Method and device for measuring proportion of organic fluorinated electrolyte

Abstract

The invention relates to a method for measuring the proportion of an organic fluorinated electrolyte, which comprises the following steps of: opening a bypass inlet valve of a liquid inlet pipeline of an electrolytic bath, and enabling the electrolyte to continuously flow through a measuring pipe section with the height of h; the pressure difference delta P between the two ends of the pipe section is obtained through reading feedback of the differential pressure sensor; calculating the real-time density of the electrolyte by using a formula rho = deltaP / (g.h); calling a pre-stored electrolyte density-proportional relation curve or a pre-stored electrolyte density-proportional relation experimental data table in the dynamic calibration database; outputting an electrolyte mass proportion value corresponding to the current density, and displaying the electrolyte mass proportion value on a human-computer interaction interface; opening a bypass outlet valve of a liquid inlet pipeline of the electrolytic cell, and discharging the electrolyte of the measuring pipe section; nitrogen is adopted to carry out purging replacement on the measuring pipe section, and electrolyte residues are reduced. The invention further relates to a measuring device which comprises the fluorination electrolytic cell, the differential pressure liquid level meter and the embedded processor which are connected in sequence, manual sampling and sample sending are not needed, the detection efficiency is higher, and the intrinsic safety requirement is better met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolyte concentration detection, and particularly relates to an organic fluorinated electrolyte proportion measurement method and device, which is especially suitable for online monitoring of electrolyte proportion in the fields of organic electrolyte fluorination and the like. BACKGROUND

[0002] Trifluoromethylsulfonyl fluoride (CF3SO2F) has wide application prospects in the field of fine chemicals, and is an important raw material for various chemical products such as pharmaceutical intermediates, ionic liquids, and lithium ion battery electrolytes. Electrolysis is an important method for preparing trifluoromethylsulfonyl fluoride, which has the advantages of easy availability of raw materials, simple operation, low cost, and suitability for large-scale application. In the process of preparing trifluoromethylsulfonyl fluoride by electrolysis, an undesirable electrolyte proportion can lead to a large amount of side reactions, thereby affecting the product yield. Therefore, controlling the electrolyte proportion and achieving real-time feedback of the electrolyte proportion have become important links to ensure production efficiency.

[0003] Chinese patent CN112630334A discloses a method for detecting the proportion of the organic phase of an electrolyte containing TMSP. TMSP reacts easily with water to generate silanol with a small molecular weight, which can be easily detected and determined by gas chromatography. Therefore, by dissolving the electrolyte with water, the lithium salt in the electrolyte is dissolved in water, a certain proportion of dichloromethane, a strong dissolving solvent, is added as an extractant, mixed thoroughly, and then centrifuged on a high-speed centrifuge to remove the water layer to obtain a pretreated sample of the electrolyte, which is then detected by gas chromatography.

[0004] However, the current methods for measuring the proportion of electrolyte have the following problems:

[0005] (1) Poor adaptability to highly corrosive environments: Organic fluorinated electrolyte has strong corrosiveness to sensor materials, and conventional online instruments for measuring the proportion of electrolyte cannot be used.

[0006] (2) Many problems in manual sampling and detection: Offline analysis involves manual sampling and sampling, which is inefficient, and the obtained electrolyte data has a lag. In addition, manual sampling inevitably poses a risk of poisoning or burns from the material.

[0007] Therefore, there is an urgent need for a non-invasive, corrosion-resistant, and real-time feedback electrolyte proportion measurement scheme. SUMMARY

[0008] The present application aims to provide an organic fluorinated electrolyte proportion measurement method and device, which measures the proportion of electrolyte by directly adding a bypass to the production line pipeline, without the need for manual sampling and sampling, and has higher detection efficiency than traditional titration or chromatography methods.

