CH4-CO2 hydrate generation prediction system based on temperature and pressure coordinated regulation and control

Abstract

The invention relates to the technical field of natural gas hydrate development and carbon dioxide sequestration, and discloses a CH4-CO2 hydrate generation prediction system based on temperature and pressure coordinated regulation, which comprises a temperature and pressure mixed phase coordinated regulation module used for simulating the real temperature and pressure-mixed phase condition of a seabed reservoir or an industrial reactor so as to control the CH4 / CO2 gas ratio and the liquid phase salinity, and the temperature and pressure mixed phase coordinated regulation module is used for simulating the real temperature and pressure-mixed phase condition of the seabed reservoir or the industrial reactor; outputting a uniform dispersion system; the in-situ pulling and Mannich combined measurement module is used for capturing the lattice embedding sequence and structural evolution of CO2 and CH4 in the hydrate generation process in real time, outputting real-time data and transmitting the real-time data to the data feedback and optimization module; and the data feedback and optimization module is used for receiving the temperature and pressure parameters, the miscible phase proportion and the Raman spectrum characteristic parameters in real time, dynamically adjusting experimental parameters and carrying out intelligent optimization control on the system. The CH4 and CO2 binary hydrate dynamic generation process in-situ monitoring device can realize CH4 and CO2 binary hydrate dynamic generation process in-situ monitoring.

Description

Technical Field

[0001] This invention relates to the field of natural gas hydrate development and carbon dioxide sequestration technology, and in particular to a CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation. Background Technology

[0002] Natural gas hydrates (CH4 hydrates), as an important future energy source, are limited by the harsh low-temperature and high-pressure formation conditions and the risk of formation instability caused by extraction. Carbon dioxide (CO2) hydrates, due to their high thermodynamic stability and environmentally friendly properties, have become an effective carrier for CO2 sequestration. Studies have shown that CO2 and CH4 coexisting can promote hydrate formation through a "displacement effect" or "co-nucleation" mechanism. However, existing technologies face the following limitations: traditional experimental setups cannot accurately simulate the dynamic processes of gas-liquid-solid multiphase systems, resulting in an unclear mechanism by which CO2 influences CH4 hydrate formation in miscible systems through lattice competition and interfacial tension changes; offline sampling can damage the original sample structure, and existing Raman spectroscopy systems lack the ability to capture transient spectral characteristics in the early stages of hydrate nucleation in real time due to the lack of high-pressure reaction chambers and dynamic temperature and pressure control; furthermore, existing technologies often control temperature or pressure parameters in isolation, ignoring the synergistic effect of gas-liquid miscibility on phase equilibrium, leading to significant differences between experimental conditions and real reservoir environments, thus hindering research on hydrate formation mechanisms and technological optimization. Summary of the Invention

[0003] To address the aforementioned problems, the purpose of this invention is to provide a CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation. This system, combined with research on the promoting mechanism of CO2 on natural gas hydrate formation, enables in-situ monitoring of the dynamic formation process of methane (CH4) and carbon dioxide (CO2) binary hydrates.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation, comprising: a temperature, pressure, and miscibility synergistic regulation module, used to simulate the real temperature, pressure, and miscibility conditions of seabed reservoirs or industrial reactors to control the CH4 / CO2 gas ratio and liquid phase salinity, and output a uniformly dispersed system; an in-situ Raman spectral analysis module, used to capture in real time the lattice embedding order and structural evolution of CO2 and CH4 during hydrate formation, output real-time data and transmit it to a data feedback and optimization module; and a data feedback and optimization module, which receives temperature and pressure parameters, miscibility ratio and Raman spectral characteristic parameters in real time, dynamically adjusts experimental parameters, and performs intelligent optimization control of the system.

[0005] Furthermore, the temperature-pressure miscibility coordinated control module includes a high-precision temperature control unit, a dynamic pressure control unit, and a gas-liquid miscibility injection module; The high-precision temperature control unit includes a double-layer constant temperature jacketed reaction chamber. It monitors the temperature gradient inside the double-layer constant temperature jacketed reaction chamber in real time and transmits the real-time monitoring data to the data feedback and optimization module. The dynamic pressure control unit is used to control the injection pressure of CH4 gas, CO2 gas and liquid respectively; The gas-liquid mixed-phase injection module includes a microfluidic mixer, which is used to inject CH4 gas, CO2 gas and liquid into the microfluidic mixer respectively, and to perform controllable mixing under the control of the dynamic pressure regulation unit to generate a uniformly dispersed system.

