Preparation device and preparation method of liquid CO2-H2O emulsion and three-phase quantification method

Abstract

The embodiment of the invention relates to a preparation device, a preparation method and a three-phase quantification method of a liquid CO2-H2O emulsion. The preparation device of the liquid CO2-H2O emulsion comprises a high-pressure reaction kettle, an injection system, a stirring device, a constant-temperature water bath system, a temperature sensor, a pressure sensor, an image acquisition system and a data acquisition system. The high-pressure reaction kettle is fully visual and has the pressure resistance of at least 50 MPa. The injection system is used for injecting gaseous CO2, liquid CO2 and an emulsifier aqueous solution into the high-pressure reaction kettle. The stirring device is used for stirring the liquid CO2 and the emulsifier water solution in the high-pressure reaction kettle. The constant-temperature water bath system is used for controlling the temperature of the high-pressure reaction kettle. The temperature sensor and the pressure sensor are used for detecting the real-time temperature and the real-time pressure of the high-pressure reaction kettle respectively. The image acquisition system is used for capturing image information of an emulsion forming process and an emulsion breaking process of the CO2-H2O emulsion in the high-pressure reaction kettle. And the data acquisition system is used for recording and analyzing real-time temperature, real-time pressure and image information.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of liquid carbon dioxide-water (CO2-H2O) emulsion preparation, and specifically, to a liquid CO2-H2O emulsion preparation device, a liquid CO2-H2O emulsion preparation method, and a liquid CO2-H2O emulsion three-phase quantitative method. Background Art

[0002] Energy consumption and climate change issues brought about by the growing global economy have become important factors restricting the further development of various countries. Carbon dioxide (CO2) is the main component of industrial waste gas and the dominant factor of the greenhouse effect. How to effectively reduce carbon dioxide emissions and achieve carbon capture and storage (CCS) and utilization of carbon dioxide has become the focus of researchers.

[0003] By preparing liquid CO2-H2O emulsion, not only the formation rate of carbon dioxide hydrate can be increased, but also the contact area between carbon dioxide and water can be increased, thereby accelerating the formation process of carbon dioxide hydrate and improving the carbon dioxide storage efficiency, which is helpful to achieve carbon dioxide capture and storage (CCS) and mitigate global warming. This plays an important guiding role in improving the efficiency of carbon dioxide capture and storage technology and is of great significance to environmental protection and sustainable development.

[0004] In addition, the preparation of carbon dioxide-water emulsion can also provide new solutions for reducing industrial waste gas emissions and reducing environmental pollution. In addition to applications in the fields of energy and environmental protection, liquid CO2-H2O emulsion can also be used in many fields such as metal nanoparticles, polymer synthesis, biotransformation, metal catalysis, etc., providing new possibilities and opportunities for the development of these fields.

[0005] However, the traditional method for preparing liquid CO2-H2O emulsion has problems of insufficient emulsion stability and low yield. Summary of the invention

[0006] The first aspect of the present application provides a device for preparing a liquid CO2-H2O emulsion. The device for preparing the liquid CO2-H2O emulsion includes an autoclave, an injection system, a stirring device, a constant temperature water bath system, a temperature sensor, a pressure sensor, an image acquisition system, and a data acquisition system. The autoclave is fully visualized and has a pressure resistance of at least 50MPa. The injection system is connected to the autoclave and is used to inject gaseous carbon dioxide, liquid carbon dioxide, and an emulsifier aqueous solution into the autoclave. The stirring device is connected to the autoclave and is used to stir the liquid carbon dioxide and the emulsifier aqueous solution in the autoclave. The constant temperature water bath system is used to accommodate the autoclave to control the temperature of the autoclave. The temperature sensor is connected to the autoclave and is used to detect the real-time temperature of the autoclave. The pressure sensor is connected to the autoclave and is used to detect the real-time pressure of the autoclave. The image acquisition system is used to capture image information of the emulsification process and demulsification process of the liquid CO2-H2O emulsion in the autoclave. The data acquisition system is respectively connected with the temperature sensor, the pressure sensor, the flow meter and the image acquisition system to record and analyze the real-time temperature, the real-time pressure and the image information.

[0007] In the preparation device of the liquid CO2-H2O emulsion of the embodiment of the present application, the high-pressure reactor is a fully visualized pressure-resistant autoclave of at least 50MPa, which can provide a high-pressure environment for the preparation of the liquid CO2-H2O emulsion, so as to help carbon dioxide dissolve in water and promote the formation of emulsion, thereby increasing the amount of emulsion generated per unit time. In addition, the high-pressure environment can make carbon dioxide exist in liquid form and more easily form a stable emulsion with water. The fully visualized design facilitates the observation of the emulsification process of the emulsion and timely adjusts the parameters to improve the stability of the emulsion. The injection system is conducive to accurately controlling the injection amount and injection rate, which can optimize the composition of the emulsion, thereby improving the emulsion yield; moreover, stable injection can avoid excessive or low local concentration, help to form a uniform emulsion, and reduce the risk of phase separation. The stirring of the stirring device can increase the contact area between the liquid carbon dioxide and the emulsifier aqueous solution, accelerate the formation of the emulsion, thereby improving the yield; and the appropriate stirring speed can make the droplets dispersed evenly, prevent the droplets from aggregating, and improve the stability of the emulsion. The constant temperature water bath system is conducive to precise temperature control, which can optimize the formation conditions of the emulsion and improve the yield. In addition, stable temperature can prevent the emulsion from phase separation due to temperature changes and improve the stability of the emulsion. Temperature sensors and pressure sensors can accurately control reaction conditions and optimize the formation of emulsions by real-time monitoring of temperature and pressure, thereby improving yields; and real-time monitoring of temperature and pressure can detect abnormal conditions in time to prevent the emulsion from becoming unstable due to changes in conditions. The image acquisition system analyzes the emulsification process of the emulsion through image information, optimizes preparation parameters, and improves yields; and analyzes the demulsification process of the emulsion through image information, and can adjust parameters in time to improve the stability of the emulsion. The data acquisition system can fully understand the emulsification process of the emulsion, optimize preparation parameters, improve yields, and improve the stability of the emulsion by collecting and analyzing data from all sensors.

[0008] The second aspect of the present application provides a method for preparing a liquid CO2-H2O emulsion. The method for preparing the liquid CO2-H2O emulsion comprises: Step S1: adding an emulsifier aqueous solution obtained by mixing water and an emulsifier in a preset ratio into a high-pressure reactor, and sealing the high-pressure reactor, wherein the high-pressure reactor is fully visible and has a pressure resistance of at least 50 MPa; Step S2: purging the autoclave with gaseous carbon dioxide to expel the air in the autoclave, then adding a preset volume of liquid carbon dioxide into the autoclave, and controlling the temperature in the autoclave to be in the range of 0° C. to 30° C. and the pressure in the autoclave to be in the range of 0 MPa to 50 MPa; and Step S3: stirring the emulsifier aqueous solution and liquid carbon dioxide in the high-pressure reactor to form a liquid CO2-H2O emulsion.

[0009] In the preparation method of the liquid CO2-H2O emulsion of the embodiment of the present application, in step S1, the water and emulsifier of the preset ratio are mixed to ensure that the emulsifier concentration is appropriate, thereby improving the formation efficiency of the emulsion, and the appropriate emulsifier concentration can reduce the interfacial tension and help to form a stable emulsion. In step S2, the air is purged to ensure that the reaction environment is pure, which helps to improve the formation efficiency of the emulsion. A preset volume of liquid carbon dioxide is added to ensure that the reaction materials are sufficient. In addition, the temperature and pressure are controlled, so that the liquid carbon dioxide can be stably present and more easily form a stable emulsion with water. In step S3, stirring increases the contact area between the liquid carbon dioxide and the emulsifier aqueous solution, accelerates the formation of the emulsion, thereby improving the yield, and stirring can make the droplets dispersed evenly, prevent the droplets from aggregating, and improve the stability of the emulsion.

