Device and method for monitoring carbon dioxide mineralization carbon sequestration reaction

Abstract

The present application belongs to the technical field of carbon dioxide capture, utilization and storage, and particularly relates to a novel device for monitoring the degree of carbon dioxide mineralization carbon sequestration reaction in multiple ways, comprising: a CO2 gas storage tank, a mineralization reaction kettle, a CO2 gas analyzer, an embedded pH electrode, a miniature optical fiber spectrometer and a data acquisition terminal. The mineralization reaction kettle is provided with a temperature control unit, a slurry bearing table and a stirring unit. The CO2 gas storage tank is connected to the reaction kettle through a pipeline with a flow control valve. The CO2 gas analyzer, the embedded pH electrode and the miniature optical fiber spectrometer are used to monitor the unreacted CO2 concentration, the slurry pH value and the amount of key phases such as calcium carbonate and calcium hydroxide, respectively. Each monitoring component is electrically connected to the data acquisition terminal. The present application realizes real-time in-situ linkage monitoring of multiple parameters, reduces the disturbance and lag of offline detection, improves the monitoring accuracy and experimental efficiency, and is suitable for monitoring the carbon dioxide mineralization carbon sequestration reaction process of industrial solid waste and natural minerals.

Description

Technical Field

[0001] This invention belongs to the field of carbon dioxide capture, utilization and storage technology, and particularly relates to a device and method for multi-element monitoring of carbon dioxide mineralization and carbon sequestration reactions. Background Technology

[0002] Carbon dioxide mineralization and carbon sequestration technology is an important technique for converting carbon dioxide into stable carbonates and achieving long-term storage. It is widely used in industrial solid waste resource utilization and natural mineral carbon sequestration. Currently, in laboratory and engineering research, batch reactors are often used for mineralization reaction experiments. The reaction process relies on manual control, and after the reaction, samples must be removed, crushed, dried, and ground before offline detection using equipment such as XRD, SEM, and gas chromatography to obtain key data such as reaction conversion rate and phase composition. Most existing monitoring devices can only detect a single parameter. Some devices attempt to integrate multiple monitoring functions, but their overall structure and sensor design have significant flaws, making it difficult to meet the requirements for high-precision and high-stability monitoring.

[0003] Existing equipment monitors only one parameter and cannot simultaneously acquire multi-dimensional data such as carbon dioxide concentration, slurry pH value, and the amount of key phases generated, making it difficult to comprehensively judge the reaction process and degree. Summary of the Invention

[0004] The purpose of this invention is to provide a device and method for multi-element monitoring of carbon dioxide mineralization and carbon fixation reactions, so as to solve the above-mentioned problems.

[0005] To achieve the above objectives, the present invention provides the following solution:

[0006] A multi-element monitoring device for carbon dioxide mineralization and carbon fixation reaction includes: a gas supply mechanism, an absorption reaction mechanism, and a monitoring mechanism.

[0007] The absorption reaction mechanism includes a mineralization reaction vessel, in which a mineralization reaction slurry is placed. A stirring unit for stirring the mineralization reaction slurry is provided on the mineralization reaction vessel, and a temperature control unit is also provided below the mineralization reaction vessel.

[0008] The monitoring device includes a CO2 gas analyzer, a fiber optic spectrometer, and an embedded pH electrode.

[0009] The CO2 gas analyzer is used to monitor the concentration of unreacted gas in the mineralization reactor, the fiber optic spectrometer is used to monitor the amount of product generated in the mineralization reactor, and the embedded pH electrode is used to monitor the pH change of the mineralization slurry.

[0010] Preferably, the mineralization reactor includes a slurry support platform, which is enclosed and placed at the heating end of the temperature control unit. A transparent container for holding the mineralization reaction slurry is located inside the slurry support platform, and the working end of the stirring unit extends into the mineralization reaction slurry.

[0011] Preferably, the material of the slurry support platform includes transparent quartz material.

[0012] Preferably, the slurry support platform is provided with a CO2 air inlet, and the gas supply mechanism includes a CO2 gas storage tank. One end of the CO2 gas storage tank is connected to a gas guide pipe, and the other end of the gas guide pipe is connected to the inner cavity of the slurry support platform through the CO2 air inlet.

[0013] Preferably, a flow control valve is provided on the gas delivery pipe, and the flow control valve is electrically connected to the data acquisition terminal. The embedded pH electrode, the fiber optic spectrometer, and the CO2 gas analyzer are all electrically connected to the data acquisition terminal.

[0014] Preferably, the fiber optic spectrometer is connected to a fiber optic probe, and the probe end of the fiber optic probe is attached to the outer wall of the transparent container.

