Gas hydrate growth rate test apparatus and method with elemental sulfur precipitation

Abstract

The application discloses a gas hydrate growth rate testing device and method with element sulfur precipitation, and belongs to the technical field of hydrate experiment testing. The device comprises an element sulfur saturated gas sample preparation and sample transfer system, a vacuum treatment system, an element sulfur content determination and tail gas treatment system, a liquid supply system and an element sulfur and hydrate coupled growth rate testing system. The method first contacts methane-hydrogen sulfide mixed gas and sulfur particles at high temperature and high pressure in a saturated gas sample preparation kettle to in-situ prepare a saturated gas sample containing polysulfide, hydrogen sulfide and element sulfur; then the gas sample is transferred to a coupling generation kettle through heat preservation and sample transfer to form a "natural gas (hydrogen sulfide, methane)-water-element sulfur-hydrate" four-phase coexistence system in a low-temperature and high-pressure environment; finally, temperature, pressure, gas phase composition, image and spectrum information in the coupling generation kettle are collected, the change of the molar number of the gas phase in the kettle is calculated by combining the real gas state equation, and the hydrate growth rate with element sulfur precipitation is obtained.

Description

Technical Field

[0001] This invention belongs to the field of experimental testing technology for hydrates, specifically relating to a device and method for testing the growth rate of gaseous hydrates accompanied by the precipitation of elemental sulfur. Background Technology

[0002] Under ultra-high pressure containing sulfur (S8, H2S, H2S) X During natural gas gathering and transportation, as the gathering and transportation temperature and pressure decrease, elemental sulfur may precipitate from the system. Supersaturated elemental sulfur (such as S8) dissolved in the gas phase precipitates first (physical phase transition). When the temperature and pressure drop below the gas hydrate formation boundary, elemental sulfur and hydrates may coexist, inducing the risk of elemental sulfur and hydrate coupling and blockage. Studies have shown that elemental sulfur precipitation in reservoirs and gathering pipelines may also be accompanied by H2S. X The decomposition process involves the reaction of H2S and S8 (a chemical reaction). Simultaneously, the dynamic changes in gaseous components within the system (such as H2S) affect the formation conditions of the hydrate, and the continuous precipitation of solid elemental sulfur influences the growth kinetics of the hydrate (such as the growth rate). Experimentally testing the growth rate of natural gas hydrates accompanied by elemental sulfur precipitation is of great significance for exploring the thermodynamic and kinetic characteristics of ultra-high pressure sulfur-containing natural gas hydrates.

[0003] Currently, most experimental testing devices for natural gas hydrates are designed for systems without sulfur or with low hydrogen sulfide content, and there is a lack of experimental devices for systems with dynamic precipitation of elemental sulfur. Patents such as CN201610826046.8 and CN201811583814.7 disclose hydrate formation and kinetic testing devices, mainly used to test the formation, growth, or decomposition kinetics of gaseous hydrates, but they are difficult to characterize the influence of elemental sulfur precipitation on hydrate formation. CN202311303691.8 discloses a testing device for high-sulfur-content gas sulfur precipitation using a light source testing mechanism and a high-voltage electron microscope. Although it can test the sulfur precipitation process, it does not have hydrate preparation capabilities. Furthermore, directly placing solid elemental sulfur into containers related to hydrate preparation makes it difficult to reproduce H2S in nature. XThe chemical reaction process involving H2S and S8 decomposes into gas samples saturated with elemental sulfur, making it impossible to obtain such gas samples and thus reproduce the formation process of gaseous hydrates accompanying elemental sulfur precipitation. In general, existing experimental apparatus and methods cannot be directly used to test the hydrate formation conditions and growth rate of solid-state elemental sulfur precipitation. The main challenges are: 1) the need to prepare a four-phase coexistence system of "natural gas (hydrogen sulfide, methane) - water - elemental sulfur - hydrate" to reproduce the coupled process of elemental sulfur precipitation and hydrate formation in engineering scenarios; and 2) the need to accurately capture the filling state of the hydrate lattice, the hydrate phase equilibrium conditions, and the nucleation timing under the influence of sulfur particles, laying the foundation for accurately determining the hydrate formation state and growth rate. Therefore, there is an urgent need to provide an apparatus and method for testing the growth rate of gaseous hydrates accompanied by elemental sulfur precipitation to solve the problems of existing apparatus in preparing saturated gas samples containing polysulfides, hydrogen sulfide, and elemental sulfur, constructing a four-phase system, and replicating the coupled formation process of elemental sulfur precipitation and hydrates. Summary of the Invention

[0004] This invention aims to overcome the shortcomings of existing technologies and provide a device and method for testing the growth rate of gaseous hydrates with elemental sulfur precipitation. It can achieve full contact reaction between methane-hydrogen sulfide mixture and solid sulfur particles under high temperature and high pressure conditions, prepare a saturated gas sample containing polysulfides, hydrogen sulfide and elemental sulfur in situ, and transfer the gas sample to a coupled generation vessel under heat preservation conditions. The gas sample and water are then used to form a hydrate generation system with elemental sulfur precipitation under low temperature and high pressure, thereby realizing the coupled simulation of the elemental sulfur precipitation process and the hydrate generation process and the test of the growth rate.