[0010] The third aspect of the present application provides a three-phase quantitative method for liquid CO2-H2O emulsion. The three-phase quantitative method for liquid CO2-H2O emulsion comprises: A series of images of the emulsification process and the demulsification process of the liquid CO2-H2O emulsion captured by the image acquisition system are converted into grayscale images using statistical software or machine learning algorithms; Performing edge detection on the grayscale image; Performing morphological processing on the grayscale image after edge detection, wherein the morphological processing includes a closing operation, creating a structural element, and then performing connected component analysis; Performing feature extraction on the grayscale image after morphological processing; Display an image of the masked area; Tracking the area changes of the emulsifier solution phase, the liquid CO2-H2O emulsion phase and the liquid carbon dioxide phase during the emulsification process of the liquid CO2-H2O emulsion by using the area changes of the mask region; and The coordinate axis positioning method was used to measure the height changes of the emulsifier solution phase, liquid CO2-H2O emulsion phase and liquid carbon dioxide phase in the autoclave during the demulsification process of the liquid CO2-H2O emulsion.

[0011] The three-phase quantitative method of liquid CO2-H2O emulsion provided in the third aspect of the present application can more accurately identify the boundaries of each phase and calculate the area and height of each phase by processing a series of images of the emulsification process and demulsification process of the liquid CO2-H2O emulsion using statistical software or machine learning algorithms, thereby facilitating accurate quantitative analysis. This accurate quantitative analysis can help researchers better understand the mechanism of emulsion formation and demulsification, optimize the process parameters for preparing liquid CO2-H2O emulsions, and improve the stability and yield of liquid CO2-H2O emulsions.

[0012] Specifically, by tracking the area changes of each phase during the emulsification process of liquid CO2-H2O emulsion, the emulsion formation process can be monitored in real time, and the effects of different emulsification process parameters (such as emulsifier concentration, stirring time, stirring speed, etc.) on the emulsion formation can be understood, and then the emulsification process parameters can be optimized to find the best emulsification conditions, thereby improving the yield and stability of the emulsion. By measuring the height changes of each phase during the demulsification process, methods to inhibit demulsification can be found to improve the stability of the emulsion. For example, if it is found that the emulsion demulsification speed is too fast, the type of emulsifier, the concentration of the emulsifier, the stirring speed, the stirring time, etc. can be adjusted to slow down the demulsification speed and improve the stability of the emulsion. In addition, through the three-phase quantitative analysis of liquid CO2-H2O emulsion, a large amount of experimental data can be obtained, which can be used to establish a mathematical model of the emulsification process and demulsification process of the emulsion. Using these mathematical models, data-driven design of process parameters for liquid CO2-H2O emulsions can be carried out, and the performance of the emulsion under different parameters can be predicted, so as to more quickly find the preparation conditions that are most conducive to improving the stability and yield of liquid CO2-H2O emulsions. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is a schematic structural diagram of a device for preparing liquid CO2-H2O emulsion according to an embodiment of the present application.

[0014] Figure 2 This is a schematic structural diagram of each step of a method for preparing a liquid CO2-H2O emulsion according to an embodiment of the present application.

[0015] Figure 3 for Figure 2 Schematic diagram of the image recognition process of liquid CO2-H2O emulsion during the emulsification process in the preparation method.

[0016] Figure 4 for Figure 2 Schematic diagram of the image recognition process of liquid CO2-H2O emulsion during the demulsification process in the preparation method.

[0017] Figure 5 for Figure 2 Schematic diagram of image information captured during the emulsification process of liquid CO2-H2O emulsion in the preparation method.

[0018] Figure 6 For Figure 5 Schematic diagram of using mask method to identify area based on image information.

[0019] Figure 7 for Figure 2 Schematic diagram of image information captured during the demulsification process of liquid CO2-H2O emulsion in the preparation method.

[0020] Figure 8For Figure 7 Schematic diagram of using mask method to identify area based on image information.

[0021] Description of main component symbols: Liquid CO2-H2O emulsion preparation device: 100; High pressure reactor: 10; Injection system: 20; Single cylinder pump: 21; CO2 injection system: 22; Stirring device: 30; Constant temperature water bath system: 40; Constant temperature water bath: 41; Water bath: 42; Temperature sensor: 50; Pressure sensor: 60; Image acquisition system: 70; Data Acquisition System:80.

[0022] The following specific implementation methods will further illustrate the present application in conjunction with the above-mentioned drawings. DETAILED DESCRIPTION

[0023] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the embodiments of the present application, and cannot be understood as limiting the present application.

[0024] In the description of the embodiments of the present application, terms such as "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the implementation methods of the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0025] In the description of the embodiments of the present application, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0026] In the description of the embodiments of the present application, unless otherwise specified, “plurality” means two or more than two.

[0027] In the description of the embodiments of the present application, unless otherwise specified, the terms "installed", "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, an electrical connection, or mutual communication; it can be a direct connection or an indirect connection through an intermediate medium; it can be the internal connection of two elements or the interaction relationship between two elements.

[0028] For those skilled in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0029] The traditional method for preparing liquid CO2-H2O emulsion is usually carried out at room temperature and pressure, which easily leads to the instability and phase separation problems of the emulsion. The embodiment of the present application prepares the liquid CO2-H2O emulsion in a high-pressure environment, which can help people to deeply study the interaction between carbon dioxide and water under different conditions (such as pressure and temperature) and understand their phase behavior and phase separation characteristics; by further studying the formation and stability of liquid CO2-H2O emulsion, the yield and stability of liquid carbon dioxide / water emulsion can be improved, which can provide important experimental basis and theoretical support for the technical development in the above-mentioned field.

[0030] like Figure 1 As shown, the preparation device 100 of liquid CO2-H2O emulsion includes a high-pressure reactor 10, an injection system 20, a stirring device 30, a constant temperature water bath system 40, a temperature sensor 50, a pressure sensor 60, an image acquisition system 70 and a data acquisition system 80.

[0031] The autoclave 10 is fully visible and has a pressure resistance of at least 50 MPa. The autoclave 10 is also equipped with a safety release valve to ensure the safety of the reaction process.

[0032] In some embodiments, the autoclave 10 is a high-pressure fully visible sapphire autoclave with a volume V=50 mL.

[0033] The injection system 20 is connected to the high-pressure reactor 10 and is used to inject gaseous carbon dioxide, liquid carbon dioxide and an emulsifier aqueous solution into the high-pressure reactor 10 .

[0034] The stirring device 30 is connected to the high-pressure reactor 10 and is used to stir the liquid carbon dioxide and the emulsifier aqueous solution in the high-pressure reactor 10 .

[0035] The constant temperature water bath system 40 is used to accommodate the autoclave 10 to control the temperature of the autoclave 10. The constant temperature water bath system 40 can realize high-precision constant temperature design and can realize temperature control of -150° C. to 350° C. The constant temperature water bath system 40 has a large heat exchange area and a fast heating / cooling rate.

[0036] The constant temperature water bath system 40 includes a constant temperature water bath box 41 with a display screen, and is equipped with a constant temperature program and a variable temperature program to achieve different reaction condition requirements.

[0037] The constant temperature water bath system 40 also includes a transparent acrylic water bath 42. By placing the autoclave 10 in the water bath 42, the environment of the autoclave 10 is controlled, and the temperature of the water bath 42 is set to the temperature of the autoclave 10.

[0038] In some embodiments, the length and width of the water bath 42 are, but not limited to, 300 mm×300 mm, and two holes are opened at the bottom of the front to connect to the circulating water pipe.

[0039] The temperature sensor 50 is connected to the autoclave 10 and is used to detect the real-time temperature of the autoclave 10 .

[0040] In some embodiments, the temperature sensor 50 is of model WZ-PT300, which is placed in the autoclave 10 and the water bath 42 respectively, with a temperature error within ±1° C., and monitors temperature changes at a frequency of once per second.

[0041] The pressure sensor 60 is connected to the high-pressure reactor 10 and is used to detect the real-time pressure of the high-pressure reactor 10 .

[0042] In some embodiments, the model of the pressure sensor 60 is DG2113-C-25, which is used to monitor the pressure changes inside the high-pressure reactor 10, with a measuring range of 0 to 25 MPa, a pressure error within ±0.01 MPa, and records the relationship between the pressure changes and the emulsion formation and demulsification process time.

