detection of copper ions and accurately detect the concentration of copper ions.
[0069] In some embodiments, referring to Figure 1 The detection device further comprises a waste liquid container 6 and a washing container 7, both of which are connected to the detection container 23;
[0070] When the gas pressure value in the detection container 23 is greater than or equal to the second high pressure threshold value, the sampling liquid in the detection container 23 can be output to the waste liquid container 6; when the gas pressure value in the detection container 23 is less than or equal to the second low pressure threshold value, the washing liquid in the washing container 7 can be input to the detection container 23.
[0071] During the detection stage of the detection container 23 by the detection electrode 21 to the sampling liquid in the detection container 23, the electrical module 5 controls the valves between the detection container 23 and the sampling pipeline 11, the valves between the detection container 23 and the waste liquid container 6, and the valves between the detection container 23 and the washing container 7 to be closed.
[0072] After the detection ends, the liquid discharge stage of the detection container 23 is entered, the electrical module 5 controls the valve between the detection container 23 and the waste liquid container 6 to be opened, inert gas is introduced into the detection container 23 to maintain the positive pressure in the detection container 23, and the gas pressure value in the detection container 23 is greater than or equal to the second high pressure threshold value, so that the sampling liquid in the detection container 23 is pressed into the waste liquid container 6.
[0073] After the liquid discharge stage ends, the washing stage of the detection container 23 is entered, the electrical module 5 controls the valve between the detection container 23 and the waste liquid container 6 to be closed, and the valve between the detection container 23 and the washing container 7 to be opened. By vacuumizing the detection container 23, the gas pressure value in the detection container 23 is less than or equal to the second low pressure threshold value, the washing liquid in the washing container 7 is introduced into the detection container 23 through negative pressure, and the process of the liquid discharge stage is repeated again. After repeated washing and liquid discharge for several times, the washing ends, and the accuracy of the next sampling detection of the detection container 23 is ensured.
[0074] In an embodiment, the pressure regulating module 3 comprises a vacuum component and a pressurizing component, the vacuum component is connected to the sampling pipeline 11 and can make the gas pressure value in the sampling pipeline 11 less than or equal to the first low pressure threshold value;
[0075] The pressurizing component is connected to the sampling pipeline 11 and can make the air pressure value in the sampling pipeline 11 greater than or equal to the first high pressure threshold.
[0076] In this embodiment, the sampling pipeline 11 can be connected to a vacuum component such as a vacuum pump, at the same time, the sampling pipeline 11 is connected to a pressurizing component with a gas storage bottle storing inert gas such as nitrogen, argon and the like, and the positive and negative pressure in the sampling pipeline 11 is controlled by the electrical module 5, for example, the electrical module 5 can control the start and stop and output power of the vacuum pump, and can adjust the opening and closing and output gas flow of the gas storage bottle.
[0077] When the sampling module 1 is in the stage of sampling the solution to be tested, the electrical module 5 controls the valve between the sampling pipeline 11 and the infusion pipeline conveying the solution to be tested to be opened, and the gas storage bottle is in the closed state, at this time the vacuum pump is opened and extracts the gas in the sampling pipeline 11, so that the sampling pipeline 11 is in negative pressure, and the solution to be tested in the infusion pipeline can be conveyed to the sampling pipeline 11 under the action of pressure difference, so as to realize the sampling of the solution to be tested in the infusion pipeline. Since the sampling pipeline 11 is connected to the detection container 23 at the terminal, after the volume of the sampling liquid in the detection container 23 meets the requirements, the vacuum pump is closed, the gas storage bottle is opened and the gas is flushed into the sampling pipeline 11, the solution in the sampling pipeline 11 is sent back to the infusion pipeline under the action of pressure difference, and then the control valve between the sampling pipeline 11 and the infusion pipeline is in the closed state. When the detection is finished and the next sampling is performed, the same operation is performed.
[0078] In one embodiment, the pressure regulating module 3 includes a piston driving component, and the piston driving component is connected to the sampling pipeline 11.
[0079] In the embodiment, the electrical module 5 can control the positive and negative pressure in the sampling pipeline 11, for example, the electrical module 5 can control the action and output power of the piston driving component.
[0080] When the sampling module 1 is in the stage of sampling the solution to be tested, the electrical module 5 controls the piston driving component to act and move the piston rod away from the sampling pipeline 11, so as to extract the gas in the sampling pipeline 11 through the first valve, so that the sampling pipeline 11 is in negative pressure, and the solution to be tested in the infusion pipeline can be conveyed to the sampling pipeline 11 under the action of pressure difference, so as to realize the sampling of the solution to be tested in the infusion pipeline. Since the sampling pipeline 11 is connected to the detection container 23 at the terminal, after the volume of the sampling liquid in the detection container 23 meets the requirements, the electrical module 5 controls the piston driving component to act and move the piston rod close to the sampling pipeline 11, so as to flush the gas into the sampling pipeline 11 through the second valve, and the solution in the sampling pipeline 11 is sent back to the infusion pipeline under the action of pressure difference, and then the control valve between the sampling pipeline 11 and the infusion pipeline is in the closed state.
