Carbon dioxide reduction liquid product detection apparatus and analysis method

Abstract

The present application relates to a device for detecting carbon dioxide reduction liquid product and an analysis method, the device comprises a carbon dioxide reduction reactor, an anode electrolyte fluid circuit, a cathode electrolyte fluid circuit, a flow valve, a liquid sample flow cell and a spectral detector, the method is to configure standard solutions with different components and different concentrations for spectral detection calibration, determine the relationship between liquid components, concentration and spectral peak intensity, and then when detecting different carbon dioxide reduction liquid products, the concentration of the liquid can be determined through the components and spectral information of the liquid. Therefore, the present application can efficiently and high-quality detect product information under different carbon dioxide reduction catalyst material systems, reactors and reaction conditions.

Description

Technical Field

[0001] This invention relates to the field of carbon dioxide reduction, and more specifically to a device and method for detecting and analyzing liquid products from carbon dioxide reduction. Background Technology

[0002] Achieving efficient conversion and utilization of carbon dioxide is one of the important ways to solve the problems of rising carbon dioxide concentration and global warming. Carbon dioxide reduction includes thermocatalysis, electrocatalysis, photocatalysis, and bio-enzymatic catalysis. The reduction products of different catalytic reactions are complex and diverse. Among them, liquid products such as formic acid and methanol are important, high-value-added chemical raw materials. Electrocatalysts, represented by bismuth metal, tin metal, and their compounds, can efficiently reduce carbon dioxide to liquid products such as formic acid. However, the carbon dioxide reduction reaction process is complex, with low single-pass conversion rate and low product concentration, making it difficult to quickly and efficiently perform qualitative and quantitative measurement and analysis of the products, thus hindering the evaluation of the reaction process and the assessment of related technologies. Currently, the most commonly used method for detecting liquid products of carbon dioxide reduction is chromatography, including liquid chromatography, ion chromatography, and liquid chromatography-mass spectrometry. Although these methods have high detection sensitivity and can measure multiple products, they suffer from problems such as the inability to detect samples online, complex sample processing methods, and long single detection times, which greatly restrict the development of carbon dioxide reduction research and application. Summary of the Invention

[0003] To address the problems existing in the prior art, the present invention aims to provide a detection device and analysis method for liquid products generated by carbon dioxide reduction. By establishing a correspondence between the concentration of characteristic samples and the intensity of spectral signals, the liquid products generated by carbon dioxide reduction can be tested and analyzed online quickly and efficiently.

[0004] To achieve the above-mentioned objectives of the present invention, in a first aspect, the present invention provides a carbon dioxide reduction liquid product detection device, comprising: a carbon dioxide reduction reactor; an anolyte fluid circuit connected to the carbon dioxide reduction reactor; a cathode electrolyte fluid circuit connected to the carbon dioxide reduction reactor; a flow valve disposed on the cathode electrolyte fluid circuit; a liquid sample flow cell disposed on the cathode electrolyte fluid circuit; and a spectrometer connected to the liquid sample flow cell.

[0005] Furthermore, it also includes a control computer connected to the spectral detector.

[0006] Furthermore, the flow valve is configured as a peristaltic pump flow controller.

[0007] Furthermore, the carbon dioxide reduction reactor, the anode electrolyte fluid circuit, the cathode electrolyte fluid circuit, the flow valve, and the control computer constitute a carbon dioxide reduction reaction section, used to realize the carbon dioxide reduction reaction and generate liquid products.

[0008] Furthermore, the liquid sample flow cell, the spectrometer, and the control computer constitute a detection unit, used to test the collected liquid products and acquire detection data.

[0009] Furthermore, the cathode electrolyte fluid circuit is non-contactly connected to the spectrometer detector through the liquid sample flow cell.

[0010] In a second aspect, the present invention provides a method for analyzing carbon dioxide reduction liquid products using the carbon dioxide reduction liquid product detection device as described in any one of the first aspects above, the method comprising:

[0011] S1, prepare standard solutions with different components and / or different concentrations;

[0012] S2, the various standard solutions in S1 are respectively delivered to the liquid injection flow cell, and the liquid spectral signal is detected by the spectral detector each time to obtain the relationship between liquid components and / or concentrations and spectral peak intensities;

[0013] S3, the liquid product produced by the carbon dioxide reduction reactor is transported to the liquid sample flow cell through the cathode electrolyte fluid circuit under the control of the flow valve;

[0014] S4, using the spectral detector, detect the spectral signal of the unreacted electrolyte in the liquid sample flow cell;

[0015] S5, based on the composition of the liquid being tested, compare it with the corresponding spectral peak intensity in S2 to determine the concentration of the liquid being tested.