[0043] The image acquisition system 70 is used to capture image information of the emulsification process and demulsification process of the liquid CO2-H2O emulsion in the autoclave 10. The image acquisition system 70 includes but is not limited to a high-resolution camera (such as a resolution of 2048×3072). After setting the parameters such as the camera position, exposure, brightness, color and frame frequency, and setting the time interval, saving method and storage location of the image recording, the camera can start to capture images of the emulsification process and demulsification process of the liquid CO2-H2O emulsion (hereinafter referred to as emulsion images). High-resolution cameras include MZL-DJ630 and other models of microscopes that can capture the whole picture. The high-resolution camera observes the changes of the emulsion during the static period, records its stabilization time, and determines the stabilization time based on the change of the emulsion volume over time in the photo at an interval of 1 time / s.

[0044] The data acquisition system 80 is connected to the temperature sensor 50, the pressure sensor 60, the flow meter and the image acquisition system 70 respectively, and is used to record and analyze the real-time temperature, real-time pressure and image information. The temperature and pressure parameters in the reaction process are monitored in real time through the integrated sensor network; the real-time data is recorded and analyzed by the data acquisition system 80 to ensure the integrity and accuracy of the data.

[0045] In addition, after the image captured by the image acquisition system 70 is transmitted to the data acquisition system 80, data storage is realized, and the emulsion image is analyzed using image processing software.

[0046] In some embodiments, the data acquisition system 80 includes a temperature collector connected to the temperature sensor 50, a pressure collector connected to the pressure sensor 60, a transformer, a data integration box, etc. The temperature collector is DAQM-4201, the pressure collector is DAQM-4206, the transformer is LRS-50-24, and the data integration box is CBT-1009. The temperature, pressure, etc. of the autoclave 10 can be recorded by the corresponding collector in the data acquisition system 80, and the relevant data can be saved.

[0047] In some embodiments, the liquid CO2-H2O emulsion preparation device 100 further includes a flow meter (not shown). The flow meter is connected to the autoclave 10 and the data acquisition system 80, and is used to detect the volume change of the liquid CO2-H2O emulsion in the autoclave 10. The data acquisition system 80 is also used to record and analyze the volume change of the liquid CO2-H2O emulsion in the autoclave 10.

[0048] In some embodiments, the flow meter model is an electromagnetic flow meter of DN4 to DN3000 with a measurement accuracy of ±2.5%, which monitors the volume change of the emulsion in the high-pressure reactor 10 in real time and records the height change of the emulsion volume. The specific monitoring range is 0-100L.

[0049] In some embodiments, the preparation device 100 of liquid CO2-H2O emulsion further includes a multiphase flow sensor (not shown). The multiphase flow sensor is connected to the autoclave 10 and the data acquisition system 80, and is used to monitor the volume ratio changes of the liquid carbon dioxide phase, the emulsifier solution phase and the liquid CO2-H2O emulsion phase at different time points in the autoclave 10, and the specific monitoring range is 0-100% volume ratio. The data acquisition system 80 is also used to record and analyze the volume ratio changes.

[0050] In some embodiments, the preparation device 100 of the liquid CO2-H2O emulsion further includes a cryo-scanning electron microscope (not shown). The cryo-scanning electron microscope is connected to the data acquisition system 80 and is used to observe and count the particle size distribution and phase interface changes of the liquid CO2-H2O emulsion; the data acquisition system 80 is used to record and analyze the particle size distribution and phase interface changes. In some embodiments, the stability of the liquid CO2-H2O emulsion at rest is at least 60 minutes, and no obvious demulsification and stratification phenomenon is observed during this period.

[0051] In some embodiments, the establishment of an emulsion evaluation system includes observing the morphological characteristics and particle size distribution of the emulsion through a cryo-scanning electron microscope, and statistically analyzing the size and shape of the droplets. The uniformity evaluation of the emulsion droplet distribution can be calculated by timing the images captured during the emulsion formation and demulsification process. The analysis of the change in the emulsion volume in the autoclave 10 can be achieved based on the height of the emulsifier solution, the liquid CO2-H2O emulsion, and the liquid carbon dioxide in the autoclave 10 as the emulsion is formed and demulsified.

[0052] In some embodiments, the preparation device 100 of the liquid CO2-H2O emulsion further includes an in-situ Raman spectrometer (not shown). The in-situ Raman spectrometer is connected to the high-pressure reactor 10 and the data acquisition system 80, and is used to measure the structural characteristics of the liquid carbon dioxide and the emulsifier aqueous solution in the liquid CO2-H2O emulsion in the emulsion system to analyze the internal mechanism of the formation of the liquid CO2-H2O emulsion; the data acquisition system 80 is also used to record and analyze the structural characteristics.

[0053] In some embodiments, the in-situ Raman spectrometer model may be, but is not limited to, SRaman-53.

[0054] In some embodiments, the preparation device 100 for liquid CO2-H2O emulsion further includes an in-situ particle size analyzer (not shown). The in-situ particle size analyzer is connected to the autoclave 10 and the data acquisition system 80, and is used to measure the droplet size of the liquid CO2-H2O emulsion; the data acquisition system 80 is also used to record and analyze the droplet size.

[0055] In some embodiments, the droplet size of the liquid CO2-H2O emulsion is between 100 nm and 10 μm.

[0056] In some embodiments, the device 100 for preparing liquid CO2-H2O emulsion further includes a rotation speed sensor (not shown). The rotation speed sensor is connected to the high-pressure reactor 10 and the data acquisition system 80, and is used to monitor the rotation speed of the stirring device 30. The data acquisition system 80 is also used to record and analyze the rotation speed.

[0057] In some embodiments, the rotation speed sensor is a KJTCS500 magnetoelectric rotation speed sensor, which has an accuracy of ±1r / min and is correlated with the emulsion generation efficiency.

[0058] In some embodiments, the liquid CO2-H2O emulsion preparation device 100 further includes a conductivity sensor (not shown). The conductivity sensor autoclave 10 is connected to the data acquisition system 80 and is used to monitor the conductivity in the autoclave 10 during the preparation of the liquid CO2-H2O emulsion. The data acquisition system 80 is also used to record and analyze the conductivity.

[0059] In some embodiments, the injection system 20 includes a single-cylinder pump 21 and a carbon dioxide injection system 22. The single-cylinder pump 21 is connected to the autoclave 10 and the data acquisition system 80. The single-cylinder pump 21 is used to inject the emulsifier aqueous solution into the autoclave 10, and the data acquisition system 80 is also used to record the injection volume and injection rate of the emulsifier aqueous solution. The carbon dioxide injection system 22 is used to be connected to the autoclave 10 to inject gaseous carbon dioxide and liquid carbon dioxide into the autoclave 10.

[0060] In some embodiments, the stirring device 30 includes at least one of an ultrasonic generator, a high shear stirrer, a constant temperature magnetic stirrer, or an electric stirring paddle.

[0061] The embodiment of the present application also provides a method for preparing a liquid CO2-H2O emulsion. The preparation method includes the following steps S1 to S3. Among them, the preparation method of the liquid CO2-H2O emulsion can be implemented by the above-mentioned preparation device of the liquid CO2-H2O emulsion, but is not limited thereto. In addition, according to different needs, the order of certain steps or sub-steps of the preparation method of the liquid CO2-H2O emulsion can be changed, and certain steps or sub-steps can be omitted or combined.

[0062] Step S1: adding an emulsifier aqueous solution obtained by mixing water and an emulsifier in a preset ratio into a high-pressure reactor, and sealing the high-pressure reactor, wherein the high-pressure reactor is fully visible and has a pressure resistance of at least 50 MPa.

[0063] In some embodiments, in step S1, the emulsifier is selected from one or more of lecithin, alkyl glycoside, sodium lignin sulfonate, sodium di(2-ethylhexyl) sulfonate of succinate, sodium dodecyl sulfate, polyvinyl alcohol, alkylphenol polyoxyethylene ether-10 (OP-10), fatty alcohol polyoxyethylene ether (AEO), polyoxyethylene sorbitan monooleate AEO Tween 80, sorbitan laurate monoester (Span 20 / 60 / 80), sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium iodide, nanomaterials, bioacids, phosphates, polyols, amino acids, fatty acids, and citric acid, but is not limited thereto. By adding different types of surfactants (such as nonionic surfactants or polymers), it is beneficial to improve the stability of the liquid CO2-H2O emulsion and reduce the interfacial tension.