[0006] Furthermore, the inner layer of the double-layer constant temperature jacketed reaction chamber is made of titanium alloy, the outer layer integrates a semiconductor cooling chip, and a viewing window is provided on the outer layer; a pressure relief valve is provided on the rear side of the double-layer constant temperature jacketed reaction chamber. The double-layer constant temperature jacketed reaction chamber is also equipped with a detachable stirring paddle, and the surface of the detachable stirring paddle blades is hydrophobic. An ultrasonic transducer is also built inside the double-layer constant temperature jacket reaction chamber to enhance gas-liquid mass transfer and improve reaction efficiency.

[0007] Furthermore, the high-precision temperature control unit also includes the Instec hot and cold stage intelligent temperature control system and distributed fiber optic temperature sensors; Distributed fiber optic temperature sensors are installed inside the double-layer constant temperature jacket reaction chamber to monitor the temperature gradient inside the reaction chamber in real time and transmit the data to the Instec hot and cold stage intelligent temperature control system and data feedback and optimization module. The instec hot and cold stage intelligent temperature control system includes a main controller, a cold stage CNC display screen, and a circulating water tank. The main controller controls the semiconductor cooling chip and the circulating water tank based on the received temperature data to control the temperature of the double-layer constant temperature jacket reaction chamber, and the temperature is displayed in real time on the cold stage CNC display screen.

[0008] Furthermore, the dynamic pressure control unit includes a three-channel servo motor, a CO2 high-pressure plunger pump, a CH4 high-pressure plunger pump, and an infusion pump. The three-channel servo motor drives the CO2 high-pressure plunger pump, the CH4 high-pressure plunger pump, and the infusion pump respectively. The CO2 high-pressure plunger pump injects pressure into the CO2 gas in the CO2 cylinder, the CH4 high-pressure plunger pump injects pressure into the CH4 gas in the CH4 high-pressure cylinder, and the infusion pump injects pressure into the liquid in the storage tank.

[0009] Furthermore, proportional control valves are installed on the pipelines between the CO2 high-pressure plunger pump and the CO2 cylinder, the pipelines between the CH4 high-pressure plunger pump and the CH4 high-pressure cylinder, and the pipelines between the infusion pump and the storage tank; the CO2 high-pressure plunger pump, the CH4 high-pressure plunger pump, and the infusion pump are linked with the proportional control valves.

[0010] Furthermore, the gas-liquid mixed-phase injection module includes a microfluidic mixer and an online conductivity meter and gas mass spectrometer; the microfluidic mixer has a CO2 gas inlet, a CH4 gas inlet and a liquid inlet, wherein the two gas inlets are connected to a CO2 gas cylinder and a CH4 high-pressure cylinder respectively, and the liquid inlet is connected to a storage tank; a CO2 pressure gauge is installed at the CO2 gas inlet, a CH4 pressure gauge is installed at the CH4 gas inlet, and a hydraulic pressure gauge is installed at the liquid inlet; An online conductivity meter and a gas mass spectrometer are connected to a microfluidic mixer to monitor the composition of the mixing system within the microfluidic mixer in real time. The microfluidic mixer is also connected to a double-layered thermostatically controlled reaction chamber via piping, which is used to input a uniformly dispersed gas-liquid system into the reaction chamber.

[0011] Furthermore, the microfluidic mixer adopts a T-joint structure with its internal channels configured as serpentine channels; the gas lines at the CO2 gas inlet and the CH4 gas inlet intersect at a 90° angle, the liquid inlet is perpendicular to the gas channels, and the liquid inlet is configured as a tapered converging structure; A micro-serrated structure is set downstream of the T-section junction as a vortex generator. It generates micro-vortices through periodic disturbances, enhances the initial dispersion of gas and liquid, and realizes the controllable mixing of gas and liquid phases from laminar to turbulent flow, outputting a uniformly dispersed system.

