System and method for detecting trace iron in manganese sulfate solution

Abstract

The invention discloses a detection system and a detection method for trace iron in a manganese sulfate solution. The detection system comprises a liquid supply unit, a detection unit and a control unit, the detection unit comprises a detection tube, a light source emitter and a light source receiver, the light source emitter and the light source receiver are arranged on the two sides of the detection tube respectively in the diameter direction of the detection tube, a stirring assembly is arranged in the detection tube, and a liquid outlet controlled by an electromagnetic valve to be opened and closed is formed in the bottom of the detection tube; the liquid supply unit is connected with the detection pipe through a liquid adding pump and a pipeline and supplies liquid to the detection pipe; the control system is used for controlling the light source emitter, the light source receiver and all the liquid adding pumps; the detection method is realized by adopting the detection system. According to the detection system and the corresponding detection method, the detection efficiency and the detection precision can be effectively improved, and the labor cost is remarkably reduced, so that online detection of trace iron in the manganese sulfate solution and real-time monitoring of the iron content are realized, and efficient information feedback is provided for production.

Description

Technical Field

[0001] The present invention relates to the technical field of material detection equipment, and in particular to a detection system and a detection method for trace iron in a manganese sulfate solution, which can improve detection efficiency and reduce detection costs. Background Art

[0002] During the manganese electrolysis process, excessive impurity iron elements enter the electrolytic cell with the solution, which may cause abnormal conditions of the electrolytic manganese cell, blackening of the plates, and decreased current efficiency. During the solution preparation process, it is necessary to frequently conduct quantitative detection of Fe in the solution. In actual production, manual sampling is used during the preparation process to detect the iron element in the solution until it meets the standard before it can be released. However, this process requires multiple solid-liquid separations and solution transfers before entering the electrolytic cell. In order to ensure that no impurities are introduced during the solution flow, detection is required in each process. Repeated sampling requires a lot of manpower, and there are situations such as untimely analysis, which will lead to slow process flow.

[0003] Similarly, in the production and liquid preparation process of other manganese-based materials such as manganese sulfate, it is also necessary to frequently analyze and test the trace iron elements in the solution to ensure that the predetermined value is reached. Especially in the middle and late stages of production, it is only necessary to confirm whether new impurities are introduced into the solution. However, in current production practices, manual sampling is carried out in the laboratory for quantitative testing, and the data is fed back before entering the next step. Summary of the invention

[0004] The invention provides a detection system and a detection method for trace iron in a manganese sulfate solution, which are used to solve the technical problems of low detection efficiency, poor effect and high cost in the prior art detection method for trace iron in manganese sulfate.

[0005] In order to solve the above technical problems, the technical solution proposed by the present invention is: A detection system for trace iron in a manganese sulfate solution, comprising a liquid supply unit, a detection unit and a control unit, wherein the liquid supply unit comprises a pure water liquid supply device, a dilute nitric acid liquid supply device, a potassium thiocyanate liquid supply device, an n-butanol liquid supply device, a standard solution liquid supply device and a test liquid liquid supply device; the detection unit comprises a detection tube, a light source transmitter and a light source receiver, wherein the light source transmitter and the light source receiver are respectively arranged on both sides of the detection tube along the diameter direction of the detection tube, a stirring assembly is arranged in the detection tube, and a liquid outlet controlled to be opened and closed by a solenoid valve is arranged at the bottom of the detection tube; The pure water supply device, the dilute nitric acid supply device, the potassium thiocyanate supply device, the n-butanol supply device, the iron standard solution supply device and the test liquid supply device are respectively connected to the detection tube through corresponding numbers of liquid adding pumps and pipelines and supply liquid to the detection tube; The control system is used to control the light source transmitter, the light source receiver and all the liquid adding pumps.

[0006] As a further preferred embodiment of the above technical solution, the test liquid supply device is connected to a product storage device of the manganese sulfate production system or a manganese sulfate solution storage device of the manganese electrolysis system through a liquid extraction pipeline.

[0007] As a further preferred embodiment of the above technical solution, the detection system for trace iron in manganese sulfate solution further includes a waste liquid collection device, and the liquid outlet of the detection tube is connected to the liquid inlet of the waste liquid collection device through a pipeline.

[0008] As a further preferred embodiment of the above technical solution, the solenoid valve is connected to a control system and is controlled by the control system.

[0009] As a further preferred embodiment of the above technical solution, the detection tube is a cylindrical glass tube with a volume of 50 mL.