[0064] In other embodiments, in step S1, the emulsifier can be selected from other surfactant emulsifiers, natural emulsifiers, solid particulate emulsifiers, and auxiliary emulsifiers.

[0065] In some embodiments, in step S1, the mass ratio of water to emulsifier is (90.00-99.999): (10.00-0.001).

[0066] Specifically, the mass ratio of water to emulsifier may be, but is not limited to, 90.00:10.00, 90.00:1.00, 90.00:0.10, 90.00:0.01, 90.00:0.001, and the like.

[0067] Step S2: Use gaseous carbon dioxide to purge the autoclave to expel the air in the autoclave, then add a preset volume of liquid carbon dioxide into the autoclave, and control the temperature range of the autoclave to be 0°C to 30°C and the pressure range to be 0MPa to 50MPa.

[0068] In some embodiments, in step S2, the volume ratio of liquid carbon dioxide to emulsifier aqueous solution is (90-10): (10-90), but is not limited thereto. In other embodiments, the volume ratio of liquid carbon dioxide to emulsifier aqueous solution can be adjusted, but the total volume is always kept consistent with the volume in the autoclave.

[0069] In some embodiments, in step S2, the autoclave is purged, and when the initial pressure is between 0.3 MPa and 0.5 MPa, carbon dioxide gas is purged into the autoclave three times, and the device used is a two-valve adapter.

[0070] In some embodiments, in step S2, liquid carbon dioxide is obtained by liquefying carbon dioxide gas, and the liquefaction step is performed in a metal pipeline.

[0071] In some embodiments, in step S2, the temperature of the autoclave can be controlled by, but not limited to, measuring the temperature of a water bath with a thermometer.

[0072] Step S3: stirring the emulsifier aqueous solution and liquid carbon dioxide in the high-pressure reactor to form a liquid CO2-H2O emulsion.

[0073] In some embodiments, in step S3, the stirring device includes at least one of an ultrasonic generator, a high shear stirrer, a constant temperature magnetic stirrer, or an electric stirring paddle.

[0074] In some embodiments, in step S3, a constant temperature magnetic stirrer is used for stirring, the stirring speed ranges from 100 rpm to 1800 rpm, and the stirring time ranges from 60 min to 300 min.

[0075] By setting the ultrasonic frequency or stirring rate, the uniformity and stability of the liquid CO2-H2O emulsion can be further improved. By setting the stirring time, the liquid carbon dioxide can fully interact with the emulsifier aqueous solution to form a uniform emulsion.

[0076] In some embodiments, in step S3, the stirrer type may be, but is not limited to, type A, type B, type C, and cross-shaped and octagonal stirrers.

[0077] In some embodiments, the method for preparing a liquid CO2-H2O emulsion further includes: detecting and recording one or more of the following data of the emulsification process and the emulsification process of the liquid CO2-H2O emulsion in the high-pressure reactor: images of the emulsification process and the emulsification process of the liquid CO2-H2O emulsion; real-time temperature; real-time pressure; conductivity; changes in the volume ratio of the liquid carbon dioxide phase, the emulsifier solution phase and the liquid CO2-H2O emulsion phase at different time points; particle size distribution and phase interface changes of the liquid CO2-H2O emulsion; structural characteristics of the liquid carbon dioxide and the emulsifier aqueous solution in the liquid CO2-H2O emulsion under the emulsion system; and droplet size of the liquid CO2-H2O emulsion.

[0078] The embodiment of the present application also provides a three-phase quantitative method for a liquid CO2-H2O emulsion. The three-phase quantitative method for the liquid CO2-H2O emulsion includes the following steps B1 to B7. Among them, the three-phase quantitative method for the liquid CO2-H2O emulsion performs a three-phase quantitative analysis of the emulsification process and the emulsification process of the liquid CO2-H2O emulsion by processing and analyzing the image information of the emulsification process and the emulsification process of the liquid CO2-H2O emulsion. Among them, the image information of the emulsification process and the emulsification process of the liquid CO2-H2O emulsion can be obtained from a certain step of the preparation method of the above-mentioned liquid CO2-H2O emulsion, but is not limited to this. In addition, according to different needs, the order of certain steps or sub-steps of the three-phase quantitative method of the liquid CO2-H2O emulsion can be changed, and certain steps or sub-steps can be omitted or combined.

[0079] Step B1: A series of images of the emulsification process and the demulsification process of the liquid CO2-H2O emulsion captured by the image acquisition system are converted into grayscale images using statistical software or a machine learning algorithm.

[0080] Step B2: Perform edge detection on the grayscale image.

[0081] Step B3: Perform morphological processing on the grayscale image after edge detection, wherein the morphological processing includes a closing operation, creating a structural element, and then performing connected component analysis.

[0082] Step B4: extracting features from the grayscale image after morphological processing.

[0083] Step B5: Display the image of the mask area.

[0084] Step B6: Using the changes in the area size of the mask region, the area changes of the emulsifier solution phase, the liquid CO2-H2O emulsion phase and the liquid carbon dioxide phase during the emulsification process of the liquid CO2-H2O emulsion are tracked.

[0085] Step B7: Using the coordinate axis positioning method, measure the height changes of the emulsifier solution phase, the liquid CO2-H2O emulsion phase, and the liquid carbon dioxide phase in the autoclave during the demulsification process of the liquid CO2-H2O emulsion.

[0086] In some embodiments, statistical software includes but is not limited to the Pandas library in Python or Matlab image processing in Matlab. Machine learning algorithms include but are not limited to linear regression, support vector machine, random forest or neural network. Specifically, Matlab image processing can be used to grayscale the collected image data, identify borders, mark different areas, etc.

[0087] In some embodiments, the three-phase quantification method for the liquid CO2-H2O emulsion further includes: establishing an area model, a height model, and a volume model for the emulsification process of the liquid CO2-H2O emulsion; predicting the correlation curves of the height, area, volume, and time of the emulsification process of the liquid CO2-H2O emulsion according to the area model, the height model, and the volume model; and optimizing at least one of the following parameters by the method of controlling variables based on the correlation curves: stirring speed, emulsifier concentration, stirring time, and stirring method.

[0088] In some embodiments, the three-phase quantification method for the liquid CO2-H2O emulsion further includes: analyzing the change in the volume ratio of the emulsifier solution phase, the liquid CO2-H2O emulsion phase, and the liquid carbon dioxide phase in the high-pressure reactor according to the rising and falling heights of the emulsifier solution phase, the liquid CO2-H2O emulsion phase, and the liquid carbon dioxide phase in the demulsification process of the liquid CO2-H2O emulsion.

[0089] In some embodiments, establishing the model for the emulsification process of the liquid CO2-H2O emulsion is to perform an area model, a height model, and a volume model on a series of images for identifying the emulsion region. The analysis refers to predicting the correlation curves of the emulsion height, area, volume, and time according to the three major models.

[0090] In some embodiments, the steps of optimizing the emulsifier concentration, stirring speed, and stirring time can adopt the method of controlling variables, and the principle of maintaining a single variable is adhered to for each optimization.

[0091] In some embodiments, the steps of optimizing the emulsifier concentration, stirring speed, and stirring time are directed at the stirring speed, and the high-speed stirring effect is higher than the low-speed stirring. Specifically, when the set stirring rate v < 800 rpm / min, the two phases of the emulsifier solution and liquid carbon dioxide cannot be dispersed; when the stirring rate 800 rpm / min < v < 1800 rpm / min, the two phases of the emulsifier solution and liquid carbon dioxide begin to be dispersed; when the stirring rate v = 1800 rpm / min, the dispersion effect of the two phases of the emulsifier solution and liquid carbon dioxide is better at high speed, and the homogeneity of the emulsion is higher.

[0092] In some embodiments, the steps of optimizing the emulsifier concentration, stirring speed, and stirring time are to optimize the setting of the stirring time, from 60 min, 120 min, 180 min, 240 min, 300 min, including extending the stirring time to improve the stability of the emulsion.

[0093] In some embodiments, the step of optimizing the emulsifier concentration, stirring speed and stirring time is to optimize the setting of the stirring mode. High-pressure ultrasonic technology is better than ordinary magnetic stirring and takes less time.