[0015] Preferably, a CO2 outlet is provided above the slurry support platform, and one end of the CO2 outlet is connected to a detection pipe, the other end of which is connected to the CO2 gas analyzer.

[0016] Preferably, the embedded pH electrode is disposed at the top of the slurry support platform and the probe end extends into the slurry support platform.

[0017] Preferably, the embedded pH electrode is provided with a wear-resistant ceramic protective sleeve on its outer side, and the electrode surface of the embedded pH electrode is coated with a PTFE anti-fouling coating.

[0018] A method for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction, based on the aforementioned device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction, comprises the following steps:

[0019] The prepared mineralization reaction slurry is fed into the mineralization reaction vessel and sealed. The temperature control unit maintains the set temperature in the mineralization reaction vessel, the stirring time of the preset stirring unit is set, and CO2 gas is introduced into the mineralization reaction vessel at the set rate. The pH value change and phase composition information of the mineralization reaction slurry in the mineralization reaction vessel are monitored in real time. The reaction is completed when the reaction time reaches the set time or the pH value of the mineralization reaction slurry stabilizes. The amount of unreacted CO2 gas after the reaction is completed is analyzed.

[0020] Compared with the prior art, the present invention has the following advantages and technical effects:

[0021] This invention achieves real-time, in-situ, linked monitoring of carbon dioxide concentration, slurry pH, and key phase formation through a synergistic design of temperature control, stirring, and online monitoring of ternary parameters. This effectively avoids system disturbances and data lag caused by offline sampling. The simultaneous acquisition and automated analysis of multi-dimensional data simplifies the experimental operation process, shortens the experimental cycle, provides real-time data support for reaction mechanism research and process parameter optimization, improves the overall efficiency of mineralization and carbon fixation experiments, and enables more accurate determination of the reaction endpoint and degree.

[0022] The sealed structure and anti-pollution and anti-wear probe design in this invention improve the service life and detection stability of the monitoring components and reduce errors in the monitoring process; precise temperature control and uniform stirring ensure the stability of the reaction system, making the mineralization reaction process more controllable and the data repeatability better, providing reliable monitoring support for the research and application of mineralization carbon fixation technology. Attached Figure Description

[0023] 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:

[0024] Figure 1 This is a schematic diagram of the overall structure of the present invention;

[0025] Figure 2 This is a flowchart of the method of the present invention;

[0026] The components include: 1. CO2 gas storage tank; 2. Gas delivery pipeline; 3. Flow control valve; 4. CO2 inlet; 5. Mineralization reactor; 51. Temperature control unit; 52. Slurry support platform; 53. Stirring unit; 6. Embedded pH electrode; 7. Fiber optic spectrometer; 8. Fiber optic probe; 9. CO2 gas analyzer; 10. Detection pipeline; 11. CO2 outlet; 12. Data acquisition terminal; and 13. Mineralization reaction slurry. Detailed Implementation

[0027] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0029] Reference Figure 1 As shown in Figure 2, this invention discloses a multi-element monitoring device for carbon dioxide mineralization and carbon fixation reaction, comprising: a gas supply mechanism, an absorption reaction mechanism, and a monitoring mechanism;

[0030] The absorption reaction mechanism includes a mineralization reactor 5, a mineralization reaction slurry 13 is placed inside the mineralization reactor 5, a stirring unit 53 for stirring the mineralization reaction slurry 13 is provided on the mineralization reactor 5, and a temperature control unit 51 is also provided below the mineralization reactor 5.

[0031] The monitoring devices include a CO2 gas analyzer 9, a fiber optic spectrometer 7, and an embedded pH electrode 6.

[0032] The CO2 gas analyzer 9 is used to monitor the concentration of unreacted gas in the mineralization reactor 5, the fiber optic spectrometer 7 is used to monitor the amount of product generated in the mineralization reactor 5, and the embedded pH electrode 6 is used to monitor the pH change of the mineralization slurry 13.

[0033] The impeller of the stirring unit 53 is made of titanium alloy and coated with an anti-corrosion coating to extend its service life.

[0034] The gas supply mechanism provides the reaction gas source, and the mineralization reaction slurry 13 is placed in the mineralization reaction vessel 5 of the absorption reaction mechanism. The reaction conditions are maintained by the stirring unit 53 and the temperature control unit 51. The monitoring mechanism uses the CO2 gas analyzer 9, the fiber optic spectrometer 7, and the embedded pH electrode 6 to monitor the concentration of unreacted gas, the amount of product generated, and the pH change of the mineralization reaction slurry 13, respectively, to achieve multi-dimensional synchronous monitoring.