[0010] Based on the same technical concept, the present invention also provides a method for detecting trace iron in a manganese sulfate solution, which uses the detection system of the above technical solution for detection, and comprises the following steps: (1) adding pure water to the pure water supply device, adding 1+1 nitric acid to the dilute nitric acid supply device, adding a potassium thiocyanate solution with a mass concentration of 18% to the potassium thiocyanate supply device, adding analytical pure n-butanol to the n-butanol supply device, adding a 2 mg / L iron standard solution to the standard solution supply device, and adding a test solution to the test solution supply device; (2) Turn on the liquid adding pump corresponding to the pure water supply device, quantitatively add 45 mL of pure water into the detection tube, and at the same time turn on the stirring component of the detection tube. After stirring and washing for 30 seconds, turn on the solenoid valve of the detection tube to discharge the washing water; (3) Turn on the dosing pump corresponding to the standard solution supply device, quantitatively add 20 mL of iron standard solution into the detection tube, then turn on the dosing pump corresponding to the dilute nitric acid supply device, quantitatively add 2 mL of 1+1 nitric acid into the detection tube, turn on the stirring component of the detection tube, and then turn on the dosing pumps corresponding to the potassium thiocyanate supply device and the n-butanol supply device in sequence, quantitatively add 2 mL of potassium thiocyanate solution and 10 mL of n-butanol into the detection tube in sequence, turn off the stirring component 10 seconds after the n-butanol is added, let it stand for 30 seconds, turn on the light source transmitter and the light source receiver, and obtain the correlation coefficient according to the light attenuation intensity between the light source transmitter and the receiver; (4) Repeat the washing operation of step (2). After washing, turn on the liquid adding pump corresponding to the test solution supply device, quantitatively add 20 mL of the test solution into the detection tube, then turn on the liquid adding pump corresponding to the dilute nitric acid supply device, quantitatively add 2 mL of 1+1 nitric acid into the detection tube, turn on the stirring component of the detection tube, and then turn on the liquid adding pumps corresponding to the potassium thiocyanate supply device and the n-butanol supply device in sequence, quantitatively add 2 mL of potassium thiocyanate solution and 10 mL of n-butanol into the detection tube in sequence, turn off the stirring component 10 seconds after the n-butanol is added, let it stand for 30 seconds, turn on the light source transmitter and the light source receiver, and calculate the iron content in the test solution according to the light attenuation intensity and correlation coefficient between the light source transmitter and the receiver.

[0011] Compared with the prior art, the present invention has the following beneficial effects: The detection system and corresponding detection method of the present invention can effectively improve the detection efficiency and detection accuracy, and significantly reduce the labor cost. Compared with manual operation, the device of the present invention can significantly improve the sample detection efficiency and the turnover efficiency of the device. The online analysis system can increase the sampling frequency and make the process control more accurate and effective, thereby realizing the online detection of trace iron in the manganese sulfate solution and the real-time monitoring of the iron content, providing efficient information feedback for production. At the same time, the device of the present invention is embedded in the manganese sulfate production system or the electrolytic manganese system, and can be connected with the integrated control system and the intelligent production control system. By setting the standard value for comparison, the function of over-standard warning or automatic release is realized, thereby improving the production intelligence and digital control level.

[0012] The present invention will be further described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The drawings constituting a part of this application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 Schematic diagram of the structure of the detection system for trace iron in manganese sulfate solution of Example 1.

[0014] Legend: 11. Pure water liquid supply device; 12. Dilute nitric acid liquid supply device; 13. Potassium thiocyanate liquid supply device; 14. n-butanol liquid supply device; 15. Standard solution liquid supply device; 16. Test liquid liquid supply device; 17. Liquid adding pump; 21. Detection tube; 22. Light source transmitter; 23. Light source receiver; 211. Stirring assembly; 212. Solenoid valve; 3. Waste liquid collection device. DETAILED DESCRIPTION

[0015] The embodiments of the present invention are described in detail below with reference to the accompanying drawings, but the present invention can be implemented in many different ways as defined and covered by the claims.

[0016] Embodiment 1: like Figure 1 As shown, the detection system for trace iron in manganese sulfate solution of this embodiment includes a liquid supply unit, a detection unit and a control unit.

[0017] The liquid supply unit includes a pure water liquid supply device 11, a dilute nitric acid liquid supply device 12, a potassium thiocyanate liquid supply device 13, a n-butanol liquid supply device 14, a standard solution liquid supply device 15 and a test liquid liquid supply device 16. The pure water liquid supply device 11, the dilute nitric acid liquid supply device 12, the potassium thiocyanate liquid supply device 13, the n-butanol liquid supply device 14, the standard solution liquid supply device 15 and the test liquid liquid supply device 16 are respectively connected to the detection tube 21 through a corresponding number of liquid adding pumps 17 and pipelines and supply liquid to the detection tube 21; the test liquid supply device 16 can be connected to the product storage device (solution storage tank) of the manganese sulfate production system through a liquid extraction pipeline, and extract the test liquid from the product storage device for detection.