[0094] The three-phase quantitative method of the liquid CO2-H2O emulsion of the embodiment of the present application can more accurately identify the boundaries of each phase and calculate the area and height of each phase by processing a series of images of the emulsification process and demulsification process of the liquid CO2-H2O emulsion using statistical software or machine learning algorithms, thereby facilitating accurate quantitative analysis. This accurate quantitative analysis can help researchers better understand the mechanism of emulsion formation and demulsification, optimize the process parameters for preparing the liquid CO2-H2O emulsion, and improve the stability and yield of the liquid CO2-H2O emulsion.

[0095] Specifically, by tracking the area changes of each phase during the emulsification process of liquid CO2-H2O emulsion, the emulsion formation process can be monitored in real time, and the effects of different emulsification process parameters (such as emulsifier concentration, stirring time, stirring speed, etc.) on the emulsion formation can be understood, and then the emulsification process parameters can be optimized to find the best emulsification conditions, thereby improving the yield and stability of the emulsion. By measuring the height changes of each phase during the demulsification process, methods to inhibit demulsification can be found to improve the stability of the emulsion. For example, if it is found that the emulsion demulsification speed is too fast, the type of emulsifier, the concentration of the emulsifier, the stirring speed, the stirring time, etc. can be adjusted to slow down the demulsification speed and improve the stability of the emulsion. In addition, through the three-phase quantitative analysis of liquid CO2-H2O emulsion, a large amount of experimental data can be obtained, which can be used to establish a mathematical model of the emulsification process and demulsification process of the emulsion. Using these mathematical models, data-driven design of process parameters for liquid CO2-H2O emulsions can be carried out, and the performance of the emulsion under different parameters can be predicted, so as to more quickly find the preparation conditions that are most conducive to improving the stability and yield of liquid CO2-H2O emulsions.

[0096] The preparation method of the liquid CO2-H2O emulsion in the embodiment of the present application is simple, low-cost, environmentally friendly and non-toxic.

[0097] The beneficial technical effects obtained by the above method for preparing liquid CO2-H2O emulsion are as follows: (1) Environmental friendliness and sustainability ① Environmental protection: Liquid carbon dioxide, as a natural refrigerant, has a lower global warming potential (GWP) and less impact on the environment than traditional refrigerants such as Freon. In the field of skin care, the use of skin care products containing carbon dioxide can reduce pollution to the environment and is in line with the green and environmentally friendly consumption concept.

[0098] ② Sustainability: Liquid carbon dioxide can be recycled and reused to achieve resource recycling, which is in line with the concept of sustainable development. In industrial applications, liquid carbon dioxide, as a chemical raw material, can participate in a variety of chemical reactions to generate useful chemical products and promote the development of a circular economy.

[0099] (2) Efficient refrigeration and preservation ③ Efficient refrigeration: Liquid carbon dioxide absorbs a large amount of heat when it vaporizes and sublimates, so it has an efficient refrigeration effect.

[0100] In refrigeration equipment, liquid carbon dioxide can quickly lower the temperature to achieve the purpose of refrigeration.

[0101] ④ Food preservation: Liquid carbon dioxide can be used to preserve food by reducing the oxygen concentration and temperature around the food and extending the shelf life of the food. Liquid carbon dioxide is particularly widely used in the preservation of perishable foods such as dairy products.

[0102] (3) Skin care and beauty effects ⑤ Improve skin environment: Skin care products containing carbon dioxide will allow carbon dioxide to enter the skin during use, causing the Bohr effect, promoting blood flow, increasing local oxygen content in the skin, and regulating local microcirculation of the skin; this helps to improve the skin environment and make the skin healthier and more vibrant.

[0103] ⑥ Deep cleansing and blackhead removal: Carbonate skin care products can cause temporary dilation of pores, which helps deep cleansing of the skin; at the same time, it can also significantly reduce skin oil and the number of blackheads and whiteheads, making the skin more refreshed and clean.

[0104] (IV) Industrial Application and Technological Innovation ⑦ Industrial raw materials: Liquid carbon dioxide is an important industrial raw material that can be used to make soda ash, urea and other chemicals. In the chemical industry, the application of liquid carbon dioxide has promoted the development of related industries and technological innovation.

[0105] ⑧ Gas shielded welding: During the welding process, liquid carbon dioxide can be used as gas protection to prevent the weld from being corroded by harmful gases such as oxygen and nitrogen in the air, which improves the welding quality and reduces the welding cost.

[0106] ⑨ Other innovative applications: Liquid carbon dioxide can also be used in artificial rainfall, gas fire extinguishing and other fields, and has broad application prospects.

[0107] ⑩ In the field of scientific research, the study of liquid carbon dioxide / water emulsion system also provides new ideas for the development of new materials and new technologies.

[0108] In summary, liquid carbon dioxide / water emulsion has significant benefits and significance in terms of environmental friendliness and sustainability, efficient refrigeration and preservation, skin care and beauty effects, industrial applications and technological innovation. With the continuous advancement of science and technology and people's increasing attention to environmental protection, health and sustainable development, the efficient preparation and quantitative calculation of liquid carbon dioxide / water emulsion will help to promote it to a broader application prospect.

[0109] The conventional method for preparing a liquid CO2-H2O emulsion may cause the emulsion to stratify or become unstable during storage or use, whereas the method for preparing a liquid CO2-H2O emulsion and the three-phase quantitative method of the embodiments of the present application can improve the stability of the emulsion.

[0110] The traditional preparation process of liquid CO2-H2O emulsion is inefficient. The preparation method of liquid CO2-H2O emulsion and the three-phase quantitative method of the embodiment of the present application improve the production efficiency by optimizing the process conditions.

[0111] The traditional method for preparing liquid CO2-H2O emulsion has complicated operation steps. The preparation method of liquid CO2-H2O emulsion and the three-phase quantitative method of the embodiment of the present application provide a simple operation process and lower the technical threshold.

[0112] The traditional method for preparing liquid CO2-H2O emulsion may have errors in the quantification of emulsion components. The method for preparing liquid CO2-H2O emulsion and the three-phase quantification method of the embodiment of the present application improve the accuracy and reliability of the analysis through advanced quantitative technology.

[0113] The traditional method for preparing liquid CO2-H2O emulsion places a burden on the environment. The method for preparing liquid CO2-H2O emulsion and the three-phase quantitative method of the embodiment of the present application are more environmentally friendly and meet the needs of sustainable development.

[0114] The following is Example 1 of a small-scale experiment: 1. Material preparation: ① Water: 97mL ② Emulsifier (such as alkyl polyglycoside, referred to as APG): 3g ③ Liquid carbon dioxide: 50mL 2. Operation steps: ① Step 1, weighing and dissolving: Deionized water and emulsifier APG were weighed according to the mass ratio of 97.00:3.00 and added into a 200mL beaker, a stirring bar was added, and the beaker was placed on a constant temperature magnetic stirrer and stirred to allow the emulsifier to be fully dissolved in the deionized water. The emulsifier was completely dissolved in 60 minutes to obtain an emulsifier solution APG-3.00wt%; ② Step 2, liquid injection and sealing: In this experiment, the volume ratio of emulsifier solution: liquid carbon dioxide is 5:5. Use a 50mL measuring cylinder to measure 25mL of the product APG-3.0wt% solution of step 1, add it to a clean and dry fully visible sapphire autoclave (autoclave V=50mL), then put a 7mmx5mm cross-shaped stirring bar, close the valve on the autoclave, and seal the autoclave; ③ Step 3, temperature and pressure data: turn on the temperature and pressure collectors of the high-pressure reactor, set the data recording time interval to 1 time / s and the location of the saved file, start running the recording program and start saving; ④ Step 4, Image, Acquisition: Turn on the camera in the image acquisition system, adjust the camera position and image acquisition parameters such as color temperature 5046, hue -3, saturation 128, contrast 0, gamma 0.65, size 2048×3072 and format RGB24, set the image recording time interval 1 / s, naming format yyyy-mm-dd-hh-mm-ss, save method jip. and storage location, and start capturing images; ⑤ Step 5, temperature setting and exhaust: Place the fully visible sapphire high-pressure reactor in a water bath, connect the carbon dioxide gas cylinder pipeline, calibrate the temperature, set the water bath to the initial temperature of the experiment T0 = 288.15K, calibrate the pressure, open the gas cylinder, set the high-pressure reactor at P = 0.3MPa, and purge the reactor with carbon dioxide gas three times by opening and closing the valve on the high-pressure reactor to exhaust all the air; ⑥ Step 6, liquefaction and pressurization: When the temperature of the solution in the kettle (i.e. the temperature of the water bath) reaches the experimental requirements, slowly open the gas cylinder to pressurize so that the carbon dioxide gas is fully liquefied in the pipeline, and the initial pressure of the experiment is P0=6.0MPa; ⑦ Step 7, constant volume, close: After the carbon dioxide is liquefied, the temperature and pressure are normal, which are the initial setting conditions, T0=288.15K, P0=6.0MPa, close the outlet valve, open the inlet valve, 25mL of liquid carbon dioxide is slowly injected into the fully visible sapphire high-pressure reactor, first close the inlet valve, then turn off the gas cylinder switch, and remove the carbon dioxide cylinder pipeline; ⑧ Step 8, speed setting and stirring: set the speed of the stirring device to v=1600rpm; after stirring time t=300min, a carbon dioxide-water emulsion is obtained.