[0005] The technical solution adopted in this invention is: A device for testing the growth rate of gaseous hydrates with elemental sulfur precipitation is characterized by comprising an elemental sulfur saturated gas sample preparation and transfer system, a vacuum processing system, an elemental sulfur content determination and tail gas treatment system, a liquid supply system, and an elemental sulfur and hydrate coupled growth rate testing system. Preferably, the elemental sulfur saturated gas sample preparation and transfer system includes a methane cylinder 001, a methane inlet control valve 002, a methane flow meter 003, a hydrogen sulfide cylinder 004, a hydrogen sulfide inlet control valve 005, a hydrogen sulfide flow meter 006, a mixed gas sample tank 007, a mixed gas inlet control valve 008, a gas booster pump 009, a hydraulic return oil pressure relief pipeline 010, a hydraulic loading device 011, a hydraulic oil inlet booster pipeline 012, a first temperature and pressure acquisition terminal 013, and a first pressure... Force sensor 014, first temperature sensor 015, double-piston sealing ring 016, saturated gas sample preparation vessel 017, solid particle trap 018, electric heater 019, solid sulfur bed 020, porous support plate with fine mesh filter 021, floating piston 022, constant temperature chamber 023, first sample transfer control valve 024, heat-insulated sample transfer pipeline 025, second sample transfer control valve 026, sample transfer flow meter 027, sample transfer pressure gauge 028, and sample transfer temperature gauge 029; Preferably, the outlet of methane cylinder 001 is connected to mixed gas sample tank 007 via methane inlet control valve 002 and methane flow meter 003 in sequence; the outlet of hydrogen sulfide cylinder 004 is connected to mixed gas sample tank 007 via hydrogen sulfide inlet control valve 005 and hydrogen sulfide flow meter 006 in sequence; the outlet of mixed gas sample tank 007 is connected to saturated gas sample preparation vessel 017 via mixed gas inlet control valve 008 and gas booster pump 009 in sequence, for preparing the required volume fraction of methane-hydrogen sulfide in the experiment; Preferably, the saturated gas sample preparation vessel 017 is located inside the constant temperature chamber 023; the solid particle trap 018 is located between the solid sulfur bed 020 and the outlet of the saturated gas sample preparation vessel 017; the pressure tapping end of the first pressure sensor 014 is located above the solid sulfur bed 020; the solid sulfur bed 020 is located above the porous support plate 021 with a fine-mesh filter; the porous support plate 021 with a fine-mesh filter is located above the floating piston 022; the detection end of the first temperature sensor 015 is located between the solid sulfur bed 020 and the porous support plate 021 with a fine-mesh filter; the floating piston 022 is located at the lower part of the saturated gas sample preparation vessel 017; the lower part of the floating piston 022 is a hydraulic chamber; a double-piston sealing ring 016 is fitted around the outer periphery of the floating piston 022 and makes sealing contact with the inner wall of the saturated gas sample preparation vessel 017; the hydraulic loading device 011 is connected to the saturated gas sample preparation vessel 017 via a hydraulic oil inlet pressurization pipeline 012 and a hydraulic oil return pressure relief pipeline 010. The hydraulic chamber is connected, and the hydraulic oil inlet booster pipe 012 is used to inject hydraulic oil into the hydraulic chamber to push the floating piston 022 upward and increase the pressure inside the saturated gas sample preparation vessel 017. The hydraulic oil return and depressurization pipe 010 is used to return the hydraulic oil in the hydraulic chamber to make the floating piston 022 move downward and reduce the pressure inside the saturated gas sample preparation vessel 017. The electric heater 019 is set on the outer wall of the saturated gas sample preparation vessel 017. The first temperature and pressure acquisition terminal 013 is electrically connected to the first pressure sensor 014 and the first temperature sensor 015, respectively. The heat-insulating sample transfer pipe 025 connects the saturated gas sample preparation vessel 017 and the coupling generation vessel 411. The heat-insulating sample transfer pipe 025 transfers samples from the saturated gas sample preparation vessel 017 to the coupling generation vessel 411. The heat-insulating sample transfer pipe 025 is equipped with a first transfer control valve 024, a second transfer control valve 026, a transfer flow meter 027, a transfer pressure gauge 028, and a transfer temperature gauge 029 in sequence. Preferably, the vacuum processing system includes a vacuum pump 101, a vacuum control valve 102, and a vacuum pipeline; one end of the vacuum pipeline is connected to the gas phase space of the coupling generation vessel 411, and the other end is connected to the exhaust port of the vacuum pump 101 via the vacuum control valve 102. Preferably, the elemental sulfur content determination and exhaust gas treatment system includes an exhaust gas treatment device 201, a gas meter 202, an elemental sulfur analyzer 203, an elemental sulfur trap 204, a sampling control valve 205, and a sampling branch; one end of the sampling branch is connected to the heat-insulated transfer pipeline 025 between the first transfer control valve 024 and the second transfer control valve 026, and the other end is connected to the elemental sulfur trap 204 via the sampling control valve 205; the outlet of the elemental sulfur trap 204 is connected to the inlet of the gas meter 202 via a pipeline, and the outlet of the gas meter 202 is connected to the inlet of the exhaust gas treatment device 201 via a pipeline; the elemental sulfur trap 204 contains liquid carbon disulfide, and is connected to the elemental sulfur analyzer 203 via a pipeline, with one end of the pipeline near the bottom of the elemental sulfur trap 204 and the other end connected to the elemental sulfur analyzer 203; Preferably, the liquid supply system includes a liquid supply container 301, a first liquid supply control valve 302, a liquid supply pump 303, a second liquid supply control valve 304, and a liquid supply pipeline; the liquid supply pipeline connects the liquid supply container 301 and the coupling generation vessel 411, and supplies liquid to the coupling generation vessel 411. The first liquid supply control valve 302, the liquid supply pump 303, and the second liquid supply control valve 304 are sequentially arranged on the liquid supply pipeline in this direction. Preferably, the elemental sulfur and hydrate coupling growth rate testing system includes a constant temperature water bath 401, a gas phase composition analyzer 402, a second temperature and pressure acquisition terminal 403, a second pressure sensor 404, a light source 405, a second temperature sensor 406, a stirring drive motor 407, a magnetic coupling sealing transmission assembly 408, an in-vessel stirring paddle 409, a spectral receiving end 410, a coupling generation vessel 411, a spectral transmission fiber optic cable 412, a spectrometer 413, a high-speed camera 414, an image receiving terminal 415, a spectral data analysis system 416, and a laser emitting end 417. Preferably, the constant temperature water bath 401 is connected to the coupling generation vessel 411 for heat exchange via a water bath circulation pipeline; the gas phase composition analyzer 402 is connected to the gas phase space of the coupling generation vessel 411 via a pipeline; the second pressure sensor 404 and the second temperature sensor 406 are connected to the gas phase space of the coupling generation vessel 411, and the second pressure sensor 404 and the second temperature sensor 406 are electrically connected to the second temperature and pressure acquisition terminal 403 respectively; the light source 405 and the high-speed camera 414 are respectively disposed on both sides of the visual observation area of ​​the coupling generation vessel 411, and the high-speed camera 414 is electrically connected to the image receiving terminal 415; the stirring... The stirring drive motor 407 is connected to the stirring paddle 409 inside the vessel via the magnetic coupling sealed transmission assembly 408; the spectral receiver 410 is connected to the coupling generation vessel 411 to receive the spectral signal generated after the laser emitter 417 irradiates the reaction system inside the coupling generation vessel 411; the spectral receiver 410 is connected to the spectrometer 413 via the spectral transmission fiber optic cable 412; the spectral data analysis system 416 is electrically connected to the laser emitter 417 and the spectrometer 413 respectively, and assists in judging the nucleation and growth process of hydrate based on the changes in the peak position, peak shape and relative intensity of the characteristic spectral peaks of methane and hydrogen sulfide during the hydrate formation process.