[0016] Furthermore, in step S3, the liquid product produced by the carbon dioxide reduction reactor is a liquid product catalyzed by a bismuth-based or tin oxide-based catalyst.

[0017] Furthermore, in step S3, the liquid product produced by the carbon dioxide reduction reactor is formic acid or methanol.

[0018] The carbon dioxide reduction liquid product detection device and analysis method of the present invention can detect product information in real time under different carbon dioxide reduction catalyst material systems, reactors and reaction conditions, which helps to quickly evaluate the reaction process and performance. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of a carbon dioxide reduction liquid product detection device according to an embodiment of the present invention;

[0021] Figure 2 This is a schematic diagram of the spectra of liquid products with the same concentration but different components;

[0022] Figure 3 Schematic diagrams of the spectra of formic acid solutions of different concentrations;

[0023] Figure 4 The graph shows the relationship between the intensity of the characteristic peak of formic acid at wavenumber 710 and its concentration.

[0024] Figure 5 The spectra of the liquid products of carbon dioxide reduction to formic acid under different time conditions are shown. Detailed Implementation

[0025] The description of the embodiments in this specification should be taken in conjunction with the accompanying drawings, which should form part of the complete specification. In the drawings, the shape or thickness of the embodiments may be exaggerated and may be indicated in a simplified or convenient manner. Furthermore, parts of the various structures in the drawings will be described separately; it is worth noting that elements not shown in the figures or not described in words are in a form known to those skilled in the art.

[0026] like Figure 1 As shown, the carbon dioxide reduction liquid product detection device of this embodiment includes a carbon dioxide reduction reactor 1; an anolyte fluid circuit 2 connected to the carbon dioxide reduction reactor 1; a cathode electrolyte fluid circuit 3 connected to the carbon dioxide reduction reactor 1; a flow valve 4 disposed on the cathode electrolyte fluid circuit 3 and the anolyte fluid circuit 2; a liquid sample flow cell 5 disposed on the cathode electrolyte fluid circuit 3; and a spectrometer 6 connected to the liquid sample flow cell 5. Furthermore, it may also include a control computer connected to the spectrometer 6 for controlling sampling and detection. The flow valve 4 is configured as a peristaltic pump flow controller.

[0027] This invention also provides a method for analyzing carbon dioxide reduction liquid products using the carbon dioxide reduction liquid product detection device described above, the method comprising:

[0028] S1, prepare standard solutions with different components and / or different concentrations.

[0029] S2, the various standard solutions in S1 are respectively delivered to the liquid injection flow cell 5, and the liquid spectral signal is detected by the spectrometer 6 each time to obtain the relationship between the liquid components and / or concentrations and the spectral peak intensities.

[0030] It can detect multiple liquids with the same concentration but different components, as well as multiple liquids with the same components but different concentrations, thereby obtaining the relationship between the spectral peak intensities corresponding to different liquid components and different liquid concentrations.

[0031] like Figure 2 The image shown is a spectrum obtained by detecting six liquids of the same concentration but different concentrations in an embodiment of the present invention, namely 1% potassium dihydrogen phosphate, 1% sodium bicarbonate, 1% ethanol, 1% methanol, 1% acetic acid and 1% formic acid.

[0032] like Figure 3 The image shows the spectra obtained by detecting six different concentrations of formic acid solutions in an embodiment of the present invention, namely 20% formic acid, 10% formic acid, 5% formic acid, 2% formic acid, 1% formic acid, 0.5% formic acid and water. Figure 4 This diagram illustrates the characteristic peak intensities of formic acid at different concentrations in the 710 beam. Calibration results show that the spectral detector exhibits excellent linearity and a low detection limit, making it suitable for testing the composition and concentration of liquid products from carbon dioxide reduction and for real-time dynamic analysis and evaluation.

[0033] Therefore, after steps S1 and S2, spectral curves of liquids with different components and concentrations can be obtained, completing the qualitative analysis and concentration calibration of the liquid by the spectral detector.

[0034] S3, the liquid product produced by the carbon dioxide reduction reactor 1 is transported to the liquid sample flow cell 5 through the cathode electrolyte fluid circuit 3 under the control of the flow valve 4.

[0035] S4, the spectral signal of the unreacted electrolyte in the liquid sample flow cell 5 is detected by the spectral detector 6.