[0115] ⑨ Step 9, let stand and observe: turn off the stirring, let the emulsion stand, observe the changes of the emulsion during the standing period, record its stability time, and take photos at an interval of 1 photo / s. The experiment ends when the emulsion is completely demulsified or no longer changes; ⑩ Step 10, drain, wash and blow: drain the emulsion / liquid from the bottom valve, then wash the sapphire high-pressure reactor 3 times with deionized water, blow dry and prepare for next use.

[0116] The preparation and quantitative method of the above-mentioned liquid carbon dioxide / water emulsion are described in detail in conjunction with Example 1.

[0117] Figure 2 Figure (a) is a schematic diagram of the high-pressure reactor being cleaned three times and then placed in a water bath. Figure 2 Figure (b) is a schematic diagram of injecting water or emulsifier solution into the high-pressure reactor. Figure 2 Figure (c) is a schematic diagram of cooling the temperature of the water bath to about T = 288.2K. Figure 2 Figure (d) is a schematic diagram of injecting carbon dioxide to P = 6.0 MPa after purging with carbon dioxide gas three times to expel the air. Figure 2 Figure (e) is a schematic diagram of setting the magnetic stirrer at the target speed to allow the system to reach dissolution equilibrium. Figure 2 Figure (f) is a schematic diagram of emulsion demulsification after stopping stirring.

[0118] like Figure 3 As shown, the image recognition process of liquid CO2-H2O emulsion during the emulsification process includes: image read by the camera → converting the image read by the camera into a grayscale image → edge detection → morphological processing-closing operation, creating a structural element, and then performing connected component analysis → feature extraction (such as the area of ​​the area bounding box) → displaying the image of the mask area.

[0119] Similar, such as Figure 4 As shown, the image recognition process of liquid CO2-H2O emulsion in the demulsification process includes: image read by camera → converting the image read by camera into grayscale image → edge detection → morphological processing-closing operation, creating a structural element, and then connecting component analysis → feature extraction (such as the area of ​​the area bounding box) → displaying the image of the mask area.

[0120] Figure 5 Figures (a) to (j) are the experimental process of emulsion formation in the APG-3.00wt%-1600 carbon dioxide-water emulsion system and Figure 6 Figures (a) to (j) are for Figure 5 The experimental process uses the mask method to identify the emulsion area and evaluate the emulsion system from a quantitative perspective. From the image, it can be seen that when stirring is turned on, a vortex is formed under the stirring of the emulsifier solution and moves up quickly. Under high-speed stirring, the emulsifier is dispersed with the solution and gradually wraps the liquid carbon dioxide to form a series of tiny carbon dioxide droplets. Then, while stirring is maintained, more liquid carbon dioxide dissolves in the emulsifier solution. At t ef=406s, the emulsifier was observed to be completely dispersed, that is, there was no carbon dioxide droplet on the interface, so we defined this moment as the emulsion formation moment. By using Matlab to identify the image and the change in the size of the mask area, we can track the quantitative analysis of the emulsion formation process.

[0121] Figure 7 Figures (a) to (j) are the experimental process and results of emulsion demulsification in the APG-3.00wt%-1600 carbon dioxide-water emulsion system. Figure 8 Figures (a) to (j) in Figure 7 The experimental process uses the coordinate method to identify the height and evaluate the emulsion system from a quantitative perspective. bf =26min image, we can see that from stopping stirring, observing the carbon dioxide-water emulsion during the standing process, as the standing time increases, the carbon dioxide-water emulsion changes from maintaining a stable state to gradually breaking and stratifying.

[0122] Under the experimental conditions of T0=288.15K and pressure P0=6.0 MPa, the density of liquid carbon dioxide is less than that of water. Therefore, the movement direction of different liquid phases during the demulsification process is that the liquid carbon dioxide droplets slowly move upwards, and the aqueous solution gradually moves downwards. In addition, when the stirring is just stopped, since the carbon dioxide is still wrapped by the emulsifier, the initial demulsification begins with the appearance of the aqueous solution phase at the bottom of the autoclave. After the stirring is stopped, at t bf =26min, it was observed that the volume of the liquid CO2-H2O emulsion was 90% of the initial liquid CO2-H2O emulsion volume; therefore, this moment was defined as the emulsion demulsification time.

[0123] Continuous static, t=202min, t=258min, t=367min, t bf = The image at 417 minutes, the emulsifier is no longer evenly dispersed around the liquid carbon dioxide, more liquid carbon dioxide droplets are released from the wrapped state, and obvious stratification appears on the top of the high-pressure reactor, where the liquid carbon dioxide that is not completely wrapped gathers and appears in the form of liquid carbon dioxide phase.

[0124] After that, more aqueous solution phase moved downward and liquid carbon dioxide phase moved upward, respectively, from the top and bottom of the autoclave to the middle. After standing for 417 minutes, the liquid CO2-H2O emulsion was completely stratified and returned to the initial unstirred state. The final liquid CO2-H2O emulsion had good emulsion stability after standing, and no stratification was found, which was suitable for further application tests. By using Matlab to recognize images and reference coordinate axes, the changes in the current emulsion height were located, and the quantitative situation of the emulsion demulsification process was achieved.

[0125] The test conditions used in the embodiments of the present application are as follows: initial setting conditions, temperature T0=288.15K, pressure P0=6.0MPa, stirring rate v=1600rpm / min, first, 25mL of emulsifier solution is prepared in proportion and injected into the fully visible sapphire high-pressure reactor in advance, after sealing the connecting pipeline, 25mL of liquid carbon dioxide obtained by liquefying high-purity (99.8%) carbon dioxide gas is slowly injected, then the temperature collector, pressure collector, and image acquisition system software are turned on, stirring is turned on, the MZL-DJ630 microscope camera starts to collect images at 1 image / s, and the temperature collector and pressure collector record the temperature and pressure changes at a time interval of 1 time / s.