[0006] A method for testing the growth rate of gas hydrates with elemental sulfur precipitation, using the aforementioned testing device for the growth rate of gas hydrates with elemental sulfur precipitation, is characterized by comprising the following steps: S1: Solid sulfur loading, vacuuming, and water injection: Solid sulfur particles are loaded onto the solid sulfur bed 020; the methane inlet control valve 002, hydrogen sulfide inlet control valve 005, mixed gas inlet control valve 008, sampling control valve 205, first liquid supply control valve 302, and second liquid supply control valve 304 are closed; the first sample transfer control valve 024, second sample transfer control valve 026, and vacuum control valve 102 are opened; the vacuum pump 101 is started to evacuate the entire system; when the absolute pressure of the system drops below 1 kPa, the vacuum pump 101 is stopped, and the vacuum control valve 102, first sample transfer control valve 024, and second sample transfer control valve 026 are closed; the first liquid supply control valve 302 and second liquid supply control valve 304 are opened, and the liquid supply pump 303 is started to fill the pre-measured volume in the liquid supply container 301. V w Water is injected into the coupling reactor 411. After the liquid supply is completed, the liquid supply pump 303, the first liquid supply control valve 302, and the second liquid supply control valve 304 are closed. Using the formula... Determine the gas phase volume within the coupled generation vessel 411 V g In the formula, V g The volume of the gas phase within the coupling reactor 411 is m³; V 0 represents the calibration volume of the coupling generation vessel 411, in m³. Vw The volume of water to be injected is measured in advance, in m³. V f The volume occupied by the fixed components inside the coupling reactor 411 is m³. S2: Preparation of methane-hydrogen sulfide mixture: With the first sample transfer control valve 024, the second sample transfer control valve 026, and the sampling control valve 205 closed, open the methane inlet control valve 002 and the hydrogen sulfide inlet control valve 005. Control the inlet flow rates of methane and hydrogen sulfide through the methane flow meter 003 and the hydrogen sulfide flow meter 006, respectively, so that the two gases enter the mixed gas sample tank 007 and form a methane-hydrogen sulfide mixture with the required hydrogen sulfide volume fraction for the experiment. After the mixture is prepared, close the methane inlet control valve 002 and the hydrogen sulfide inlet control valve 005, open the mixed gas inlet control valve 008, start the gas booster pump 009, and pressurize and deliver the methane-hydrogen sulfide mixture to the saturated gas sample preparation vessel 017. After the delivery is completed, stop the gas booster pump 009 and close the mixed gas inlet control valve 008. S3: High-temperature and high-pressure in-situ preparation of elemental sulfur saturated gas sample: Keep the first sample transfer control valve 024, the second sample transfer control valve 026, and the sampling control valve 205 closed, start the electric heater 019, and control the hydraulic loading device 011 to push the floating piston 022 upward. Monitor the temperature and pressure inside the saturated gas sample preparation vessel 017 through the first pressure sensor 014, the first temperature sensor 015, and the first temperature and pressure acquisition terminal 013. Adjust the pressure and temperature inside the saturated gas sample preparation vessel 017 to 60 MPa and 160 °C, respectively. Allow the methane-hydrogen sulfide mixture to react with the sulfur particles in the solid sulfur bed 020 for 12 hours, promoting the reaction of hydrogen sulfide with elemental sulfur to form polysulfides (H2S). X A saturated gas sample containing hydrogen polysulfide, hydrogen sulfide, and elemental sulfur was obtained. S4: Determination of elemental sulfur mass concentration: Maintain the reaction temperature and pressure in the saturated gas sample preparation vessel 017, close the second sample transfer control valve 026, and open the first sample transfer control valve 024 and the sampling control valve 205; allow the gas sample to be introduced into the pre-filled vessel containing a mass of... m The elemental sulfur trap 204 uses carbon disulfide liquid to trap elemental sulfur in a gas sample, and the gas volume after passing through the elemental sulfur trap 204 is measured by a gas meter 202. V 1. The exhaust gas is treated by exhaust gas treatment device 201, and the mass fraction of elemental sulfur in the carbon disulfide liquid is determined by elemental sulfur analyzer 203. S 0; using the formula Calculate the mass concentration of elemental sulfur in an elemental sulfur-saturated gas sample. C In the formula, C The mass concentration of elemental sulfur in the gas sample is g / m³. 3 ; mThe amount of carbon disulfide liquid pre-loaded into elemental sulfur trap 204, in g; S 0 represents the mass fraction of elemental sulfur in liquid carbon disulfide, as measured by the elemental sulfur analyzer 203, in percentages (%). V 1 represents the gas volume after passing through liquid carbon disulfide under standard conditions, in m. 3 ;when C When the required sulfur mass concentration range for the experiment is reached, the measurement is complete, and the first sample transfer control valve 024 and the sampling control valve 205 are closed. S5: Transfer of saturated sulfur gas sample: Start the constant temperature water bath 401 to maintain the temperature of the liquid phase in the coupling generation vessel 411 at 100℃; close the sampling control valve 205, and open the first transfer control valve 024 and the second transfer control valve 026 to transfer the gas sample intercepted by the solid particle interceptor 018 into the coupling generation vessel 411 via the heat-insulated transfer pipeline 025; during the transfer process, the pressure in the saturated gas sample preparation vessel 017 and the coupling generation vessel 411 is monitored by the first pressure sensor 014 and the second pressure sensor 404 respectively, and the hydraulic loading device 01 is controlled. 1. Push the floating piston 022 upward to continuously pressurize the saturated gas sample preparation vessel 017, ensuring that the pressure inside the saturated gas sample preparation vessel 017 is always higher than the pressure inside the coupling generation vessel 411. When the second pressure sensor 404 measures that the pressure inside the coupling generation vessel 411 reaches 60MPa, close the first sample transfer control valve 024 and the second sample transfer control valve 026. Monitor the sample transfer flow rate, pressure, and temperature through the sample transfer flow meter 027, sample transfer pressure gauge 028, and sample transfer temperature gauge 029. Insulate the sample transfer pipeline 025 to prevent the gas sample temperature from dropping and causing premature precipitation of elemental sulfur. S6: Elemental sulfur precipitation and hydrate coupling: Keep the first sample transfer control valve 024, the second sample transfer control valve 026 and the sampling control valve 205 closed, reduce the temperature of the reaction system in the coupling generation vessel 411 by cooling the constant temperature water bath 401 at a cooling rate of 0.1℃ / min, and start the stirring drive motor 407 to drive the stirring paddle 409 in the vessel to rotate through the magnetic coupling sealing transmission component 408 to enhance gas-liquid mass transfer; when the temperature of the reaction system drops to the elemental sulfur saturation boundary, the polysulfide decomposes and precipitates solid-phase elemental sulfur, and continues to cool below the hydrate generation boundary, so that methane and hydrogen sulfide react with water to form hydrates. The precipitated elemental sulfur acts as a heterogeneous nucleation interface to participate in hydrate nucleation and growth, forming a sulfur-containing natural gas (hydrogen sulfide, methane)-water-elemental sulfur-hydrate four-phase system; S7: Hydrate growth rate calculation: Upon the start of cooling and stirring, the gas phase composition analyzer 402, the second temperature and pressure acquisition terminal 403, the light source 405, the spectrometer 413, the high-speed camera 414, the image receiving terminal 415, the spectral data analysis system 416, and the laser emitter 417 are simultaneously activated; the gas phase pressure inside the coupled generation vessel 411 is collected according to the sampling interval. P (t ),temperature T ( t Based on the concentrations, images, and spectral information of each gaseous component, and considering the phenomena of elemental sulfur precipitation and hydrate formation in the images, combined with the peak positions, shapes, and relative intensity changes of characteristic spectral peaks of methane and hydrogen sulfide, the nucleation and growth processes of hydrates are determined; based on the concentrations and pressures of the gaseous components... P ( t ),temperature T ( t The compressibility factor is calculated by combining the cubic additional associated term state equation (i.e., the CPA state equation). Z ( t ), using formula Calculate the number of gaseous moles in reactor 411 during hydrate formation. n g ( t In the formula, n g ( t )for t Moles of gas phase in reactor 411 at any given time, in mol; V g The volume of the gas phase within the coupling reactor 411 is m³; P ( t )for t The gas phase pressure inside the coupled generation vessel 411, measured by the second pressure sensor 404 at any given time, in Pa; T ( t )for t The temperature inside the coupling generation vessel 411 measured by the second temperature sensor 406 at any given time, in K; Z ( t )for t At all times, the gas phase is under pressure P ( t ),temperature T ( t The compressibility factor under the given gas phase composition conditions, wherein the gas phase composition is measured by a gas phase composition analyzer 402; R is the gas constant, 8.314 J / (mol·K); and the formula is used... Calculation based on sampling time t i Until the next sampling time t i+1 The growth rate of hydrates accompanied by elemental sulfur precipitation during this period r g In the formula, r g The hydrate growth rate is expressed in mol / s as the number of moles of gas phase consumed in the coupled generation vessel 411. t i and ti+1 The records of the second temperature and pressure acquisition terminal 403 are respectively the first i The sampling time and the first sampling time i +1 sampling time, s; n g ( t i )and n g ( t i+1 ) are respectively t i and t i+1 The number of moles of gas phase in the coupled reactor 411 at any given time, in mol.