[0009] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0010] A method for measuring the proportion of organic fluorinated electrolyte, comprising the following steps:

[0011] (1) opening the inlet valve of the electrolytic tank liquid inlet pipeline bypass, making the electrolyte continuously flow through the measuring pipe section with a height of h;

[0012] (2) obtaining the pressure difference ΔP between the two ends of the pipe section through the feedback of the differential pressure sensor;

[0013] (3) calculating the real-time density of the electrolyte by the formula ρ = ΔP / (g·h), wherein g is the acceleration of gravity;

[0014] (4) retrieving the electrolyte density-proportion relationship curve or electrolyte density-proportion relationship experimental data table in the dynamic calibration database, and obtaining the result by mutual evidence of production experience and experimental determination;

[0015] (5) outputting the electrolyte mass proportion value corresponding to the current density and displaying it on the human-computer interaction interface;

[0016] (6) opening the outlet valve of the electrolytic tank liquid inlet pipeline bypass, and discharging the electrolyte in the measuring pipe section;

[0017] (7) using nitrogen to purge and replace the measuring pipe section to reduce the electrolyte residue.

[0018] Preferably, the electrolyte comprises three components, namely sulfuryl organic material, fluorinating agent and conductive agent;

[0019] The sulfuryl organic material is methylsulfonyl chloride or methylsulfonyl fluoride;

[0020] The fluorinating agent is anhydrous hydrogen fluoride;

[0021] The conductive agent is one of lithium fluoride, sodium fluoride, potassium fluoride, potassium bifluoride, antimony pentafluoride and antimony trifluoride.

[0022] Preferably, the measuring pipe section is a vertical pipe with an inner diameter of 10-50 mm and a height h = 0.5-2 m, and the inner wall is coated with a polytetrafluoroethylene layer.

[0023] Preferably, the differential pressure sensor is a double-flange type liquid level transmitter with a range of 0-100 kPa and an accuracy of ±0.2% FS, and the pressure-sensitive diaphragm is made of fluorine-resistant alloy.

[0024] Preferably, steps (3), (4) and (5) are completed by an embedded processor, and the dynamic calibration database is stored.

[0025] Preferably, the source of the dynamic calibration database data is a plurality of electrolyte solutions prepared from a plurality of sets of sulfuryl organic material, fluorination agent and conductive agent, data obtained from densitometer experiments and curve fitting results based on the experimental data.

[0026] Preferably, the measurement tube section is connected to a nitrogen purging tube section, and nitrogen purging is performed after the test is completed, the nitrogen purging time is 1-5 minutes and the purging times is 5-20 times.

[0027] Preferably, the measurement tube section in step (1) is connected to a nitrogen purging device to prevent electrolyte residue.

[0028] Further, an organic fluorinated electrolyte proportion measuring device, comprising a fluorination electrolysis tank, a differential pressure liquid level meter and an embedded processor connected in sequence, the fluorination electrolysis tank is provided with a fluorination electrolysis tank feed pipe, the fluorination electrolysis tank feed pipe is provided with a bypass pipe which is communicated with the fluorination electrolysis tank feed pipe at both ends, the bypass pipe is provided with a bypass feed valve and a bypass discharge valve, a differential pressure liquid level meter is arranged on the pipe between the bypass feed valve and the bypass discharge valve, a nitrogen purging inlet pipe is arranged between the bypass feed valve and the differential pressure liquid level meter, a nitrogen inlet valve is arranged on the nitrogen purging inlet pipe, a nitrogen purging outlet pipe is arranged between the bypass discharge valve and the differential pressure liquid level meter, and a nitrogen outlet valve is arranged on the nitrogen purging outlet pipe.

[0029] The present application has the following advantages:

[0030] The measuring method can measure the proportion of electrolyte by directly adding a bypass to the production line pipeline, without manual sampling and sampling, and compared with the traditional titration method or chromatography method, the detection efficiency is higher and more in line with the intrinsic safety requirements.

[0031] The measuring device has a more easily implemented corrosion prevention scheme, and has a longer service life compared to the probe type detection method. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The present application is an organic fluorinated electrolyte proportion measuring device structure diagram.