[0018] The detection unit includes a waste liquid collection device 3, a detection tube 21, a light source transmitter 22 and a light source receiver 23. The light source transmitter 22 and the light source receiver 23 are respectively arranged on both sides of the detection tube 21 along the diameter direction of the detection tube 21. The detection tube 21 has a volume of 50 mL and a cylindrical shape. A stirring assembly 211 (magnetic stirrer) is arranged therein. A liquid outlet controlled by a solenoid valve 212 is arranged at the bottom of the detection tube 21. The liquid outlet of the detection tube 21 is connected to the liquid inlet of the waste liquid collection device 3.

[0019] The control system is a PLC controller, which is connected to the solenoid valve 212, the light source transmitter 22, the light source receiver 23 and each liquid adding pump 17, and controls the operation of the above devices.

[0020] The detection system for detecting trace iron in manganese sulfate solution of this embodiment is used for detection, comprising the following steps: (1) The control system controls the liquid adding pump 17 to quantitatively add 45 ml of pure water from the pure water supply device 11 into the detection tube 21. At the same time, the magnetic stirrer is controlled to start stirring and washing for 30 seconds. After washing is completed, the solenoid valve 212 at the bottom of the detection tube 21 is controlled to open, so that the washing water enters the wastewater collection device 3.

[0021] (2) After washing is completed, the analysis work begins. First, the control system controls the liquid adding pump 17 to work, and quantitatively add 20 ml of iron standard solution from the standard solution supply device 15 to the detection tube 21. Then, the liquid adding pump 17 is controlled to work, and 2 ml of 1+1 nitric acid is quantitatively added from the dilute nitric acid supply device 12 to the detection tube 21. Then, the magnetic stirrer is controlled to start, and 2 ml of 18% potassium thiocyanate solution is quantitatively added from the potassium thiocyanate supply device 13 to the detection tube 21. Then, 10 ml of n-butanol is added from the n-butanol supply device 14 to the detection tube 21. The stirring is continued for 10 seconds and then stopped. The mixture is allowed to stand for 30 seconds. The control system controls the light source transmitter 22 to emit light, and records the light attenuation intensity between the light source transmitter 22 and the light source receiver 23. The correlation coefficient (and standard curve) is calculated with the standard solution for subsequent analysis and calculation of the solution to be tested.

[0022] (3) After the standard solution analysis is completed, the electromagnetic valve 212 at the bottom of the detection tube is controlled to open, and the solution flows into the waste liquid collection device 3 to continue the analysis of the solution to be tested.

[0023] (4) The control system controls the liquid adding pump 17 to add 45 ml of pure water from the pure water supply device 11 to the detection tube, and at the same time controls the magnetic stirrer to start, stirring and washing for 30 seconds. After the washing is completed, the electromagnetic valve 212 at the bottom of the detection tube is controlled to open, and the washing water enters the wastewater collection device 3. After the washing is completed, the analysis of the test liquid begins. First, the control system controls the liquid adding pump 17 to add 20 ml of the test solution from the test solution supply device 16 to the detection tube 21. Then, the liquid adding pump 17 is controlled to add 2 ml of 1+1 nitric acid from the dilute nitric acid supply device 12 to the detection tube 21. Then, the magnetic stirrer is controlled to start, and 2 ml of potassium thiocyanate is added from the potassium thiocyanate supply device 13 to the detection tube 21. 18% potassium thiocyanate solution, continue to add 10ml of n-butanol from the n-butanol liquid supply device 14 to the detection tube 21, continue stirring for 10s and then stop, let it stand for 30s, the control system controls the light source transmitter 22 to emit light, and records the light attenuation intensity between the light source transmitter 22 and the light source receiver 23, and calculates the iron content in the test solution according to the correlation coefficient (and the standard curve), and the analysis is completed.