[0007] By adopting the above technical solutions, the present invention can achieve the following beneficial effects: (1) This invention allows a methane-hydrogen sulfide mixture to react with solid sulfur particles under high temperature and high pressure conditions, which promotes the reaction of hydrogen sulfide with elemental sulfur to form polysulfide. A saturated gas sample containing polysulfide, hydrogen sulfide and elemental sulfur is obtained in situ, which reproduces the composition of real sulfur-containing gas samples in nature. Through the elemental sulfur content determination and tail gas treatment system, the continuous and quantitative characterization of the mass concentration of elemental sulfur in the gas sample is realized, which provides a basis for setting the mass concentration of elemental sulfur in hydrate formation experiments. (2) The present invention adopts a heat preservation and sample transfer method to transfer the elemental sulfur saturated gas sample to the coupling generation vessel 411, so as to avoid the gas sample precipitating elemental sulfur in the heat preservation and sample transfer pipeline 025 due to cooling. At the same time, the coupling generation vessel 411 is continuously cooled at a certain rate through the constant temperature water bath 401, and the polysulfide decomposes and first precipitates elemental sulfur particles. Subsequently, when the temperature inside the vessel is further reduced, on the one hand, the decomposition reaction product hydrogen sulfide and the original methane molecules in the system react with water to form hydrates; on the other hand, the precipitated elemental sulfur particles act as heterogeneous nucleation interfaces to participate in the hydrate nucleation and growth process, thereby forming a four-phase system of sulfur-containing natural gas (hydrogen sulfide, methane)-water-elemental sulfur-hydrate coexisting. The growth rate test of hydrate with dynamic precipitation of elemental sulfur is realized under indoor conditions, overcoming the inability of existing experimental devices and methods to reproduce the coupling process of elemental sulfur precipitation and hydrate formation. (3) The present invention collects visual images and spectral information inside the coupling generation vessel 411 to help identify the stages of elemental sulfur precipitation, hydrate formation and growth; calculates the compressibility factor based on the gas phase composition, pressure and temperature using the cubic additional association term equation of state (i.e., CPA equation of state); and determines the hydrate growth rate based on the change in the number of gas moles during the hydrate growth stage, thereby realizing the test of the growth rate of high-pressure sulfur-containing natural gas hydrates precipitated by elemental sulfur. Attached Figure Description

[0008] Figure 1This is a schematic diagram of the overall structure of the gas hydrate growth rate testing device with elemental sulfur precipitation according to the present invention. The right side of the figure shows the elemental sulfur saturated gas sample preparation and transfer system, the lower middle part shows the elemental sulfur content determination and tail gas treatment system, and the left side shows the liquid supply system, vacuum treatment system, and elemental sulfur and hydrate coupled growth rate testing system. In the diagram: 001-Methane cylinder; 002-Methane inlet control valve; 003-Methane flow meter; 004-Hydrogen sulfide cylinder; 005-Hydrogen sulfide inlet control valve; 006-Hydrogen sulfide flow meter; 007-Mixed gas sample container; 008-Mixed gas inlet control valve; 009-Gas booster pump; 010-Hydraulic return oil pressure relief pipeline; 011-Hydraulic loading device; 012-Hydraulic oil inlet booster pipeline; 013-First temperature and pressure acquisition terminal; 014-The... 015-Pressure sensor; 016-First temperature sensor; 017-Double-stage piston seal; 018-Saturated gas sample preparation vessel; 019-Solid particle trap; 020-Electric heater; 021-Solid sulfur bed; 022-Porous support plate with fine-mesh filter; 023-Floating piston; 024-Thermostatic chamber; 025-First sample transfer control valve; 026-Insulated sample transfer pipeline; 027-Second sample transfer control valve; 028-Sample flow meter; Sample transfer pressure gauge; 029-Sample transfer temperature gauge; 101-Vacuum pump; 102-Vacuum control valve; 201-Tail gas treatment device; 202-Gas meter; 203-Elemental sulfur analyzer; 204-Elemental sulfur trap; 205-Sampling control valve; 301-Liquid supply container; 302-First liquid supply control valve; 303-Liquid supply pump; 304-Second liquid supply control valve; 401-Constant temperature water bath; 402-Gas phase composition analyzer; 403-Second temperature... Pressure acquisition terminal; 404-Second pressure sensor; 405-Light source; 406-Second temperature sensor; 407-Stirring drive motor; 408-Magnetic coupling sealing transmission assembly; 409-Stirring paddle inside the vessel; 410-Spectrum receiver; 411-Coupled generation vessel; 412-Spectrum transmission fiber optic cable; 413-Spectrometer; 414-High-speed camera; 415-Image receiving terminal; 416-Spectrum data analysis system; 417-Laser emitting end. Detailed Implementation

[0009] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described below in conjunction with the accompanying drawings and examples.