[0033] In the drawings, 1 is a fluorination electrolysis tank, 2 is a differential pressure liquid level meter, 3 is an embedded processor, 4 is a fluorination electrolysis tank feed pipe, 5 is a bypass pipe, 6 is a bypass feed valve, 7 is a bypass discharge valve, 8 is a nitrogen purging inlet pipe, 9 is a nitrogen inlet valve, 10 is a nitrogen purging outlet pipe, and 11 is a nitrogen outlet valve. DETAILED DESCRIPTION

[0034] Device example:

[0035] As Figure 1As shown, an organic fluorinated electrolyte proportioning device includes a fluorinated electrolytic tank 1, a differential pressure liquid level meter 2 and an embedded processor 3 connected in sequence, the fluorinated electrolytic tank 1 is provided with a fluorinated electrolytic tank feed pipeline 4, the fluorinated electrolytic tank feed pipeline 4 is provided with a bypass pipeline 5 which is communicated with the fluorinated electrolytic tank feed pipeline 4 at both ends, the bypass pipeline 5 is provided with a bypass feed valve 6 and a bypass discharge valve 7, a differential pressure liquid level meter 2 is arranged on the pipeline between the bypass feed valve 6 and the bypass discharge valve 7, a nitrogen blowing inlet pipeline 8 is arranged between the bypass feed valve 6 and the differential pressure liquid level meter 2, a nitrogen inlet valve 9 is arranged on the nitrogen blowing inlet pipeline 8, a nitrogen blowing outlet pipeline 10 is arranged between the bypass discharge valve 7 and the differential pressure liquid level meter 2, and a nitrogen outlet valve 11 is arranged on the nitrogen blowing outlet pipeline 10.

[0036] During detection, it is confirmed that the nitrogen inlet valve 9 and the nitrogen outlet valve 11 are in closed state, the bypass feed valve 6 and the bypass discharge valve 7 are opened, the electrolyte enters the bypass pipeline 5 through the fluorinated electrolytic tank feed pipeline 4, after 5-10 minutes, the bypass discharge valve 7 is closed first, then the bypass feed valve 6 is closed, after the embedded processor 3 converts the data of the differential pressure liquid level meter 2 into proportional information and feeds back to the human-computer interaction interface, the bypass discharge valve 7 is opened, 5-10 minutes are waited again, the bypass discharge valve 7 is closed, the nitrogen inlet valve 9 and the nitrogen outlet valve 11 are opened, the nitrogen blows away the excess electrolyte through the nitrogen blowing inlet pipeline 8, the blowing time is 3 minutes each time, the electrolyte and the nitrogen after blowing are blown out through the nitrogen blowing outlet pipeline 10, the blowing times are 10 times, after the operation is completed, the nitrogen inlet valve 9 and the nitrogen outlet valve 11 are closed.

[0037] The examples are all tested by using the device of the device example.

[0038] Example 1

[0039] Taking the three-component electrolyte of methylsulfonyl fluoride, hydrogen fluoride and lithium fluoride as an example:

[0040] (1) opening the electrolytic tank inlet pipeline bypass inlet valve, making the electrolyte continuously flow through the measuring pipe section with an inner diameter of 20 mm and a height of 1 m; (2) through the feedback of the indication of the differential pressure sensor, the pressure difference ΔP between the two ends of the pipe section is obtained, which is 11.22 kPa; the differential pressure sensor is a double-flange type liquid level transmitter, the range is 0-100 kPa, the accuracy is ±0.2% FS, and the pressure-sensitive diaphragm is made of fluorine-resistant alloy.

[0041] (3) calculating the real-time density ρ of the electrolyte by using the formula ρ=ΔP / (g·h), which is 1145.33 kg / m 3 ;

[0042] (4) calling the pre-stored electrolyte density-proportionality calibration data table;

[0043] (5) Output the electrolyte mass proportion value corresponding to the current density: ω (HF) = 52.52%, ω (CH3SO2F) = 41.64%, ω (lithium fluoride) = 5.84%;

[0044] (6) Open the electrolytic tank liquid inlet pipeline bypass outlet valve, and drain the electrolyte in the measuring pipe section;

[0045] (7) Use nitrogen to replace the electrolyte in the measuring pipe section to reduce the electrolyte residue.