[0081] Referring toFigure 2 The embodiment of the present application provides a recycling system, which comprises the infusion pipeline 200 and the detection device 100.
[0082] The infusion pipeline 200 is used for conveying the solution to be detected, and the sampling pipeline 11 is connected to the infusion pipeline 200.
[0083] In the embodiment, the detection device 100 directly samples the solution to be detected in the infusion pipeline 200 to the detection module 2 for detection through the sampling pipeline 11, so that the detection device integrates sampling, pressure adjustment and detection, and simplifies the structure of the recycling system while ensuring detection efficiency and stability.
[0084] In some embodiments, referring to Figure 2 The recycling system comprises the acid immersion device 300, the first filtering device 400, the first pH adjusting device 500 and the second filtering device 600 connected in sequence.
[0085] The acid immersion device 300 is used for acid treatment of the recycling material, and the second filtering device 600 is connected to the input end of the infusion pipeline 200.
[0086] In the above embodiment, when the recycling system is used for recycling metal ions in the lithium ion battery recycling material, the black powder separated from the recycling material needs to be acid immersed and extracted, for example, the acid immersion device 300 is used for acid treatment of the recycling material to dissolve the metal ions in the recycling material, and the residues that are difficult to dissolve can be filtered through the first filtering device 400; then the pH is adjusted through the first pH adjusting device 500, because different metal ions will form precipitates at different pH values, so as to realize extraction of different metal ions, for example, Fe, Al and Cu are precipitated respectively, so as to obtain salt precipitates of Fe, Al and Cu through the second filtering device 600. After the corresponding metal ions are extracted in each step, it should be ensured that the metal ion extraction is completed to avoid affecting the purity of the subsequent extracted ions.
[0087] In some embodiments, referring to Figure 2 The recycling system comprises the second pH adjusting device 700, the centrifugal extraction device 800 and the crystallization device 900 connected in sequence.
[0088] The second pH adjusting device 700 is connected to the output end of the infusion pipeline 200 and is used for adjusting the pH value of the solution to be detected, and the centrifugal extraction device 800 and the crystallization device 900 are used for obtaining at least part of the metal ions in the solution to be detected.
[0089] In the above embodiment, the second pH adjusting device 700 can cooperate with the first pH adjusting device 500 to form step-by-step adjustment, so as to realize recycling of abundant lithium, nickel, copper and other metal elements in the lithium ion battery recycling material.
[0090] The centrifugal extraction device 800 can adopt a centrifugal extractor, which can efficiently separate the solution containing metal elements by the centrifugal force generated by high-speed rotation, so as to realize selective recovery of metal elements. In this process, the extractant fully contacts the metal ions in the waste liquid and an extraction reaction occurs, thereby improving the recovery rate and purity of the metal elements.
[0091] In addition, the metal elements such as lithium, nickel and cobalt in the lithium ion battery recycling material can be effectively extracted from the waste liquid through crystallization treatment, so as to realize the recycling of resources, avoid the waste of resources, and reduce the demand for new resources.
[0092] The application will be further described in detail below by taking the monitoring of the copper ion concentration in the ternary battery material recycling solution as an example.
[0093] Firstly, based on the detection electrode of the application, the relationship between copper ions and current is established, a series of gradient concentrations (0.1, 0.5 ppm, 1 ppm, 2 ppm, 10 ppm, 20 ppm, 50 ppm) of copper ion solution are configured, and the current intensity generated by the reduction of copper ions is determined by the detection subject by differential pulse voltammetry, and the relationship between current and copper ion concentration is established as the following linear calibration formula:
[0094] y = 3.2x + 0.17
[0095] Wherein, y is the current density, unit: μA / cm 2 , x is the copper ion concentration, unit: ppm.
[0096] Secondly, after the black powder of the broken waste ternary battery is leached by sulfuric acid, the black powder acidic solution is obtained. Then, the insoluble substances are filtered out, and the sulfidation agent sodium sulfide is added to the filtrate for copper removal by sulfidation, and then the copper sulfide precipitate is filtered out. The filtrate after removing the copper sulfide precipitate is sampled by the detection device of the application, the diameter of the sampling pipeline is 1.5 mm, 30 mL of sample is taken, and the liquid enters the detection container through the sampling pipeline, and the concentration of copper ions in the sample is determined by the electrochemical differential pulse voltammetry method.
[0097] According to the current intensity 5.85 μA / cm 2 determined by the detection subject, the concentration of copper ions in the sampling solution is inferred to be 1.78 ppm according to the above linear calibration formula.
[0098] The detection device provided in the embodiment of the application is used to measure the solution recovered by the wet method for 6 times, and the measurement results of the above embodiment (Example 1) and other 5 embodiments (Examples 2-6) are shown in Table 1.