[0010] Figure 1This is a schematic diagram of a device for testing the growth rate of gaseous hydrates accompanied by elemental sulfur precipitation. It includes a methane cylinder (001), a methane inlet control valve (002), a methane flow meter (003), a hydrogen sulfide cylinder (004), a hydrogen sulfide inlet control valve (005), a hydrogen sulfide flow meter (006), a mixed gas sample container (007), a mixed gas inlet control valve (008), a gas booster pump (009), a hydraulic return oil pressure relief pipeline (010), a hydraulic loading device (011), a hydraulic oil inlet booster pipeline (012), a first temperature and pressure acquisition terminal (013), a first pressure sensor (014), a first temperature sensor (015), a double-piston sealing ring (016), a saturated gas sample preparation vessel (017), a solid particle trap (018), an electric heater (019), a solid sulfur bed (020), a porous support plate with a fine-mesh filter (021), a floating piston (022), a constant temperature chamber (023), a first sample transfer control valve (024), an insulated sample transfer pipeline (025), and a second sample transfer control valve (026). 1. Sample transfer flow meter 027, sample transfer pressure gauge 028, sample transfer temperature gauge 029, vacuum pump 101, vacuum control valve 102, tail gas treatment device 201, gas metering instrument 202, elemental sulfur analyzer 203, elemental sulfur trap 204, sampling control valve 205, liquid supply container 301, first liquid supply control valve 302, liquid supply pump 303, second liquid supply control valve 304, constant temperature water bath 401, gas phase composition analyzer 402, second temperature and pressure acquisition terminal 403, second pressure sensor 404, light source 405, second temperature sensor 406, stirring drive motor 407, magnetic coupling sealing transmission assembly 408, in-vessel stirring paddle 409, spectral receiver 410, coupling generation vessel 411, spectral transmission fiber optic cable 412, spectrometer 413, high-speed camera 414, image receiving terminal 415, spectral data analysis system 416, laser emitter 417.

[0011] The growth rate of hydrates with elemental sulfur precipitation was tested using the above-mentioned apparatus, and the specific steps are as follows: S1: Solid sulfur loading, vacuuming, and water injection: Solid sulfur particles are loaded onto the solid sulfur bed 020; the methane inlet control valve 002, hydrogen sulfide inlet control valve 005, mixed gas inlet control valve 008, sampling control valve 205, first liquid supply control valve 302, and second liquid supply control valve 304 are closed; the first sample transfer control valve 024, second sample transfer control valve 026, and vacuum control valve 102 are opened; the vacuum pump 101 is started to evacuate the entire system; when the absolute pressure of the system drops below 1 kPa, the vacuum pump 101 is stopped, and the vacuum control valve 102, first sample transfer control valve 024, and second sample transfer control valve 026 are closed; the first liquid supply control valve 302 and second liquid supply control valve 304 are opened, and the liquid supply pump 303 is started to fill the pre-measured volume in the liquid supply container 301. V wWater is injected into the coupling reactor 411. After the liquid supply is completed, the liquid supply pump 303, the first liquid supply control valve 302, and the second liquid supply control valve 304 are closed. Using the formula... Determine the gas phase volume within the coupled generation vessel 411 V g In the formula, V g The volume of the gas phase within the coupling reactor 411 is m³; V 0 represents the calibration volume of the coupling generation vessel 411, in m³. V w The volume of water to be injected is measured in advance, in m³. V f The volume occupied by the fixed components inside the coupling reactor 411 is m³. S2: Preparation of methane-hydrogen sulfide mixture: With the first sample transfer control valve 024, the second sample transfer control valve 026, and the sampling control valve 205 closed, open the methane inlet control valve 002 and the hydrogen sulfide inlet control valve 005. Control the inlet flow rates of methane and hydrogen sulfide through the methane flow meter 003 and the hydrogen sulfide flow meter 006, respectively, so that the two gases enter the mixed gas sample tank 007 and form a methane-hydrogen sulfide mixture with a volume fraction of 3% hydrogen sulfide. After the mixture is prepared, close the methane inlet control valve 002 and the hydrogen sulfide inlet control valve 005, open the mixed gas inlet control valve 008, start the gas booster pump 009, and pressurize and deliver the methane-hydrogen sulfide mixture to the saturated gas sample preparation vessel 017. After the delivery is completed, stop the gas booster pump 009 and close the mixed gas inlet control valve 008. S3: High-temperature and high-pressure in-situ preparation of elemental sulfur saturated gas sample: Keep the first sample transfer control valve 024, the second sample transfer control valve 026, and the sampling control valve 205 closed, start the electric heater 019, and control the hydraulic loading device 011 to push the floating piston 022 upward. Monitor the temperature and pressure inside the saturated gas sample preparation vessel 017 through the first pressure sensor 014, the first temperature sensor 015, and the first temperature and pressure acquisition terminal 013. Adjust the pressure and temperature inside the saturated gas sample preparation vessel 017 to 60 MPa and 160 °C, respectively. Allow the methane-hydrogen sulfide mixture to react with the sulfur particles in the solid sulfur bed 020 for 12 hours, promoting the reaction of hydrogen sulfide with elemental sulfur to form polysulfides (H2S). X A saturated gas sample containing hydrogen polysulfide, hydrogen sulfide, and elemental sulfur was obtained. S4: Determination of elemental sulfur mass concentration: Maintain the reaction temperature and pressure in the saturated gas sample preparation vessel 017, close the second sample transfer control valve 026, and open the first sample transfer control valve 024 and the sampling control valve 205; allow the gas sample to be introduced into the pre-filled vessel containing a mass of... mThe elemental sulfur trap 204 uses carbon disulfide liquid to trap elemental sulfur in a gas sample, and the gas volume after passing through the elemental sulfur trap 204 is measured by a gas meter 202. V 1. The exhaust gas is treated by exhaust gas treatment device 201, and the mass fraction of elemental sulfur in the carbon disulfide liquid is determined by elemental sulfur analyzer 203. S 0; using the formula Calculate the mass concentration of elemental sulfur in an elemental sulfur-saturated gas sample. C In the formula, C The mass concentration of elemental sulfur in the gas sample is g / m³. 3 ; m The amount of carbon disulfide liquid pre-loaded into elemental sulfur trap 204, in g; S 0 represents the mass fraction of elemental sulfur in liquid carbon disulfide, as measured by the elemental sulfur analyzer 203, in percentages (%). V 1 represents the gas volume after passing through liquid carbon disulfide under standard conditions, in m. 3 ;when C When the required sulfur mass concentration range for the experiment is reached, the measurement is complete, and the first sample transfer control valve 024 and the sampling control valve 205 are closed. S5: Transfer of saturated sulfur gas sample: Start the constant temperature water bath 401 to maintain the temperature of the liquid phase in the coupling generation vessel 411 at 100℃; close the sampling control valve 205, and open the first transfer control valve 024 and the second transfer control valve 026 to transfer the gas sample intercepted by the solid particle interceptor 018 into the coupling generation vessel 411 via the heat-insulated transfer pipeline 025; during the transfer process, the pressure in the saturated gas sample preparation vessel 017 and the coupling generation vessel 411 is monitored by the first pressure sensor 014 and the second pressure sensor 404 respectively, and the hydraulic loading device 01 is controlled. 1. Push the floating piston 022 upward to continuously pressurize the saturated gas sample preparation vessel 017, so that the pressure in the saturated gas sample preparation vessel 017 is always higher than the pressure in the coupling generation vessel 411. When the second pressure sensor 404 measures that the pressure in the coupling generation vessel 411 reaches 60MPa, close the first transfer control valve 024 and the second transfer control valve 026. Monitor the transfer flow rate, pressure and temperature through the transfer flow meter 027, transfer pressure gauge 028 and transfer temperature gauge 029. Insulate the transfer pipeline 025 to prevent the gas sample temperature from dropping and causing elemental sulfur to precipitate prematurely. S6: Elemental sulfur precipitation and hydrate coupling: Keep the first sample transfer control valve 024, the second sample transfer control valve 026 and the sampling control valve 205 closed, reduce the temperature of the reaction system in the coupling generation vessel 411 by cooling the constant temperature water bath 401 at a cooling rate of 0.1℃ / min, and start the stirring drive motor 407 to drive the stirring paddle 409 in the vessel to rotate through the magnetic coupling sealing transmission component 408 to enhance gas-liquid mass transfer; when the temperature of the reaction system drops to the elemental sulfur saturation boundary, the polysulfide decomposes and precipitates solid-phase elemental sulfur, and continues to cool below the hydrate generation boundary, so that methane and hydrogen sulfide react with water to form hydrates. The precipitated elemental sulfur acts as a heterogeneous nucleation interface to participate in hydrate nucleation and growth, forming a sulfur-containing natural gas (hydrogen sulfide, methane)-water-elemental sulfur-hydrate four-phase system; S7: Hydrate growth rate calculation: Upon the start of cooling and stirring, the following components are simultaneously activated: gas phase composition analyzer 402, second temperature and pressure acquisition terminal 403, light source 405, spectrometer 413, high-speed camera 414, image receiving terminal 415, spectral data analysis system 416, and laser emitter 417; the gas phase pressure inside the coupled generation vessel 411 is collected at 1-second intervals. P ( t ),temperature T ( t Based on the concentrations, images, and spectral information of each gaseous component, and considering the phenomena of elemental sulfur precipitation and hydrate formation in the images, combined with the peak positions, shapes, and relative intensity changes of characteristic spectral peaks of methane and hydrogen sulfide, the nucleation and growth processes of hydrates are determined; based on the concentrations and pressures of the gaseous components... P ( t ),temperature T ( t The compressibility factor is calculated by combining the cubic additional associated term state equation (i.e., the CPA state equation). Z ( t ), using formula Calculate the number of gaseous moles in reactor 411 during hydrate formation. n g ( t In the formula, n g ( t )for t Moles of gas phase in reactor 411 at any given time, in mol; V g The volume of the gas phase within the coupling reactor 411 is m³; P ( t )for t The gas phase pressure inside the coupled generation vessel 411, measured by the second pressure sensor 404 at any given time, in Pa; T ( t )for tThe temperature inside the coupling generation vessel 411 measured by the second temperature sensor 406 at any given time, in K; Z ( t )for t At all times, the gas phase is under pressure P ( t ),temperature T ( t The compressibility factor under the given gas phase composition conditions, wherein the gas phase composition is measured by a gas phase composition analyzer 402; R is the gas constant, 8.314 J / (mol·K); and the formula is used... Calculation based on sampling time t i Until the next sampling time t i+1 The growth rate of hydrates accompanied by elemental sulfur precipitation during this period r g In the formula, r g The hydrate growth rate is expressed in mol / s as the number of moles of gas phase consumed in the coupled generation vessel 411. t i and t i+1 The records of the second temperature and pressure acquisition terminal 403 are respectively the first i The sampling time and the first sampling time i +1 sampling time, s; n g ( t i )and n g ( t i+1 ) are respectively t i and t i+1 The number of moles of gas phase in the coupled reactor 411 at any given time, in mol.