[0036] S5. Based on the composition of the liquid being tested, compare it with the corresponding spectral peak intensity in step S2 to determine the concentration of the liquid being tested.

[0037] Since the liquid concentration and spectral characteristic peaks have been calibrated using a standard solution in step S2, the concentration of the current liquid can be deduced after obtaining the spectral characteristic peaks of the current liquid (with known components) in step S5.

[0038] like Figure 5The image shows the spectra of the liquid products after 10 min and 20 min of the carbon dioxide reduction reaction in step S3. The results indicate that this invention can accurately and effectively acquire product concentration information dynamically during the carbon dioxide reduction process. The concentration of the liquid product increases with increasing reaction time, which is consistent with the actual reaction situation. This demonstrates that this invention can be used for rapid online detection and qualitative and quantitative analysis of carbon dioxide reduction products, while effectively solving the problems of long testing cycles, slow speed, and inability to dynamically assess the reaction process in real time using chromatographic methods.

[0039] Furthermore, in the carbon dioxide reduction liquid product detection device and analysis method of this invention, preferably, the carbon dioxide reduction liquid product is a liquid product catalyzed by a bismuth-based or tin oxide-based catalyst, such as formic acid or methanol. Preferably, the flow rate of the cathode electrolyte circuit is kept stable at a fixed value within the range of 1 sccm to 50 sccm to ensure uniform electrolyte flow rate and uniform product concentration distribution. Preferably, the correspondence between the calibrated concentration and the characteristic peak intensity is ensured by testing as many different components and concentrations as possible.

[0040] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A device for detecting liquid products from carbon dioxide reduction, characterized in that, include: Carbon dioxide reduction reactor (1); The anolyte fluid circuit (2) is connected to the carbon dioxide reduction reactor (1); The cathode electrolyte fluid circuit (3) is connected to the carbon dioxide reduction reactor (1); A flow valve (4) is installed on the cathode electrolyte fluid circuit (3); A liquid sample flow cell (5) is installed on the cathode electrolyte fluid circuit (3); A spectrometer (6) is connected to the liquid sample flow cell (5).

2. The carbon dioxide reduction liquid product detection device according to claim 1, characterized in that, It also includes a control computer connected to the spectral detector (6).

3. The carbon dioxide reduction liquid product detection device according to claim 1, characterized in that, The flow valve (4) is configured as a peristaltic pump flow controller.

4. The carbon dioxide reduction liquid product detection device according to claim 2, characterized in that, The carbon dioxide reduction reactor (1), the anode electrolyte fluid circuit (2), the cathode electrolyte fluid circuit (3), the flow valve (4), and the control computer constitute the carbon dioxide reduction reaction section, which is used to realize the carbon dioxide reduction reaction and generate liquid products.

5. The carbon dioxide reduction liquid product detection device according to claim 2, characterized in that, The liquid sample flow cell (5), the spectrometer (6), and the control computer constitute the detection part, which is used to test the collected liquid products and obtain detection data.

6. The carbon dioxide reduction liquid product detection device according to claim 1, characterized in that, The cathode electrolyte fluid circuit (3) is non-contactly connected to the spectrometer detector (6) through the liquid sample flow cell (5).

7. A method for analyzing carbon dioxide reduction liquid products using the carbon dioxide reduction liquid product detection device as described in any one of claims 1-6, characterized in that, The method includes: S1, prepare standard solutions with different components and / or different concentrations; S2, the various standard solutions in S1 are respectively delivered to the liquid injection flow cell (5), and the liquid spectral signal is detected by the spectral detector (6) each time to obtain the relationship between liquid components and / or concentration and spectral peak intensity; S3, the liquid product produced by the carbon dioxide reduction reactor (1) is transported to the liquid sample flow cell (5) through the cathode electrolyte fluid circuit (3) under the control of the flow valve (4); S4, the spectral signal of the unreacted electrolyte in the liquid sample flow cell (5) is detected by the spectral detector (6); S5, based on the composition of the liquid being tested, compare it with the corresponding spectral peak intensity in S2 to determine the concentration of the liquid being tested.

8. The method for analyzing liquid products from carbon dioxide reduction according to claim 7, characterized in that, In S3, the liquid product produced by the carbon dioxide reduction reactor (1) is a liquid product catalyzed by a bismuth-based or tin oxide-based catalyst.

9. The method for analyzing liquid products from carbon dioxide reduction according to claim 7, characterized in that, In S3, the liquid product produced by the carbon dioxide reduction reactor (1) is formic acid or methanol.

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