[0046] Table 1 Density-proportionality experimental data table of electrolyte with methylsulfonyl fluoride, hydrogen fluoride and lithium fluoride as electrolyte

[0047]

[0048] Table 1 is four groups of selected experimental calibration values measured by three-component electrolyte, which is only used for the description of the example here.

[0049] Example 2:

[0050] Take the three-component electrolyte of methylsulfonyl chloride, hydrogen fluoride and sodium fluoride as an example:

[0051] (1) Open the electrolytic tank liquid inlet pipeline bypass inlet valve, and make the electrolyte continuously flow through the measuring pipe section with an inner diameter of 10 mm and a height of 0.5 m;

[0052] (2) Through the feedback of the differential pressure sensor, the pressure difference ΔP = 5.084 kPa between the two ends of the pipe section is obtained; the differential pressure sensor is a double-flange type liquid level transmitter, with a range of 0-100 kPa, an accuracy of ±0.2% FS, and a pressure-sensitive diaphragm treated with fluorine-resistant alloy.

[0053] (3) Calculate the real-time density of the electrolyte ρ = 1037.63 kg / m 3 ;

[0054] (4) Retrieve the pre-stored electrolyte density-proportionality calibration data table;

[0055] (5) Output the electrolyte mass proportion value corresponding to the current density: ω (HF) = 74.51%, ω (CH3SO2Cl) = 20.59%, ω (sodium fluoride) = 4.90%;

[0056] (6) Open the electrolytic tank liquid inlet pipeline bypass outlet valve, and drain the electrolyte in the measuring pipe section;

[0057] (7) Use nitrogen to replace the electrolyte in the measuring pipe section to reduce the electrolyte residue.

[0058] Table 2 is a table of experimental calibration data for the electrolyte of methylsulfonyl chloride, hydrogen fluoride, and sodium fluoride

[0059]

[0060]

[0061] Table 2 is a table of experimental calibration data for the electrolyte of methylsulfonyl chloride, hydrogen fluoride, and sodium fluoride

[0062] Example 3:

[0063] For example, the electrolyte of methylsulfonyl fluoride, hydrogen fluoride, and antimony pentafluoride is used as an example:

[0064] (1) Open the bypass inlet valve of the electrolysis tank liquid inlet pipeline, so that the electrolyte continuously flows through the measuring pipe section with an inner diameter of 50 mm and a height of 2 m; (2) Through the reading feedback of the differential pressure sensor, the pressure difference ΔP = 22.30 kPa between the two ends of the pipe section is obtained; the differential pressure sensor is a double-flange type liquid level transmitter, with a range of 0-100 kPa and an accuracy of ±0.2% FS, and the pressure-sensitive diaphragm is made of fluorine-resistant alloy.

[0065] (3) Calculate the real-time density of the electrolyte ρ = 1137.43 kg / m 3 ;

[0066] (4) Retrieve the pre-stored electrolyte density-proportionality calibration data table;

[0067] (5) Output the electrolyte mass proportion value corresponding to the current density: ω(HF) = 66.82%, ω(CH3SO2F) = 19.73%, and ω(antimony pentafluoride) = 13.45%;

[0068] (6) Open the bypass outlet valve of the electrolysis tank liquid inlet pipeline to drain the electrolyte in the measuring pipe section;

[0069] (7) Use nitrogen to purge and replace the measuring pipe section to reduce the residual electrolyte.

[0070] Table 3 is a table of experimental calibration data for the electrolyte of methylsulfonyl fluoride, hydrogen fluoride, and antimony pentafluoride

[0071]

[0072] Table 3 is a table of experimental calibration data for the electrolyte of methylsulfonyl fluoride, hydrogen fluoride, and antimony pentafluoride

[0073] The above-mentioned embodiments are described in more detail and specifically, express the preferred embodiments of the present application, only for illustrating the technical ideas and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, but not only limited to the present application, and cannot be limited to the patent scope of the present application only by the present embodiment, that is, any equivalent changes or modifications made in the spirit disclosed by the present application, for researchers or technicians in the art, without departing from the structure of the present application, the internal improvement of the system and the change between the subsystems, etc., are still within the patent scope of the present application.