[0099] Table 1 results of copper ion online electrochemical detection device embodiments of the present application
[0100]
[0101] As can be seen from Table 1, the detection device (using an electrochemical detection module and an AAS detection module) provided in the embodiments of the present application can accurately detect the ion concentration in the sampling liquid, and the detection is fast and the detection result is stable. By comparing the electrochemical detection method with the atomic absorption spectrometry (AAS), it can be known that the measurement result error of the electrochemical detection method is small, and the electrochemical detection method can be used for accurate measurement of copper ion residues in the wet recovery process of lithium ion batteries.
[0102] Although some specific embodiments of the present application have been described in detail through examples, those skilled in the art should understand that the above examples are only for illustration, and are not intended to limit the scope of the present application. Those skilled in the art should understand that the above embodiments can be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.
Claims
1. A detection device, characterized in that, The application relates to a sampling device for detecting ions in a solution, comprising: a sampling module (1) comprising a sampling pipeline (11); a detection module (2), one end of the sampling pipeline (11) being used for obtaining sampling liquid from a solution to be detected, and the other end of the sampling pipeline (11) being located in the detection module (2), the detection module (2) being used for detecting the concentration of set ions in the sampling liquid in real time; a pressure regulating module (3) connected to the sampling pipeline (11) and used for controlling the air pressure value in the sampling pipeline (11); when the air pressure value in the sampling pipeline (11) is less than or equal to a first low pressure threshold value, the sampling liquid is transported to the detection module (2) through the sampling pipeline (11); and when the air pressure value in the sampling pipeline (11) is greater than or equal to a first high pressure threshold value, the sampling liquid in the sampling pipeline (11) flows back to the solution to be detected.
2. The detection device of claim 1, wherein, The detection module (2) is an electrochemical detection module or an AAS detection module.
3. The detection device of claim 2, wherein, The electrochemical detection module comprises a detection electrode (21), a detection main body (22) and a detection container (23), one end of the detection electrode (21) being connected to the detection main body (22), and the other end of the detection electrode (21) being located in the detection container (23); when the air pressure value in the sampling pipeline (11) is less than or equal to a first low pressure threshold value, the sampling liquid is transported to the detection container (23) through the sampling pipeline (11).
4. The detection device of claim 3, wherein, The detection electrode (21) comprises a detection electrode, a reference electrode and a counter electrode, the surface of the detection electrode being provided with a metal organic framework layer, and the metal organic framework layer being used for complexing with set ions in the sampling liquid.
5. The detection device of claim 4, wherein, The material of the metal organic framework layer is a material synthesized by at least one of nickel, cobalt and manganese and an organic ligand of benzoic acid, or the material of the metal organic framework layer is a material synthesized by at least one of nickel, cobalt and manganese and a derivative of the organic ligand of benzoic acid.
6. The detection device of claim 3, wherein, The device further comprises a waste liquid container (6) and a washing container (7), and the waste liquid container (6) and the washing container (7) are both communicated to the detection container (23); when the air pressure value in the detection container (23) is greater than or equal to a second high pressure threshold value, the sampling liquid in the detection container (23) can be output to the waste liquid container (6); and when the air pressure value in the detection container (23) is less than or equal to a second low pressure threshold value, the washing liquid in the washing container (7) can be input to the detection container (23).
7. The detection device of claim 1, wherein, The pressure regulating module (3) comprises a vacuum component and a pressurizing component, the vacuum component being connected to the sampling pipeline (11) and being capable of making the air pressure value in the sampling pipeline (11) less than or equal to a first low pressure threshold value; the pressurizing component being connected to the sampling pipeline (11) and being capable of making the air pressure value in the sampling pipeline (11) greater than or equal to a first high pressure threshold value.
8. The detection device of claim 1, wherein, The pressure regulating module (3) comprises a piston driving component, and the piston driving component is connected to the sampling pipeline (11).
9. A recycling system characterized by, The detection device (100) according to any one of claims 1-8 is connected to a liquid delivery pipeline (200). The liquid delivery pipeline (200) is used for delivering a solution to be detected, and the sampling pipeline (11) is connected to the liquid delivery pipeline (200).
10. The recycling system of claim 9, wherein, The recovery system comprises, in sequence, an acid leaching device (300), a first filtering device (400), a first pH adjusting device (500), and a second filtering device (600). The acid leaching device (300) is used for acid treatment of the recovered material, and the second filtering device (600) is connected to an input end of the liquid delivery pipeline (200).
11. The recycling system of claim 9, wherein, The recovery system comprises, in sequence, a second pH adjusting device (700), a centrifugal extraction device (800), and a crystallization device (900). The second pH adjusting device (700) is connected to an output end of the liquid delivery pipeline (200) and is used for adjusting the pH value of the solution to be detected, and the centrifugal extraction device (800) and the crystallization device (900) are used for obtaining at least part of metal ions in the solution to be detected.