[0012] This invention constructs a gas hydrate growth rate testing device with elemental sulfur precipitation by using an elemental sulfur saturated gas sample preparation and transfer system, a vacuum processing system, an elemental sulfur content determination and tail gas treatment system, a liquid supply system, and an elemental sulfur and hydrate coupling growth rate testing system. This device enables in-situ preparation of elemental sulfur saturated gas samples, determination of elemental sulfur mass concentration, heat preservation and sample transfer, elemental sulfur precipitation and hydrate coupling generation, and hydrate growth rate testing. The apparatus reacts a methane-hydrogen sulfide mixture with solid sulfur particles under high temperature and pressure to form hydrogen polysulfide, producing a saturated gas sample containing hydrogen polysulfide, hydrogen sulfide, and elemental sulfur. The gas sample is transferred to the coupling generation vessel 411 via a heat-insulated transfer pipeline 025 to prevent premature precipitation of elemental sulfur during the transfer process. After the gas sample enters the coupling generation vessel 411, the cooling rate is controlled to decompose the hydrogen polysulfide and precipitate solid elemental sulfur first. Further cooling causes methane and hydrogen sulfide to react with water to form hydrates. The precipitated elemental sulfur acts as a heterogeneous nucleation interface to participate in the formation and growth of hydrates, forming a four-phase system of sulfur-containing natural gas (hydrogen sulfide, methane)-water-elemental sulfur-hydrate. By collecting temperature, pressure, gas phase composition, images, and spectral information inside the coupled generation vessel 411, the nucleation and growth process of hydrates can be identified. Based on the gas phase composition, pressure, and temperature, the compressibility factor and gas phase molar number changes are calculated using the cubic additional association term equation of state (i.e., CPA equation of state), and the growth rate of sulfur-containing natural gas hydrates with elemental sulfur precipitation is calculated.