[0035] Further optimization of the scheme: the mineralization reactor 5 includes a slurry support platform 52, which is enclosed and placed at the heating end of the temperature control unit 51. A transparent container for holding the mineralization reaction slurry 13 is located inside the slurry support platform 52, and the working end of the stirring unit 53 extends into the mineralization reaction slurry 13.

[0036] The mineralization reactor 5 is equipped with a closed slurry support platform 52 and is placed at the heating end of the temperature control unit 51. The mineralization reaction slurry 13 is located inside the slurry support platform 52. The working end of the stirring unit 53 extends into the mineralization reaction slurry 13 to ensure uniform mixing and heating of the slurry.

[0037] The design was further optimized so that the material of the slurry support platform 52 includes transparent quartz.

[0038] The slurry support platform 52 is made of transparent quartz material, which has both corrosion resistance and good light transmittance, making it suitable for reaction observation and spectral monitoring needs.

[0039] To further optimize the design, a CO2 inlet 4 is provided on the slurry support platform 52. The gas supply mechanism includes a CO2 gas storage tank 1, one end of which is connected to a gas guide pipe 2. The other end of the gas guide pipe 2 is connected to the inner cavity of the slurry support platform 52 through the CO2 inlet 4.

[0040] The slurry support platform 52 has a CO2 inlet 4. The CO2 gas storage tank 1 is connected to the CO2 inlet 4 through the gas guide pipe 2, forming a stable and sealed CO2 supply channel.

[0041] The scheme is further optimized by installing a flow control valve 3 on the gas delivery pipe 2. The flow control valve 3 is electrically connected to the data acquisition terminal 12. The embedded pH electrode 6, fiber optic spectrometer 7, and CO2 gas analyzer 9 are all electrically connected to the data acquisition terminal 12.

[0042] Data acquisition terminal 12 has built-in data processing software that can simultaneously analyze CO. 22 Gas concentration, pH value, and spectral signal data are used to analyze the phase content of calcium carbonate and calcium hydroxide in the slurry through a spectral characteristic peak matching algorithm, and real-time change curves and quantitative analysis reports are generated.

[0043] The temperature control unit 51 is an electric heating mantle or a semiconductor cooling chip, with a temperature adjustment range of 0-100℃ and a temperature control accuracy of ±0.5℃. It is used to maintain a constant temperature in the reaction system and avoid temperature fluctuations from affecting the mineralization reaction rate.

[0044] The gas delivery pipe 2 is equipped with a flow control valve 3. The flow control valve 3, the embedded pH electrode 6, the fiber optic spectrometer 7, and the CO2 gas analyzer 9 are all electrically connected to the data acquisition terminal 12 to realize flow regulation and synchronous acquisition and processing of multi-parameter data.

[0045] To further optimize the design, the fiber optic spectrometer 7 is connected to a fiber optic probe 8, with the probe end of the fiber optic probe 8 attached to the outer wall of the transparent container.

[0046] The fiber optic probe 8 has an optical lens at its detection end, and a fluororubber sealing gasket is provided at the connection between the fiber optic probe 8 and the slurry support platform 52 to prevent CO2 buildup. 22 Gas leak.

[0047] The fiber optic spectrometer 7 is connected to the fiber optic probe 8. The probe 8 extends into the slurry support platform 52 to directly acquire the slurry spectral signal.

[0048] To further optimize the design, a CO2 outlet 11 is provided above the slurry support platform 52. The CO2 outlet 11 is connected to one end of the detection pipe 10, and the other end of the detection pipe 10 is connected to the CO2 gas analyzer 9.

[0049] A CO2 outlet 11 is opened above the slurry support platform 52, which is connected to the CO2 gas analyzer 9 through the detection pipeline 10 to form a closed tail gas detection channel.

[0050] The design was further optimized by placing the embedded pH electrode 6 at the top of the slurry support platform 52 and extending the probe end into the slurry support platform 52.

[0051] An embedded pH electrode 6 is fixed to the top of the slurry support platform 52, and the probe extends into the slurry support platform 52 to monitor the pH change of the mineralization reaction slurry 13 in situ in real time.

[0052] Further optimization of the design: the outer side of the embedded pH electrode 6 is equipped with a wear-resistant ceramic protective sleeve, and the electrode surface of the embedded pH electrode 6 is coated with a PTFE anti-fouling coating.

[0053] The embedded pH electrode 6 is equipped with a wear-resistant ceramic protective sleeve on the outside, and the surface is coated with a PTFE anti-fouling coating to reduce wear and contamination and ensure monitoring accuracy.