[0024] The above are only preferred embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and modifications. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application. The above are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. For those skilled in the art, improvements and changes obtained without departing from the technical concept of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A detection system for trace iron in manganese sulfate solution, characterized in that: The invention comprises a liquid supply unit, a detection unit and a control unit, wherein the liquid supply unit comprises a pure water liquid supply device (11), a dilute nitric acid liquid supply device (12), a potassium thiocyanate liquid supply device (13), an n-butanol liquid supply device (14), a standard solution liquid supply device (15) and a test liquid liquid supply device (16); the detection unit comprises a detection tube (21), a light source transmitter (22) and a light source receiver (23), wherein the light source transmitter (22) and the light source receiver (23) are respectively arranged on both sides of the detection tube (21) along the diameter direction of the detection tube (21); a stirring assembly (211) is arranged in the detection tube (21), and a liquid outlet whose opening and closing is controlled by a solenoid valve (212) is arranged at the bottom of the detection tube; The pure water supply device (11), the dilute nitric acid supply device (12), the potassium thiocyanate supply device (13), the n-butanol supply device (14), the standard solution supply device (15) and the test solution supply device (16) are respectively connected to the detection tube (21) through corresponding numbers of liquid adding pumps (17) and pipelines and supply liquid to the detection tube (21); The control system is used to control the light source transmitter (22), the light source receiver (23) and all the liquid adding pumps (17).

2. The detection system according to claim 1, characterized in that: The test liquid supply device (16) is connected to a product storage device of a manganese sulfate production system or a manganese sulfate solution storage device of a manganese electrolysis system via a liquid extraction pipeline.

3. The detection system according to claim 1, characterized in that: It also comprises a waste liquid collection device (3), wherein the liquid outlet of the detection tube (21) is connected to the liquid inlet of the waste liquid collection device (3) via a pipeline.

4. The detection system according to claim 3, characterized in that: The solenoid valve (212) is connected to a control system and is controlled by the control system.

5. The detection system according to any one of claims 1 to 4, characterized in that: The detection tube (21) is a cylindrical glass tube with a volume of 50 mL.

6. A method for detecting trace iron in manganese sulfate solution, characterized in that: The detection system according to any one of claims 1 to 4 is used for detection, comprising the following steps: (1) adding pure water to the pure water supply device (11), adding 1+1 nitric acid to the dilute nitric acid supply device (12), adding a potassium thiocyanate solution with a mass concentration of 18% to the potassium thiocyanate supply device (13), adding analytical pure n-butanol to the n-butanol supply device (14), adding a 2 mg / L iron standard solution to the standard solution supply device (15), and adding a test solution from a product storage device of a manganese sulfate production system or a manganese sulfate solution storage device of a manganese electrolysis system to the test solution supply device (15) through a liquid extraction pipeline; (2) turning on the liquid adding pump (17) corresponding to the pure water supply device (11), quantitatively adding 45 mL of pure water into the detection tube (21), and at the same time turning on the stirring assembly (211) of the detection tube (21), stirring and washing for 30 seconds, and then turning on the detection tube solenoid valve (212) to discharge the washing water; (3) turning on the dosing pump (17) corresponding to the standard solution supply device (15), quantitatively adding 20 mL of the iron standard solution into the detection tube (21), then turning on the dosing pump (17) corresponding to the dilute nitric acid supply device (12), quantitatively adding 2 mL of 1+1 nitric acid into the detection tube (21), turning on the stirring assembly (211) of the detection tube (21), and then turning on the dosing pumps (17) corresponding to the potassium thiocyanate supply device (13) and the n-butanol supply device (14), quantitatively adding 2 mL of potassium thiocyanate solution and 10 mL of n-butanol into the detection tube (21), turning off the stirring assembly (211) 10 seconds after the n-butanol is added, leaving the sample to stand for 30 seconds, then turning on the light source transmitter (22) and the light source receiver (23), and obtaining a correlation coefficient based on the light attenuation intensity between the light source transmitter (22) and the light source receiver (23); (4) Repeat the washing operation of step (2). After the washing is completed, the liquid adding pump (17) corresponding to the liquid supply device (16) of the liquid to be tested is turned on to quantitatively add 20 mL of the liquid to be tested into the detection tube (21). The liquid adding pump (17) corresponding to the dilute nitric acid liquid supply device is then turned on to quantitatively add 2 mL of 1+1 nitric acid into the detection tube (21). After turning on the stirring component (211) of the detection tube (21), the liquid adding pumps (17) corresponding to the potassium thiocyanate liquid supply device (13) and the n-butanol liquid supply device (21) are turned on in sequence to quantitatively add 2 mL of potassium thiocyanate solution and 10 mL of n-butanol into the detection tube (21). After 10 seconds after the n-butanol is added, the stirring component (211) is turned off. After standing for 30 seconds, the light source transmitter (22) and the light source receiver (23) are turned on to calculate the iron content in the liquid to be tested according to the light attenuation intensity and the correlation coefficient between the light source transmitter (22) and the light source receiver (23).

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