[0012] Furthermore, the in-situ Raman spectroscopy module includes a double-layer constant-temperature jacketed reaction chamber, a Raman spectroscopy system, and a computer and numerical control system. The Raman spectroscopy system is used for in-situ high-precision monitoring of the double-layer constant-temperature jacketed reaction chamber during the hydrate formation process, and transmits the monitored spectral data to the computer and numerical control system. The computer and numerical control system is equipped with a signal processing and modeling unit to realize real-time online analysis of spectral data to component ratios.

[0013] Furthermore, the Raman spectroscopy system includes an integrated confocal micro Raman probe and a laser source, which are on the same horizontal plane as the double-layered thermostatic jacketed reaction chamber. The laser source is used to provide laser light to the confocal micro Raman probe, so as to provide lasers of different wavelengths to the sapphire window of the double-layered thermostatic jacketed reaction chamber to alternately excite the sample, and the spectral signal is acquired by the confocal micro Raman probe.

[0014] The present invention has the following advantages due to the adoption of the above technical solutions: This invention simulates the real temperature, pressure, and miscibility conditions of seabed reservoirs or industrial reactors, precisely controlling the CH4 / CO2 gas ratio and liquid phase salinity; it captures the lattice embedding order and structural evolution of CO2 and CH4 in real time during hydrate formation through in-situ Raman spectroscopy; and it establishes a thermodynamic-kinetic model for CO2-promoted hydrate formation based on experimental data, realizing in-situ monitoring of the dynamic formation process of methane (CH4) and carbon dioxide (CO2) binary hydrates. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation in an embodiment of the present invention; Figure 2 This is a schematic diagram of the microfluidic mixer structure in an embodiment of the present invention; Figure label: 1. Three-channel servo motor; 2. CO2 high-pressure plunger pump; 3. CO2 cylinder; 4. CH4 high-pressure plunger pump; 5. CH4 high-pressure cylinder; 6. Storage tank; 7. Infusion pump; 8. CO2 pressure gauge; 9. CH4 pressure gauge; 10. Hydraulic gauge; 11. Tapered conical structure; 12. Microfluidic mixer outlet pressure gauge; 13. Miniature sawtooth (vortex generator); 14. Microfluidic mixer; 15. Serpentine channel; 16. Laser light source; 17. Double-layer constant temperature jacketed reaction chamber; 18. Semiconductor refrigeration chip; 19. Online conductivity meter and gas mass spectrometer; 20. Cold stage CNC display screen; 21. Circulating water tank; 22. Computer and CNC system; 23. Proportional regulating valve; 24. Pressure relief valve; 25. Viewing window; 26. Confocal micro Raman probe; 27. Detachable stirring paddle. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, 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, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0017] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0018] In one embodiment of the present invention, a CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation is provided. This system integrates temperature and pressure regulation, gas-liquid miscibility optimization, and in-situ Raman monitoring, solving the problem of studying the promoting mechanism of CO2 on CH4 hydrate formation. In this embodiment, as... Figure 1 As shown, the system includes: The temperature-pressure-miscibility synergistic control module is used to simulate the real temperature-pressure-miscibility conditions of seabed reservoirs or industrial reactors to control the CH4 / CO2 gas ratio and liquid phase salinity, and output a uniformly dispersed system. The in-situ La Manganese monitoring module is used to capture the lattice embedding order and structural evolution of CO2 and CH4 during the hydrate formation process in real time, output real-time data and transmit it to the data feedback and optimization module. The data feedback and optimization module receives temperature and pressure parameters, mixing ratios, and Raman spectral characteristic parameters in real time, dynamically adjusts experimental parameters, and performs intelligent optimization control of the system.

[0019] In the above embodiments, the temperature-pressure mixed-phase coordinated control module includes a high-precision temperature control unit, a dynamic pressure control unit, and a gas-liquid mixed-phase injection module.

[0020] The high-precision temperature control unit includes a double-layer constant temperature jacketed reaction chamber 17, which monitors the temperature gradient inside the double-layer constant temperature jacketed reaction chamber 17 in real time and transmits the real-time monitoring data to the data feedback and optimization module. A dynamic pressure control unit is used to control the injection pressure of CH4 gas 5, CO2 gas 3 and liquid 6 respectively; The gas-liquid mixed-phase injection module includes a microfluidic mixer, which is used to inject CH4 gas 5, CO2 gas 3 and liquid 6 into the microfluidic mixer respectively, and to perform controllable mixing under the control of the dynamic pressure regulation unit to generate a uniformly dispersed system.