[0126] Example 2: Large-scale production 1. Material preparation: ① Water: 970 mL ② Emulsifier (such as alkyl polyglycoside, referred to as APG): 30g ③ Liquid carbon dioxide: 500mL 2. Operation steps: ① Step 1, weighing and dissolving: Deionized water and emulsifier APG were weighed in a mass ratio of 970.00:30.00 and added into a 2000mL beaker, a stirring bar was added, and the beaker was placed on a constant temperature magnetic stirrer and stirred to allow the emulsifier to be fully dissolved in the deionized water. The emulsifier was completely dissolved in 600 minutes to obtain an emulsifier solution APG-3.00wt%; ② Step 2, liquid injection and sealing: In this experiment, the volume ratio of emulsifier solution: liquid carbon dioxide is 5:5. Use a 500mL measuring cylinder to measure 250mL of the product APG-3.0wt% solution of step 1, add it to a clean and dry fully visible sapphire autoclave (autoclave V=500mL), then put a 70mmx50mm cross-shaped stirring bar, close the valve on the autoclave, and seal the autoclave; ③ Step 3, temperature and pressure data: turn on the temperature collector and pressure collector of the high-pressure reactor, set the data recording time interval to 1 time / s and the location of the saved file, start running the recording program and start saving; ④ Step 4, Image, Acquisition: Turn on the camera of the image acquisition system, adjust the camera position and image acquisition parameters such as color temperature 5046, hue -3, saturation 128, contrast 0, gamma 0.65, size 20480×30720 and format RGB24, set the image recording time interval 1 / s, naming format yyyy-mm-dd-hh-mm-ss, save method jip. and storage location, and start capturing images; ⑤ Step 5, temperature setting and exhaust: Place the fully visible sapphire high-pressure reactor in a water bath, connect the carbon dioxide gas cylinder pipeline, calibrate the temperature, set the water bath to the initial temperature of the experiment T0 = 288.15K, calibrate the pressure, open the gas cylinder, set the high-pressure reactor at P = 0.3MPa, and purge the reactor with carbon dioxide gas three times by opening and closing the valve on the high-pressure reactor to exhaust all the air; ⑥ Step 6, liquefaction and pressurization: When the temperature of the solution in the kettle (i.e. the temperature of the water bath) reaches the experimental requirements, slowly open the gas cylinder to pressurize so that the carbon dioxide gas is fully liquefied in the pipeline, and the initial pressure of the experiment is P0=6.0MPa; ⑦ Step 7, constant volume, close: After the carbon dioxide is liquefied, the temperature and pressure are normal, which are the initial setting conditions, T0=288.15K, P0=6.0MPa, close the outlet valve, open the inlet valve, 25mL of liquid carbon dioxide is slowly injected into the fully visible sapphire high-pressure reactor, first close the inlet valve, then turn off the gas cylinder switch, and remove the carbon dioxide cylinder pipeline; ⑧ Step 8, speed setting and stirring: set the speed of the stirring device to v=1600rpm / min; after stirring time t=300min, a carbon dioxide-water emulsion is obtained.

[0127] ⑨ Step 9, let stand and observe: turn off the stirring, let the emulsion stand, observe the changes of the emulsion during the standing period, record its stability time, and take photos at an interval of 1 photo / s. The experiment ends when the emulsion is completely demulsified or no longer changes; ⑩ Step 10, drain, wash and blow: drain the emulsion / liquid from the bottom valve, then wash the sapphire kettle 3 times with deionized water, blow dry and prepare for next use.

[0128] 3. Result analysis: In large-scale experiments, from the images of emulsion formation in the carbon dioxide-water emulsion system, it can be seen that when stirring is turned on, a vortex is formed under the stirring of the emulsifier solution and moves up quickly. Under high-speed stirring, the emulsifier is dispersed with the solution and gradually wraps the liquid carbon dioxide to form a series of tiny carbon dioxide droplets. Then, the stirring state is maintained, and as more liquid carbon dioxide dissolves in the emulsifier solution, at t ef =t0+300s At the moment, the emulsifier is observed to be completely dispersed by naked eyes, that is, there are no carbon dioxide droplets on the interface. Emulsion demulsification is observed after stopping stirring and the carbon dioxide-water emulsion is allowed to stand. As the standing time increases, the carbon dioxide-water emulsion changes from maintaining a stable state to gradually demulsifying and stratifying. Under the experimental conditions of T0=288.15K and pressure P0=6.0MPa, the density of liquid carbon dioxide is less than that of water. Therefore, the movement direction of different liquid phases during the demulsification process is that the liquid carbon dioxide droplets slowly move upward, and the aqueous solution gradually moves downward. In addition, when stirring is just stopped, since the carbon dioxide is still in a state of being wrapped by the emulsifier, the initial demulsification is the appearance of the aqueous solution phase from the bottom of the high-pressure reactor. After stopping stirring, at t bf =650min, it was observed that the volume of the liquid CO2-H2O emulsion was 90% of the initial liquid CO2-H2O emulsion volume. Under continuous standing, the emulsifier no longer remained uniformly dispersed around the liquid carbon dioxide, and more liquid carbon dioxide droplets were released from the wrapped state. Obvious stratification also appeared on the top of the autoclave, where the liquid carbon dioxide that was not completely wrapped gathered and appeared in the form of liquid carbon dioxide phase. After that, more aqueous solution phase moved downward and liquid carbon dioxide phase moved upward, respectively, expanding from the top and bottom of the autoclave to the middle. The liquid CO2-H2O emulsion was completely stratified and returned to the initial unstirred state. The final liquid CO2-H2O emulsion had good emulsion stability after standing, and no stratification was found, making it suitable for further application tests.

[0129] The test conditions used in the embodiments of the present application are as follows: initial setting conditions, temperature T0=288.15K, pressure P0=6.0MPa, stirring rate v=1600rpm / min, first 25mL of emulsifier solution is prepared in proportion and injected into the fully visible sapphire high-pressure reactor in advance, after sealing the connecting pipeline, 25mL of liquid carbon dioxide obtained by liquefying high-purity (99.8%) carbon dioxide gas is slowly injected, then the temperature, pressure, and image capture system software are turned on, stirring is turned on, the MZL-DJ630 microscope camera starts to collect images at 1 image / s, and the data acquisition device records the temperature and pressure changes at a time interval of 1 time / s.

[0130] When the above method was applied to different emulsifiers, such as sodium lignin sulfonate, slight changes in the stability and droplet size of the emulsions were observed, but they generally remained within an acceptable range, indicating that the method has wide applicability.

[0131] The embodiment of the present application provides an innovative method for preparing liquid carbon dioxide / water emulsion under high pressure and low temperature conditions through advanced high pressure ultrasonic conditions, which has the advantages of simple operation, high efficiency, and good emulsion stability, and proposes an intuitive, accurate, and automatic recognition image quantitative calculation method, thereby coupling an efficient and comprehensive emulsion emulsion process monitoring and optimization system, which has high innovation and practical value for deeper research on emulsions. Therefore, this method not only improves the preparation efficiency of emulsions, but also provides reliable technical support for research in related fields, helping people to better track changes in the emulsion formation and demulsification process, and meeting the needs of related industries for emulsion systems.

[0132] The present application example proposes a method for preparing a liquid carbon dioxide-water emulsion in a high-pressure reactor using advanced high-pressure ultrasonic technology. The method is simple to operate, highly efficient, and the emulsion has good stability, and has significant innovation and practical value.

[0133] The embodiment of the present application proposes an image quantitative calculation method, which is intuitive, accurate and has automatic recognition capabilities. Through advanced algorithms, it can effectively process and analyze image data, achieve fast and accurate quantitative analysis, significantly improve image processing efficiency and accuracy, and has broad application prospects.

[0134] The present application embodiment proposes an efficient and comprehensive emulsion emulsion process monitoring and optimization system, which can deeply study the formation mechanism of emulsion. The system combines advanced monitoring technology and optimization algorithm to analyze the emulsion characteristics in real time, improve the efficiency and quality of emulsion production, has significant innovation and practical value, and can provide important technical support for related fields.

[0135] The above implementation modes are only used to illustrate the technical solutions of the present application and are not intended to limit the present application. Although the present application has been described in detail with reference to the above preferred implementation modes, a person skilled in the art should understand that the technical solutions of the present application may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A device for preparing liquid CO2-H2O emulsion, characterized in that: include: A high-pressure reactor, which is fully visible and has a pressure resistance of at least 50 MPa; an injection system, connected to the high-pressure reactor, for injecting gaseous carbon dioxide, liquid carbon dioxide and an emulsifier aqueous solution into the high-pressure reactor; a stirring device, connected to the high-pressure reactor, and used for stirring the liquid carbon dioxide and the emulsifier aqueous solution in the high-pressure reactor; A constant temperature water bath system, used to accommodate the high pressure reactor to control the temperature of the high pressure reactor; A temperature sensor connected to the high-pressure reactor and used to detect the real-time temperature of the high-pressure reactor; A pressure sensor connected to the high-pressure reactor and used to detect the real-time pressure of the high-pressure reactor; An image acquisition system, used to capture image information of the emulsification process and the demulsification process of the liquid CO2-H2O emulsion in the high-pressure reactor; as well as The data acquisition system is respectively connected to the temperature sensor, the pressure sensor, the flow meter and the image acquisition system, and is used to record and analyze the real-time temperature, the real-time pressure and the image information.