[0054] A method for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction, based on a device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction, comprises the following steps:

[0055] The prepared mineralization reaction slurry 13 is fed into the mineralization reaction vessel 5 and sealed. The temperature control unit 51 maintains the set temperature in the mineralization reaction vessel 5. The stirring time of the stirring unit 53 is preset. CO2 gas is introduced into the mineralization reaction vessel 5 at the set rate. The pH value change and phase composition information of the mineralization reaction slurry 13 in the mineralization reaction vessel 5 are monitored in real time. When the reaction time reaches the set time or the pH value of the mineralization reaction slurry 13 stabilizes, the reaction is completed. The amount of unreacted CO2 gas after the reaction is completed is analyzed.

[0056] First, the prepared mineralization reaction slurry 13 is placed into the slurry support platform 52. After sealing the vessel, the reaction temperature is set through the temperature control unit 51. Once the temperature stabilizes, the stirring unit 53 is started, and the flow control valve 3 is adjusted to control the CO2 injection rate, thus initiating the mineralization reaction. During the reaction, the embedded pH electrode 6 monitors the pH value changes in real time. Once the pH value stabilizes or the preset time is reached, the reaction ends. The flow control valve 3 and the temperature control unit 51 are then closed. The CO2 gas analyzer 9 and the miniature fiber optic spectrometer 7 complete data acquisition, and all data is transmitted to the data acquisition terminal 12 for analysis and output.

[0057] Example:

[0058] Take fly ash with a particle size of 100-200 mesh and water at a mass ratio of 2:3 to prepare mineralization reaction slurry 13. After stirring evenly, put it into the slurry support platform 52.

[0059] The temperature of the temperature control unit 51 is set at 24.85℃, with fluctuations... Once the temperature is considered stable, start the stirring unit 53, set the stirring speed to 200 r / min, and the stirring time to 30 min; open the flow control valve 3 and adjust the CO2. 22 The infusion rate is 50 ml / min, CO 22 The gas is dispersed into the mineralization reaction slurry 13 through the gas guide pipe 2 and the CO2 inlet 4;

[0060] During the reaction, the probe end of the embedded pH electrode 6 was moved into the mineralization reaction slurry 13, and the pH value of the slurry was monitored to gradually decrease from the initial 11.2 to 7.8 and stabilize; after the reaction, CO 22 Gas analyzer 9 detected an unreacted CO2 concentration of 5%. Using an incoming concentration of 100% as a baseline, the CO2 concentration was calculated. 22 The absorption rate was 95%; fiber optic spectrometer 7 was used for spectral analysis to determine the amounts of calcium carbonate and calcium hydroxide formed, with the characteristic peak located at 29.4°C. Corresponding to calcium carbonate, 34.1 Corresponding calcium hydroxide;

[0061] Data acquisition terminal 12 synchronously generates CO 22 Concentration change curves, pH value change curves, and phase content analysis diagrams were used to verify the accuracy of the device.

[0062] Signal Acquisition and Preprocessing: During the reaction process, the data acquisition terminal 12 synchronously acquires signals from each sensor at a frequency of 1 second / time. For the spectral signals acquired by the fiber optic spectrometer 7, the terminal's built-in software first uses the Savitzky-Golay smoothing filter algorithm to remove noise interference and performs baseline correction to eliminate the influence of background light.

[0063] Data fitting and quantitative calculation:

[0064] The terminal is based on the formula Real-time integral calculation of CO 22 Cumulative absorption. (Among them) The gas flow rate is... Inlet concentration, Let t be the outlet concentration.

[0065] The terminal employs the characteristic peak area integration method combined with a preset standard curve for quantitative analysis. The software automatically identifies the characteristic spectral band of calcium carbonate, calculates the integrated area of ​​the characteristic peak, substitutes it into the pre-established "peak area-concentration" standard curve equation, and calculates the correlation coefficient. Real-time inversion of the concentration of calcium carbonate formation in the slurry (g / L).

[0066] Experimental results verify:

[0067] When the reaction proceeded for 30 minutes, the real-time curve displayed on the data acquisition terminal indicated that the reaction had reached equilibrium. The pH value decreased rapidly from the initial 11.2 and stabilized at 7.82±0.05 around the 25th minute; CO at the outlet... 22 The concentration gradually decreased from the initial 100% (displacement phase), stabilizing at 5.1% at the end of the reaction. The calculated CO... 22 The total absorption was 95.2%. Spectroscopic analysis showed that the intensity of the characteristic peak of calcium carbonate continued to increase as the reaction proceeded. According to the algorithm inversion calculation, the amount of calcium carbonate generated in the slurry at the end of the reaction was 12.5 g / L, which was in high agreement with the value of 12.3 g / L obtained by offline thermogravimetric analysis (TGA) after the reaction. The relative error was only 1.6%, which verified the accuracy and reliability of the in-situ monitoring of this device.