[0021] In this embodiment, the inner layer of the double-layer thermostatic jacketed reaction chamber 17 is made of titanium alloy, and the outer layer integrates a semiconductor cooling chip 18, with a viewing window 25 provided on the outer layer. A pressure relief valve 23 is provided on the rear side of the double-layer thermostatic jacketed reaction chamber 17 for pressure relief after the experiment, facilitating disassembly of the reaction vessel. The viewing window 25 is made of sapphire, which can withstand high-pressure environments and provides good optical transmittance; preferably, the sapphire window has a thickness of 10 mm and a pressure resistance of 60 MPa.

[0022] The double-layered constant-temperature jacketed reaction chamber 17 is equipped with a detachable stirring paddle 27, the rotation speed of which can be adjusted within the range of 0~2000 rpm. The surface of the detachable stirring paddle 27 is hydrophobically treated to effectively reduce the interference of bubble bursting on the experiment. An ultrasonic transducer is also built into the double-layered constant-temperature jacketed reaction chamber 17 to enhance gas-liquid mass transfer and improve reaction efficiency.

[0023] In this embodiment, the high-precision temperature control unit, in addition to the double-layer constant-temperature jacketed reaction chamber 17, also includes the Instec hot and cold stage intelligent temperature control system and a distributed fiber optic temperature sensor. The distributed fiber optic temperature sensor is installed inside the double-layer constant-temperature jacketed reaction chamber 17 to monitor the temperature gradient within the reaction chamber in real time and transmit the data to the Instec hot and cold stage intelligent temperature control system and the data feedback and optimization module. The Instec hot and cold stage intelligent temperature control system includes a main controller, a cold stage CNC display screen 20, and a circulating water tank 21. Based on the received temperature data, the main controller controls the semiconductor cooling chip 18 and the circulating water tank 21 to control the temperature of the double-layer constant-temperature jacketed reaction chamber 17, which is then displayed in real time on the cold stage CNC display screen 20. The temperature range controlled within the double-layer constant-temperature jacketed reaction chamber 17 is 30℃~60℃, with a fluctuation accuracy of ≤±0.05℃.

[0024] In this embodiment, the dynamic pressure control unit includes a three-channel servo motor 1, a CO2 high-pressure plunger pump 2, a CH4 high-pressure plunger pump 4, and an infusion pump 7. The three-channel servo motor 1 drives the CO2 high-pressure plunger pump 2, the CH4 high-pressure plunger pump 4, and the infusion pump 7, respectively. The CO2 high-pressure plunger pump 2 injects pressure into the CO2 gas cylinder 3, the CH4 high-pressure plunger pump 4 injects pressure into the CH4 high-pressure gas cylinder 5, and the infusion pump 7 injects pressure into the liquid (deionized water / saline) in the storage tank 6. In this embodiment, the purity of the CO2 gas in the CO2 gas cylinder 3 is ≥99.99%; the salinity of the saline is 0~5 wt%.

[0025] Proportional regulating valves 23 are installed on the pipelines between the CO2 high-pressure plunger pump 2 and the CO2 cylinder 3, the pipelines between the CH4 high-pressure plunger pump 4 and the CH4 high-pressure cylinder 5, and the pipelines between the infusion pump 7 and the storage tank 6. The three pumps (CO2 high-pressure plunger pump 2, CH4 high-pressure plunger pump 4 and infusion pump 7) are linked with the proportional regulating valves 23 to ensure dynamic adjustment within the pressure range of 0.1~50 MPa. The linkage structure adopted in this embodiment effectively improves the system's response speed and control accuracy, and reduces energy loss.

[0026] In use, the system can achieve precise pressure adjustment through the control of the three-channel servo motor 1, with an accuracy of ±0.01 MPa.