2. The device for preparing liquid CO2-H2O emulsion according to claim 1, characterized in that: The device for preparing the liquid CO2-H2O emulsion further comprises a flow meter; the flow meter is connected to the high-pressure reactor and the data acquisition system, and is used to detect the volume change of the liquid CO2-H2O emulsion in the high-pressure reactor; the data acquisition system is also used to record and analyze the volume change; and / or, The liquid CO2-H2O emulsion preparation device also includes a multiphase flow sensor; the multiphase flow sensor is connected to the high-pressure reactor and the data acquisition system, and is used to monitor the volume ratio changes of the liquid carbon dioxide phase, the emulsifier solution phase and the liquid CO2-H2O emulsion phase at different time points in the high-pressure reactor; the data acquisition system is also used to record and analyze the volume ratio changes; and / or, The preparation device of the liquid CO2-H2O emulsion also includes a cryo-scanning electron microscope; the cryo-scanning electron microscope is connected to the data acquisition system and is used to observe and count the particle size distribution and phase interface changes of the liquid CO2-H2O emulsion; the data acquisition system is used to record and analyze the particle size distribution and phase interface changes; and / or, The preparation device of the liquid CO2-H2O emulsion also includes an in-situ Raman spectrometer; the in-situ Raman spectrometer is connected to the high-pressure reactor and the data acquisition system, and is used to measure the structural characteristics of the liquid carbon dioxide and the emulsifier aqueous solution in the liquid CO2-H2O emulsion under the emulsion system, so as to analyze the internal mechanism of forming the liquid CO2-H2O emulsion; the data acquisition system is also used to record and analyze the structural characteristics; and / or, The preparation device of the liquid CO2-H2O emulsion also includes an in-situ particle size analyzer; the in-situ particle size analyzer is connected to the high-pressure reactor and the data acquisition system, and is used to measure the droplet size of the liquid CO2-H2O emulsion; the data acquisition system is also used to record and analyze the droplet size; and / or, The device for preparing the liquid CO2-H2O emulsion further comprises a rotation speed sensor; the rotation speed sensor is connected to the high-pressure reactor and the data acquisition system and is used to monitor the rotation speed of the stirring device; the data acquisition system is also used to record and analyze the rotation speed; and / or, The device for preparing the liquid CO2-H2O emulsion also includes a conductivity sensor; the conductivity sensor is connected to the high-pressure reactor and the data acquisition system, and is used to monitor the conductivity in the high-pressure reactor during the preparation of the liquid CO2-H2O emulsion; the data acquisition system is also used to record and analyze the conductivity.

3. The device for preparing liquid CO2-H2O emulsion according to claim 1 or 2, characterized in that: The injection system includes a single cylinder pump and a carbon dioxide injection system; The single-cylinder pump is connected to the high-pressure reactor and the data acquisition system, and the single-cylinder pump is used to inject the emulsifier aqueous solution into the high-pressure reactor. The data acquisition system is also used to record the injection volume and injection rate of the emulsifier aqueous solution; The carbon dioxide injection system is used to be connected to the high-pressure reactor to inject gaseous carbon dioxide and liquid carbon dioxide into the high-pressure reactor.

4. The device for preparing liquid CO2-H2O emulsion according to claim 1 or 2, characterized in that: The stirring device includes at least one of an ultrasonic generator, a high shear stirrer, a constant temperature magnetic stirrer or an electric stirring paddle.

5. A method for preparing a liquid CO2-H2O emulsion, characterized in that: include: Step S1: adding an emulsifier aqueous solution obtained by mixing water and an emulsifier in a preset ratio into a high-pressure reactor, and sealing the high-pressure reactor, wherein the high-pressure reactor is fully visible and has a pressure resistance of at least 50 MPa; Step S2: purging the autoclave with gaseous carbon dioxide to discharge the air in the autoclave, then adding a preset volume of liquid carbon dioxide into the autoclave, and controlling the temperature in the autoclave to be in the range of 0° C. to 30° C. and the pressure in the autoclave to be in the range of 0 MPa to 50 MPa; as well as Step S3: stirring the emulsifier aqueous solution and the liquid carbon dioxide in the high-pressure reactor to form a liquid CO2-H2O emulsion.

6. The method for preparing the liquid CO2-H2O emulsion according to claim 5, characterized in that: In the step S1, the emulsifier is selected from one or more of lecithin, alkyl glucoside, sodium lignin sulfonate, sodium di(2-ethylhexyl) sulfonate succinate, sodium dodecyl sulfate, polyvinyl alcohol, alkylphenol polyoxyethylene ether-10, fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan monooleate, sorbitan laurate monoester, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, nanomaterials, bioacids, phosphates, polyols, amino acids, fatty acids, and citric acid, and the mass ratio of water to emulsifier is (90.00-99.999):(10.00-0.001); and / or, In the step S2, the volume ratio of the liquid carbon dioxide to the emulsifier aqueous solution is (90-10): (10-90); and / or, In the step S3, a constant temperature magnetic stirrer is used for stirring, the stirring speed ranges from 100 rpm to 1800 rpm, and the stirring time ranges from 60 min to 300 min.

7. The method for preparing the liquid CO2-H2O emulsion according to claim 5 or 6, characterized in that: The method for preparing the liquid CO2-H2O emulsion further includes: detecting and recording one or more of the following data during the emulsification process and the demulsification process of the liquid CO2-H2O emulsion in the high-pressure reactor: Images of the emulsification process and demulsification process of the liquid CO2-H2O emulsion; Real-time temperature; Real-time pressure; Conductivity; Changes in the volume ratio of the liquid carbon dioxide phase, emulsifier solution phase, and liquid CO2-H2O emulsion phase at different time points; Particle size distribution and phase interface changes of the liquid CO2-H2O emulsion; Structural characteristics of liquid carbon dioxide and emulsifier aqueous solution in the liquid CO2-H2O emulsion under the emulsion system; and The droplet size of the liquid CO2-H2O emulsion.

8. A three-phase quantitative method for liquid CO2-H2O emulsion, characterized in that: include: A series of images of the emulsification process and the demulsification process of the liquid CO2-H2O emulsion captured by the image acquisition system are converted into grayscale images using statistical software or machine learning algorithms; Performing edge detection on the grayscale image; Performing morphological processing on the grayscale image after edge detection, wherein the morphological processing includes a closing operation, creating a structural element, and then performing connected component analysis; Performing feature extraction on the grayscale image after morphological processing; Display an image of the masked area; Tracking the area changes of the emulsifier solution phase, the liquid CO2-H2O emulsion phase and the liquid carbon dioxide phase during the emulsification process of the liquid CO2-H2O emulsion by using the area changes of the mask region; and The coordinate axis positioning method was used to measure the height changes of the emulsifier solution phase, liquid CO2-H2O emulsion phase and liquid carbon dioxide phase in the autoclave during the demulsification process of the liquid CO2-H2O emulsion.

9. The three-phase quantitative method of liquid CO2-H2O emulsion according to claim 8, characterized in that: The three-phase quantitative method of the liquid CO2-H2O emulsion also includes: Establish the area model, height model and volume model of the emulsification process of liquid CO2-H2O emulsion; Predicting the height, area, volume and time correlation curve of the emulsification process of the liquid CO2-H2O emulsion according to the area model, the height model and the volume model; and Based on the correlation curve, at least one of the following parameters is optimized using a control variable method: stirring speed, emulsifier concentration, stirring time and stirring mode.

10. The three-phase quantitative method of liquid CO2-H2O emulsion according to claim 8 or 9, characterized in that: The three-phase quantitative method of the liquid CO2-H2O emulsion also includes: The change in the volume ratio of the emulsifier solution phase, liquid CO2-H2O emulsion phase, and liquid carbon dioxide phase in the high-pressure reactor was analyzed according to the rising and falling heights of the emulsifier solution phase, liquid CO2-H2O emulsion phase, and liquid carbon dioxide phase in the high-pressure reactor during the demulsification of the liquid CO2-H2O emulsion.

Images