[0013] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for testing the growth rate of gaseous hydrates accompanied by elemental sulfur precipitation, characterized in that, Includes the following steps: S1: Solid sulfur loading, vacuuming, and water injection: Solid sulfur particles are loaded onto the solid sulfur bed (020); the methane inlet control valve (002), hydrogen sulfide inlet control valve (005), mixed gas inlet control valve (008), sampling control valve (205), first liquid supply control valve (302), and second liquid supply control valve (304) are closed; the first sample transfer control valve (024), second sample transfer control valve (026), and vacuum control valve (102) are opened; the vacuum pump (101) is started to evacuate the entire system; when the absolute pressure of the system drops below 1 kPa, the vacuum pump (101) is stopped, and the vacuum control valve (102), first sample transfer control valve (024), and second sample transfer control valve (026) are closed; the first liquid supply control valve (302) and second liquid supply control valve (304) are opened, and the liquid supply pump (303) is started to fill the liquid supply container (301) with a pre-measured volume of [missing information]. Water is injected into the coupling reactor (411). After the liquid supply is completed, the liquid supply pump (303), the first liquid supply control valve (302), and the second liquid supply control valve (304) are closed. Using the formula... Determine the gas phase volume within the coupled generation vessel (411) In the formula, The volume of the gas phase inside the coupling reactor (411) is m³; The calibration volume of the coupling generation vessel (411) is m³; The volume of water to be injected is measured in advance, in m³. The volume occupied by the fixed components inside the coupling generation vessel (411) is m³; S2: Preparation of methane-hydrogen sulfide mixture: With the first sample transfer control valve (024), the second sample transfer control valve (026), and the sampling control valve (205) closed, open the methane inlet control valve (002) and the hydrogen sulfide inlet control valve (005). Control the inlet flow rates of methane and hydrogen sulfide through the methane flow meter (003) and the hydrogen sulfide flow meter (006) respectively, so that the two gases enter the mixed gas sample tank (007) and form a methane-hydrogen sulfide mixture with the required hydrogen sulfide volume fraction for the experiment. After the mixture is prepared, close the methane inlet control valve (002) and the hydrogen sulfide inlet control valve (005), open the mixed gas inlet control valve (008), start the gas booster pump (009), and pressurize and deliver the methane-hydrogen sulfide mixture to the saturated gas sample preparation vessel (017). After the delivery is completed, stop the gas booster pump (009) and close the mixed gas inlet control valve (008). S3: High-temperature and high-pressure in-situ preparation of elemental sulfur saturated gas sample: Keep the first sample transfer control valve (024), the second sample transfer control valve (026), and the sampling control valve (205) closed, start the electric heater (019), and control the hydraulic loading device (011) to push the floating piston (022) upward. Monitor the temperature and pressure inside the saturated gas sample preparation vessel (017) through the first pressure sensor (014), the first temperature sensor (015), and the first temperature and pressure acquisition terminal (013). Adjust the pressure and temperature inside the saturated gas sample preparation vessel (017) to 60MPa and 160℃, respectively. Allow the methane-hydrogen sulfide mixture to react with the sulfur particles in the solid sulfur bed (020) for 12 hours to promote the reaction of hydrogen sulfide with elemental sulfur to form polysulfide H2S. X A saturated gas sample containing hydrogen polysulfide, hydrogen sulfide, and elemental sulfur was obtained. S4: Transfer of elemental sulfur saturated gas sample: Start the constant temperature water bath (401) and keep the temperature of the liquid phase in the coupling generation vessel (411) at 100℃; close the sampling control valve (205), open the first transfer control valve (024) and the second transfer control valve (026) so that the gas sample after being intercepted by the solid particle interceptor (018) is transferred into the coupling generation vessel (411) through the heat-insulated transfer pipeline (025); During the sample transfer process, the pressure inside the saturated gas sample preparation vessel (017) and the coupling generation vessel (411) is monitored by the first pressure sensor (014) and the second pressure sensor (404), respectively. The hydraulic loading device (011) is controlled to push the floating piston (022) upward to continuously replenish the pressure inside the saturated gas sample preparation vessel (017), so that the pressure inside the saturated gas sample preparation vessel (017) is always higher than the pressure inside the coupling generation vessel (411). When the pressure inside the coupling generation vessel (411) measured by the second pressure sensor (404) reaches 60MPa, the first transfer control valve (024) and the second transfer control valve (026) are closed. The transfer flow rate, pressure and temperature are monitored by the transfer flow meter (027), the transfer pressure gauge (028) and the transfer temperature gauge (029). The heat-insulating transfer pipeline (025) is used to prevent the gas sample temperature from dropping and causing premature precipitation of elemental sulfur. S5: Elemental sulfur precipitation and hydrate coupling: Keep the first sample transfer control valve (024), the second sample transfer control valve (026) and the sampling control valve (205) closed, reduce the temperature of the reaction system in the coupling generation vessel (411) by cooling the constant temperature water bath (401) at a cooling rate of 0.1℃ / min, and start the stirring drive motor (407) to drive the stirring paddle (409) in the vessel to rotate through the magnetic coupling sealed transmission component (408) to enhance gas-liquid mass transfer; when the temperature of the reaction system drops to the elemental sulfur saturation boundary, the polysulfide decomposes and precipitates solid elemental sulfur, and continues to cool down to below the hydrate generation boundary, so that methane and hydrogen sulfide react with water to form hydrates, and the precipitated elemental sulfur participates in hydrate nucleation and growth as a heterogeneous nucleation interface, forming a sulfur-containing natural gas (hydrogen sulfide, methane)-water-elemental sulfur-hydrate four-phase system; S6: Calculation of hydrate growth rate: At the start of cooling and stirring, the gas phase composition analyzer (402), the second temperature and pressure acquisition terminal (403), the light source (405), the spectrometer (413), the high-speed camera (414), the image receiving terminal (415), the spectral data analysis system (416), and the laser emitter (417) are started simultaneously; the gas phase pressure in the coupled generation vessel (411) is collected according to the sampling interval. ,temperature Based on the concentrations, images, and spectral information of each gaseous component, and considering the phenomena of elemental sulfur precipitation and hydrate formation in the images, combined with the peak positions, shapes, and relative intensity changes of characteristic spectral peaks of methane and hydrogen sulfide, the nucleation and growth processes of hydrates can be determined; based on the concentrations and pressures of the gaseous components... ,temperature The compressibility factor is calculated by combining the cubic additional association term state equation (i.e., the CPA state equation). Using the formula Calculate the number of gaseous moles in the coupled generation vessel (411) during hydrate formation. In the formula, for Moles of gas phase in the coupled reactor (411) at any given time, in mol; The volume of the gas phase inside the coupling reactor (411) is m³; for The gas phase pressure inside the coupled generator (411) measured by the second pressure sensor (404) at any given time, in Pa; for The temperature inside the coupling reactor (411) measured by the second temperature sensor (406) at any given time, in K; for At all times, the gas phase is under pressure ,temperature The compressibility factor under the gas phase composition conditions, wherein the gas phase composition is measured by a gas phase composition analyzer (402); R is the gas constant, 8.314 J / (mol·K); and according to the formula Calculation based on sampling time Until the next sampling time The growth rate of hydrates accompanied by elemental sulfur precipitation during this period In the formula, The hydrate growth rate is expressed as the number of moles of gas phase consumed in the coupled generation vessel (411), in mol / s; and The records of the second temperature and pressure acquisition terminal (403) are respectively the first The sampling time and the first sampling time Each sampling time, s; and They are respectively and The number of gaseous moles in the coupled reactor (411) at any given time, in mol.