[0027] In this embodiment, the gas-liquid mixed-phase injection module includes a microfluidic mixer 14 and an online conductivity meter and gas mass spectrometer 19. The microfluidic mixer 14 has a CO2 gas inlet, a CH4 gas inlet, and a liquid inlet. The two gas inlets are connected to a CO2 cylinder 3 and a CH4 high-pressure cylinder 5, respectively, and the liquid inlet is connected to a storage tank 6. A CO2 pressure gauge 8 is installed at the CO2 gas inlet, a CH4 pressure gauge 9 is installed at the CH4 gas inlet, and a hydraulic gauge 10 is installed at the liquid inlet. The online conductivity meter and gas mass spectrometer 19 are connected to the microfluidic mixer 14 for real-time monitoring of the composition of the mixed system within the microfluidic mixer 14. The microfluidic mixer 14 is also connected to a double-layered constant-temperature jacketed reaction chamber 17 via piping for inputting a uniformly dispersed gas-liquid system into the reaction chamber.

[0028] Among them, such as Figure 2 As shown, the microfluidic mixer 14 adopts a T-joint structure, and its internal channels are configured as serpentine channels 15. The gas lines at the CO2 gas inlet and the CH4 gas inlet intersect at a 90° angle, and both gas inlets have a diameter of 0.3 mm; the liquid inlet is perpendicular to the gas channels, has a diameter of 0.5 mm, and is configured with a tapered converging structure 11 (preferably, the cone angle of the tapered converging structure 11 is 15°) to accelerate liquid flow.

[0029] A micro-serrated structure 13 is installed downstream of the T-junction junction (i.e., at the CH4 gas inlet) as a vortex generator. This structure generates micro-vortices through periodic perturbation, thereby enhancing the initial dispersion of the gas and liquid phases to achieve controllable mixing from laminar to turbulent flow, resulting in a uniformly dispersed system. Preferably, the micro-serrated structure 13 has a tooth height of 50 μm and a tooth pitch of 100 μm.

[0030] In the above embodiments, the in-situ Raman spectroscopy module includes a double-layered isothermal jacketed reaction chamber 17, a Raman spectroscopy system, and a computer and numerical control system 22. The Raman spectroscopy system is used for in-situ high-precision monitoring of the double-layered isothermal jacketed reaction chamber 17 during the hydrate formation process, and transmits the monitored spectral data to the computer and numerical control system 22. The computer and numerical control system 22 is equipped with a signal processing and modeling unit to realize real-time online analysis of spectral data and component ratios.

[0031] In this embodiment, the Raman spectroscopy system includes an integrated confocal micro Raman probe 26 and a laser source 16, which are mounted on the same horizontal plane as the double-layered thermostatically controlled reaction chamber 17. The laser source 16 provides a laser source for the confocal micro Raman probe 26, supplying lasers of different wavelengths to the sapphire window 25 of the double-layered thermostatically controlled reaction chamber 17 to alternately excite the sample, and the spectral signals are acquired by the confocal micro Raman probe 26.

[0032] Specifically, the laser source 16 employs a dual-wavelength laser source, preferably a 532 nm laser, to excite the CH bond stretching vibration of CH4 (characteristic peak at 2917 cm⁻¹). - ¹), using a 785 nm laser to match the Fermi resonance double peaks (1388 / 1285 cm⁻¹) of CO₂. - ¹), effectively avoiding fluorescence interference. The power of the two lasers is adjustable, with the 532 nm laser power range of 0~100 mW and the 785 nm laser power range of 0~150 mW, and they are coupled to the same optical path through a beam splitter (50:50 beam splitting ratio).

[0033] The confocal micro-Raman probe 26 employs a microscope objective; this objective is a 50x long working distance objective with a numerical aperture (NA) of 0.55, a working distance of 10.6 mm, and a spatial resolution of 1 μm, capable of focusing on micro-regions (diameter ≤ 2 μm) at the gas-liquid interface. The confocal optical path of the confocal micro-Raman probe 26 uses a 25 μm pinhole aperture, effectively suppressing defocus signals and improving the signal-to-noise ratio by over 20 dB.

[0034] In terms of dynamic signal processing, the Raman signal acquired by the confocal micro Raman probe 26 is transmitted to the spectrometer through an optical fiber with a core diameter of 50 μm and a numerical aperture of 0.22. The spectral data is synchronized to the signal processing and modeling unit in the computer and numerical control system 22 at a frequency of 100 Hz.