Claims

1. A method for measuring the proportion of an organofluorineized electrolyte, characterized in that, Includes the following steps: (1) Open the bypass inlet valve of the electrolytic cell inlet pipeline to allow the electrolyte to flow continuously through the measuring pipe section with a height of h; (2) Obtain the pressure difference ΔP between the two ends of the pipe section by means of the reading feedback of the differential pressure sensor; (3) Calculate the real-time density of the electrolyte using the formula ρ=ΔP / (g·h), where g is the acceleration due to gravity; (4) Retrieve the electrolyte density-proportion relationship curve or the electrolyte density-proportion relationship experimental data table from the dynamic calibration database; (5) Output the electrolyte mass ratio corresponding to the current density; (6) Open the bypass outlet valve of the electrolytic cell inlet pipeline and drain the electrolyte from the measuring tube section; (7) Nitrogen gas was used to purge and replace the measuring pipe section.

2. The method for measuring the proportion of an organofluorineized electrolyte according to claim 1, characterized in that: The electrolyte consists of three components: sulfonyl organic raw material, fluorinating agent, and conductive agent; The sulfonyl organic raw material is methylsulfonyl chloride or methylsulfonyl fluoride; The fluorinating agent is anhydrous hydrogen fluoride; The conductive agent is one of lithium fluoride, sodium fluoride, potassium fluoride, potassium hydrogen fluoride, antimony pentafluoride, and antimony trifluoride.

3. The method for measuring the proportion of an organofluorine electrolyte according to claim 1, characterized in that: The measuring tube section is a vertical tube with an inner diameter of 10-50 mm and a height of h = 0.5-2 m, and the inner wall is coated with a polytetrafluoroethylene layer.

4. The method for measuring the proportion of an organofluorine electrolyte according to claim 1, characterized in that: The differential pressure sensor is a dual-flange type level transmitter with a range of 0 to 100 kPa and an accuracy of ±0.2% FS. The pressure-sensitive diaphragm is treated with a fluorine-resistant alloy.

5. The method for measuring the proportion of an organofluorineized electrolyte according to claim 1, characterized in that: Steps (3), (4), and (5) are all performed by the embedded processor, which stores a dynamic calibration database.

6. The method for measuring the proportion of an organofluorineized electrolyte according to claim 5, characterized in that: The data for the dynamic calibration database comes from multiple electrolytes prepared by dispersive sulfonyl organic raw materials, fluorinating agents and conductive agents, measured by a densitometer, and curve fitting results based on the experimental data.

7. The method for measuring the proportion of an organofluorineized electrolyte according to claim 1, characterized in that: The measuring tube section is connected to a nitrogen purging tube section, and nitrogen purging and replacement are performed after the test. The nitrogen purging and replacement time is 1 to 5 minutes and the number of replacements is 5 to 20.

8. The method for measuring the proportion of an organofluorineized electrolyte according to claim 1, characterized in that: In step (1), the measuring tube section is connected to a nitrogen purging device.

9. A device for measuring the proportion of an organofluorineized electrolyte, characterized in that, The device includes a fluorinated electrolytic cell, a differential pressure level gauge, and an embedded processor connected in sequence. The fluorinated electrolytic cell is equipped with a fluorinated electrolytic cell feed pipe, and a bypass pipe with both ends connected to the fluorinated electrolytic cell feed pipe is provided on the fluorinated electrolytic cell feed pipe. The bypass pipe is equipped with a bypass feed valve and a bypass discharge valve. A differential pressure level gauge is installed on the pipe between the bypass feed valve and the bypass discharge valve. A nitrogen purging inlet pipe is provided between the bypass feed valve and the differential pressure level gauge. A nitrogen inlet valve is installed on the nitrogen purging inlet pipe. A nitrogen purging outlet pipe is provided between the bypass discharge valve and the differential pressure level gauge. A nitrogen outlet valve is installed on the nitrogen purging outlet pipe.

Images