2. The method for testing the growth rate of gas hydrates with elemental sulfur precipitation according to claim 1, characterized in that, The device for testing the growth rate of gaseous hydrates with elemental sulfur precipitation includes a system for preparing and transferring saturated gas samples of elemental sulfur, a vacuum processing system, a system for determining elemental sulfur content and treating tail gas, a liquid supply system, and a system for testing the coupled growth rate of elemental sulfur and hydrates. The elemental sulfur saturated gas sample preparation and transfer system includes a methane cylinder (001), a methane inlet control valve (002), a methane flow meter (003), a hydrogen sulfide cylinder (004), a hydrogen sulfide inlet control valve (005), a hydrogen sulfide flow meter (006), a mixed gas sample tank (007), a mixed gas inlet control valve (008), a gas booster pump (009), a hydraulic return oil pressure relief pipeline (010), a hydraulic loading device (011), a hydraulic oil inlet booster pipeline (012), a first temperature and pressure acquisition terminal (013), and a first pressure sensor. The apparatus includes (014), a first temperature sensor (015), a double-piston sealing ring (016), a saturated gas sample preparation vessel (017), a solid particle trap (018), an electric heater (019), a solid sulfur bed (020), a porous support plate with a fine-mesh filter (021), a floating piston (022), a constant temperature chamber (023), a first transfer control valve (024), a heat-insulated transfer pipeline (025), a second transfer control valve (026), a transfer flow meter (027), a transfer pressure gauge (028), and a transfer temperature gauge (029). The outlet of the methane cylinder (001) is connected to the mixed gas sample tank (007) via a methane inlet control valve (002) and a methane flow meter (003) in sequence; the outlet of the hydrogen sulfide cylinder (004) is connected to the mixed gas sample tank (007) via a hydrogen sulfide inlet control valve (005) and a hydrogen sulfide flow meter (006) in sequence; the outlet of the mixed gas sample tank (007) is connected to the saturated gas sample preparation vessel (017) via a mixed gas inlet control valve (008) and a gas booster pump (009) in sequence, for preparing the required volume fraction of methane-hydrogen sulfide in the experiment; The saturated gas sample preparation vessel (017) is placed inside a constant temperature chamber (023); a solid particle trap (018) is placed between the solid sulfur bed (020) and the outlet of the saturated gas sample preparation vessel (017); the pressure tap of the first pressure sensor (014) is located above the solid sulfur bed (020); the solid sulfur bed (020) is placed above a porous support plate (021) with a fine-mesh filter; the porous support plate (021) with a fine-mesh filter is located above a floating piston (022); and the first temperature sensor (014) is placed above the outlet of the saturated gas sample preparation vessel (017). The detection end of 15) is located between the solid sulfur bed (020) and the porous support plate (021) with a fine pore filter. The floating piston (022) is set at the lower part of the saturated gas sample preparation vessel (017). Below the floating piston (022) is a hydraulic chamber. The double piston sealing ring (016) is sleeved on the outer periphery of the floating piston (022) and makes a sealing contact with the inner wall of the saturated gas sample preparation vessel (017). The hydraulic loading device (011) is connected to the above-mentioned hydraulic oil inlet pressurization pipeline (012) and hydraulic oil return pressure relief pipeline (010) respectively. The hydraulic chamber is connected, and the hydraulic oil inlet booster pipe (012) is used to inject hydraulic oil into the hydraulic chamber to push the floating piston (022) upward and increase the pressure inside the saturated gas sample preparation vessel (017). The hydraulic oil return pressure relief pipe (010) is used to return the hydraulic oil in the hydraulic chamber to make the floating piston (022) move downward and reduce the pressure inside the saturated gas sample preparation vessel (017). The electric heater (019) is set on the outer wall of the saturated gas sample preparation vessel (017). The first temperature and pressure acquisition terminal (013) is connected to the first pressure sensor (022) respectively. 14) The first temperature sensor (015) is electrically connected; the heat-insulated sample transfer pipeline (025) connects the saturated gas sample preparation vessel (017) and the coupling generation vessel (411). The heat-insulated sample transfer pipeline (025) transfers samples from the saturated gas sample preparation vessel (017) to the coupling generation vessel (411). The heat-insulated sample transfer pipeline (025) in this direction is provided with a first sample transfer control valve (024), a second sample transfer control valve (026), a sample transfer flow meter (027), a sample transfer pressure gauge (028), and a sample transfer temperature gauge (029) in sequence. The vacuum processing system includes a vacuum pump (101), a vacuum control valve (102), and a vacuum pipeline; one end of the vacuum pipeline is connected to the gas phase space of the coupling generation vessel (411), and the other end is connected to the exhaust port of the vacuum pump (101) via the vacuum control valve (102); The elemental sulfur content determination and tail gas treatment system includes a tail gas treatment device (201), a gas meter (202), an elemental sulfur analyzer (203), an elemental sulfur trap (204), a sampling control valve (205), and a sampling branch; one end of the sampling branch is connected to the heat-insulated transfer pipeline (025) between the first transfer control valve (024) and the second transfer control valve (026), and the other end is connected to the elemental sulfur trap (204) via the sampling control valve (205). The outlet of the elemental sulfur trap (204) is connected to the inlet of the gas meter (202) via a pipeline, and the outlet of the gas meter (202) is connected to the inlet of the tail gas treatment device (201) via a pipeline. The elemental sulfur trap (204) contains liquid carbon disulfide, and is connected to the elemental sulfur analyzer (203) via a pipeline. One end of the pipeline is close to the bottom of the elemental sulfur trap (204), and the other end is connected to the elemental sulfur analyzer (203). The liquid supply system includes a liquid supply container (301), a first liquid supply control valve (302), a liquid supply pump (303), a second liquid supply control valve (304), and a liquid supply pipeline; the liquid supply pipeline connects the liquid supply container (301) and the coupling generation vessel (411) and supplies liquid to the coupling generation vessel (411). The first liquid supply control valve (302), the liquid supply pump (303), and the second liquid supply control valve (304) are sequentially installed on the liquid supply pipeline in this direction. The aforementioned elemental sulfur and hydrate coupling growth rate testing system includes a constant temperature water bath (401), a gas phase composition analyzer (402), a second temperature and pressure acquisition terminal (403), a second pressure sensor (404), a light source (405), a second temperature sensor (406), a stirring drive motor (407), a magnetic coupling sealed transmission assembly (408), an in-vessel stirring paddle (409), a spectral receiver (410), a coupling generation vessel (411), a spectral transmission fiber (412), a spectrometer (413), a high-speed camera (414), an image receiving terminal (415), a spectral data analysis system (416), and a laser emitter (417). The constant temperature water bath (401) is connected to the coupling generation vessel (411) for heat exchange through a water bath circulation pipeline; the gas phase composition analyzer (402) is connected to the gas phase space of the coupling generation vessel (411) through a pipeline; the second pressure sensor (404) and the second temperature sensor (406) are connected to the gas phase space of the coupling generation vessel (411), and the second pressure sensor (404) and the second temperature sensor (406) are electrically connected to the second temperature and pressure acquisition terminal (403) respectively; the light source (405) and the high-speed camera (414) are respectively set on both sides of the visible observation area of ​​the coupling generation vessel (411), and the high-speed camera (414) is electrically connected to the image receiving terminal (415); The stirring drive motor (407) is connected to the stirring paddle (409) inside the vessel via the magnetic coupling sealed transmission assembly (408); the spectral receiver (410) is connected to the coupling generation vessel (411) to receive the spectral signal generated after the laser emitter (417) irradiates the reaction system inside the coupling generation vessel (411); the spectral receiver (410) is connected to the spectrometer (413) via the spectral transmission fiber (412); the spectral data analysis system (416) is electrically connected to the laser emitter (417) and the spectrometer (413) respectively, and assists in judging the nucleation and growth process of hydrate based on the changes in peak position, peak shape and relative intensity of the characteristic spectral peaks of methane and hydrogen sulfide during the hydrate formation process.

Images