[0035] The confocal Raman microscope probe 26 also features three-dimensional scanning capabilities, equipped with an XYZ three-axis motorized translation stage, a positioning accuracy of ±0.1 μm, and a preset spiral scanning path (5 μm step size), capable of generating spatial distribution maps of hydrates. The autofocus function, based on reflected light intensity feedback, dynamically adjusts the objective lens focal length with a response time of less than 100 ms, ensuring stable focus of the light spot at the interface. The confocal Raman microscope probe 26 used in this embodiment has a resolution of 1 μm, and laser wavelengths include 532 nm (for CH4C-H bond vibration) and 785 nm (for the CO2 Fermi resonance band). The spectral acquisition frequency can reach up to 100 Hz, covering a wavenumber range of 100–4000 cm⁻¹. - ¹.

[0036] In this embodiment, the signal processing and modeling unit is composed of a convolutional neural network (CNN). The preprocessing unit performs baseline correction and normalization on the obtained Raman spectrum, and automatically identifies CH4 (2917 cm⁻¹). - ¹), CO2 (1388 cm³) - ¹) and hydrate cage-like structure (OH vibration 3100~3700 cm) -¹) Characteristic peaks were identified, and a quantitative regression model (error < 2%) was established between the CO2 / CH4 molar ratio and the integral value of the characteristic peak area. The optimal model was obtained after the model was validated by the training set and the test set (7:3 ratio), realizing real-time online analysis of spectral data to component ratios.

[0037] When in use, the computer and CNC system 22 automatically identifies the CH4 / CO2 characteristic peaks, calculates the molar ratio (with an error of less than 2%), and associates the hydrate crystal form (sI / sII) classification with an accuracy of over 95%.

[0038] In the above embodiments, the data feedback and optimization module consists of a computer and a numerical control system 22. It receives temperature and pressure parameters, miscibility ratio, and Raman spectral characteristics in real time, and dynamically adjusts the temperature and pressure setpoints through a built-in PID-PSO (particle swarm optimization) algorithm to optimize experimental conditions. It predicts the hydrate formation rate threshold and feeds the results back to the gas-liquid miscibility injection module to dynamically adjust the CO2 injection ratio, thereby achieving intelligent optimization control of the system.

[0039] The following examples further illustrate the real-time process of the present invention. Specifically, it is achieved through the coordinated operation of the temperature-pressure miscibility control module, the in-situ pull-out measurement module, and the data feedback and optimization module.

[0040] First, the operator sets the experimental parameters through the human-machine interface of the computer and CNC system 22, including the target temperature (e.g., 4℃), pressure (e.g., 10 MPa), gas mixing ratio (e.g., CH4:CO2=7:3) and liquid phase salinity (e.g., 3 wt% NaCl). The temperature-pressure-mixing coordinated control module is then activated: the semiconductor cooling chip 18 of the high-precision temperature control unit uses the Peltier effect to adjust the temperature of the double-layer titanium alloy reaction chamber through the PID algorithm, and the distributed fiber optic sensor monitors the temperature gradient inside the chamber in real time to ensure that the axial temperature difference is ≤0.03℃ / cm; the three-channel servo motor 1 of the dynamic pressure control unit drives the CH4 and CO2 high-pressure gas pumps 4 (2) and the saline infusion pump 7 respectively, and adjusts the flow rate with the proportional regulating valve 23 to stabilize the pressure within the set value ±0.01 MPa range. The gas-liquid mixed phase injection module realizes the controllable mixing of gas and liquid phases through the microfluidic mixer 14, in which the laminar flow zone of the serpentine channel 15 (Re=80) promotes molecular diffusion, and the turbulent zone of the T-shaped section structure of the microfluidic mixer 14 (Re=500) uses vortex to break the phase interface. The online conductivity meter and mass spectrometer 19 monitor the salinity and gas ratio of the mixed liquid in real time and output a uniformly dispersed system (droplet D32=20±5 μm).