[0068] Finally, the terminal automatically generates a data entry containing absorbed CO. 22 Experimental report on concentration curves, pH dynamic change curves, and key phase growth kinetics curves.

[0069] In the description of this invention, it should be understood that the terms "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this invention, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.

[0070] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A device for monitoring the carbon dioxide mineralization and carbon fixation reaction, characterized in that, include: Gas supply system, absorption and reaction system, and monitoring system; The absorption reaction mechanism includes a mineralization reaction vessel (5), a mineralization reaction slurry (13) is placed inside the mineralization reaction vessel (5), a stirring unit (53) for stirring the mineralization reaction slurry (13) is provided on the mineralization reaction vessel (5), and a temperature control unit (51) is also provided below the mineralization reaction vessel (5). The monitoring device includes a CO2 gas analyzer (9), a fiber optic spectrometer (7), and an embedded pH electrode (6). The CO2 gas analyzer (9) is used to monitor the concentration of unreacted gas in the mineralization reactor (5), the fiber optic spectrometer (7) is used to monitor the amount of product generated in the mineralization reactor (5), and the embedded pH electrode (6) is used to monitor the pH change of the mineralization reaction slurry (13).

2. The device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to claim 1, characterized in that: The mineralization reactor (5) includes a slurry support platform (52), which is enclosed and placed at the heating end of the temperature control unit (51). A transparent container for holding the mineralization reaction slurry (13) is located inside the slurry support platform (52), and the working end of the stirring unit (53) extends into the mineralization reaction slurry (13).

3. The device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to claim 2, characterized in that: The slurry support platform (52) is made of transparent quartz material.

4. The device for monitoring the carbon dioxide mineralization and carbon fixation reaction according to claim 2, characterized in that: The slurry support platform (52) is provided with a CO2 inlet (4), and the gas supply mechanism includes a CO2 gas storage tank (1). One end of the CO2 gas storage tank (1) is connected to a gas guide pipe (2), and the other end of the gas guide pipe (2) is connected to the inner cavity of the slurry support platform (52) through the CO2 inlet (4).

5. The device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to claim 4, characterized in that: A flow control valve (3) is provided on the gas guide pipe (2). The flow control valve (3) is electrically connected to the data acquisition terminal (12). The embedded pH electrode (6), the fiber optic spectrometer (7), and the CO2 gas analyzer (9) are all electrically connected to the data acquisition terminal (12).

6. The apparatus for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to claim 2, characterized in that: The fiber optic spectrometer (7) is connected to a fiber optic probe (8), and the probe end of the fiber optic probe (8) is attached to the outer wall of the transparent container.

7. The device for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to claim 2, characterized in that: A CO2 outlet (11) is provided above the slurry support platform (52). The CO2 outlet (11) is connected to one end of a detection pipe (10), and the other end of the detection pipe (10) is connected to the CO2 gas analyzer (9).

8. The device for monitoring the carbon dioxide mineralization and carbon fixation reaction according to claim 2, characterized in that: The embedded pH electrode (6) is located at the top of the slurry support platform (52) and its probe extends into the mineralization reaction slurry (13).

9. The device for monitoring the carbon dioxide mineralization and carbon fixation reaction according to claim 1, characterized in that: The embedded pH electrode (6) is provided with a wear-resistant ceramic protective sleeve on the outside, and the electrode surface of the embedded pH electrode (6) is coated with a PTFE anti-fouling coating.

10. A method for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction, based on the apparatus for multi-element monitoring of carbon dioxide mineralization and carbon fixation reaction according to any one of claims 1-9, characterized in that, The steps are as follows: The prepared mineralization reaction slurry (13) is fed into the mineralization reactor (5) and sealed. The temperature control unit (51) keeps the mineralization reactor (5) at the set temperature. The stirring time of the stirring unit (53) is preset. CO2 gas is introduced into the mineralization reactor (5) at the set rate. The pH value change and phase composition information of the mineralization reaction slurry (13) in the mineralization reactor (5) are monitored in real time. When the reaction time reaches the set time or the pH value of the mineralization reaction slurry (13) stabilizes, the reaction is completed. The amount of unreacted CO2 gas after the reaction is completed is analyzed.

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