[0041] The in-situ Raman spectroscopy module is activated simultaneously: the sapphire window 25 of the high-pressure resistant reaction chamber 17 allows the confocal micro Raman probe 26 (50× objective, NA=0.55) to focus on the gas-liquid interface. Dual-wavelength lasers (532 nm / 50 mW and 785 nm / 120 mW) alternately excite the sample, and a low-temperature CCD detector (cooled to -70℃) acquires spectral signals at a frequency of 100 Hz, covering wavenumbers from 100 to 4000 cm⁻¹. - ¹; The ultrasonic transducer (1 MHz) operates in pulse mode to enhance mass transfer efficiency, and the hydrophobic stirring paddle 27 (500 rpm) suppresses bubble coalescence. The signal processing and modeling unit in the computer and numerical control system 22 performs baseline correction (airPLS algorithm) and normalization on the original spectrum, and automatically identifies CH4 (2917 cm⁻¹) through a pre-trained convolutional neural network (CNN). - ¹), CO2 (1388 cm³) - ¹) and the OH vibration peak of hydrate (3100~3700 cm⁻¹) - ¹), and calculate the integral value of the characteristic peak area to establish a quantitative regression model of the CO2 / CH4 molar ratio (error < 2%). The model output is transmitted to the data feedback module in real time.

[0042] The data feedback and optimization module dynamically adjusts system parameters based on a PID-PSO hybrid algorithm: In the initial stage, the PID controller maintains steady-state conditions (e.g., 4℃±0.05℃, 10 MPa±0.01 MPa). When the CH4 peak area growth rate is detected to be >2% / min, the particle swarm optimization (PSO) algorithm is activated to maximize the hydrate formation rate. It searches for temperature-pressure-miscibility parameter combinations (e.g., heating to 4.2℃, depressurizing to 9.5 MPa, and increasing the CO2 percentage to 40%), and executes the adjustment command through the proportional control valve 23 in conjunction with the servo motor 1. If the pressure drops suddenly >0.1 MPa / min or the temperature gradient >0.2℃ / cm, the system triggers a three-level safety mechanism: the electronic pressure relief valve 24 opens instantaneously to release pressure, the power of the semiconductor cooling chip 18 is adaptively adjusted, and the stirring speed is increased to 800 rpm to restore mass transfer balance.

[0043] After the experiment was terminated, the system was automatically depressurized to atmospheric pressure (at a rate of 0.5 MPa / min), and the temperature-pressure curve, spectral sequence, and optimization log were exported.

[0044] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation, characterized in that, include: The temperature-pressure-miscibility synergistic control module is used to simulate the real temperature-pressure-miscibility conditions of seabed reservoirs or industrial reactors to control the CH4 / CO2 gas ratio and liquid phase salinity, and output a uniformly dispersed system. The in-situ La Manganese monitoring module is used to capture the lattice embedding order and structural evolution of CO2 and CH4 during the hydrate formation process in real time, output real-time data and transmit it to the data feedback and optimization module. The data feedback and optimization module receives temperature and pressure parameters, mixing ratios, and Raman spectral characteristic parameters in real time, dynamically adjusts experimental parameters, and performs intelligent optimization control of the system.

2. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 1, characterized in that, The temperature and pressure mixed phase coordinated control module includes a high-precision temperature control unit, a dynamic pressure control unit, and a gas-liquid mixed phase injection module; The high-precision temperature control unit includes a double-layer constant temperature jacketed reaction chamber. It monitors the temperature gradient inside the double-layer constant temperature jacketed reaction chamber in real time and transmits the real-time monitoring data to the data feedback and optimization module. The dynamic pressure control unit is used to control the injection pressure of CH4 gas, CO2 gas and liquid respectively; The gas-liquid mixed-phase injection module includes a microfluidic mixer, which is used to inject CH4 gas, CO2 gas and liquid into the microfluidic mixer respectively, and to perform controllable mixing under the control of the dynamic pressure regulation unit to generate a uniformly dispersed system.

3. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 2, characterized in that, The inner layer of the double-layer constant temperature jacketed reaction chamber is made of titanium alloy, and the outer layer integrates a semiconductor cooling chip and has a viewing window; a pressure relief valve is located at the rear of the double-layer constant temperature jacketed reaction chamber. The double-layer constant temperature jacketed reaction chamber is also equipped with a detachable stirring paddle, and the surface of the detachable stirring paddle blades is hydrophobic. An ultrasonic transducer is also built inside the double-layer constant temperature jacket reaction chamber to enhance gas-liquid mass transfer and improve reaction efficiency.

4. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 2, characterized in that, The high-precision temperature control unit also includes the Instec hot and cold stage intelligent temperature control system and distributed fiber optic temperature sensors; Distributed fiber optic temperature sensors are installed inside the double-layer constant temperature jacket reaction chamber to monitor the temperature gradient inside the reaction chamber in real time and transmit the data to the Instec hot and cold stage intelligent temperature control system and data feedback and optimization module. The instec hot and cold stage intelligent temperature control system includes a main controller, a cold stage CNC display screen, and a circulating water tank. The main controller controls the semiconductor cooling chip and the circulating water tank based on the received temperature data to control the temperature of the double-layer constant temperature jacket reaction chamber, and the temperature is displayed in real time on the cold stage CNC display screen.

5. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 2, characterized in that, The dynamic pressure control unit includes a three-channel servo motor, a CO2 high-pressure plunger pump, a CH4 high-pressure plunger pump, and an infusion pump. The three-channel servo motor drives the CO2 high-pressure plunger pump, the CH4 high-pressure plunger pump, and the infusion pump respectively. The CO2 high-pressure plunger pump injects pressure into the CO2 gas cylinder, the CH4 high-pressure plunger pump injects pressure into the CH4 gas cylinder, and the infusion pump injects pressure into the liquid in the storage tank.

6. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 5, characterized in that, Proportional regulating valves are installed on the pipelines between the CO2 high-pressure plunger pump and the CO2 cylinder, the pipelines between the CH4 high-pressure plunger pump and the CH4 high-pressure cylinder, and the pipelines between the infusion pump and the storage tank; the CO2 high-pressure plunger pump, the CH4 high-pressure plunger pump, and the infusion pump are linked with the proportional regulating valves.

7. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 2, characterized in that, The gas-liquid mixed-phase injection module includes a microfluidic mixer and an online conductivity meter and gas mass spectrometer; the microfluidic mixer has a CO2 gas inlet, a CH4 gas inlet and a liquid inlet, wherein the two gas inlets are connected to a CO2 gas cylinder and a CH4 high-pressure cylinder respectively, and the liquid inlet is connected to a storage tank; a CO2 pressure gauge is installed at the CO2 gas inlet, a CH4 pressure gauge is installed at the CH4 gas inlet, and a hydraulic pressure gauge is installed at the liquid inlet; An online conductivity meter and a gas mass spectrometer are connected to a microfluidic mixer to monitor the composition of the mixing system within the microfluidic mixer in real time. The microfluidic mixer is also connected to a double-layered thermostatically controlled reaction chamber via piping, which is used to input a uniformly dispersed gas-liquid system into the reaction chamber.

8. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 7, characterized in that, The microfluidic mixer adopts a T-joint structure with a serpentine internal channel. The gas lines at the CO2 gas inlet and the CH4 gas inlet intersect at a 90° angle, and the liquid inlet is perpendicular to the gas channel and has a tapered converging structure. A micro-serrated structure is set downstream of the T-section junction as a vortex generator. It generates micro-vortices through periodic disturbances, enhances the initial dispersion of gas and liquid, and realizes the controllable mixing of gas and liquid phases from laminar to turbulent flow, outputting a uniformly dispersed system.

9. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 1, characterized in that, The in-situ Raman spectroscopy module includes a double-layer constant-temperature jacketed reaction chamber, a Raman spectroscopy system, and a computer and numerical control system. The Raman spectroscopy system is used for in-situ high-precision monitoring of the double-layer constant-temperature jacketed reaction chamber during the hydrate formation process, and transmits the monitored spectral data to the computer and numerical control system. The computer and numerical control system is equipped with a signal processing and modeling unit to realize real-time online analysis of spectral data to component ratios.

10. The CH4-CO2 hydrate formation prediction system based on temperature and pressure synergistic regulation as described in claim 9, characterized in that, The Raman spectroscopy system includes an integrated confocal micro Raman probe and a laser source, which are on the same horizontal plane as the double-layered thermostatically controlled reaction chamber. The laser source provides a laser source for the confocal micro Raman probe, which provides lasers of different wavelengths to the sapphire window of the double-layered thermostatically controlled reaction chamber to alternately excite the sample, and the spectral signal is acquired by the confocal micro Raman probe.

Images