CN110487771B - Gas hydrate generation/decomposition system and method for in-situ Raman analysis - Google Patents
Gas hydrate generation/decomposition system and method for in-situ Raman analysis Download PDFInfo
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- CN110487771B CN110487771B CN201910899770.7A CN201910899770A CN110487771B CN 110487771 B CN110487771 B CN 110487771B CN 201910899770 A CN201910899770 A CN 201910899770A CN 110487771 B CN110487771 B CN 110487771B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Abstract
The invention provides a gas hydrate generation/decomposition system and a method for in-situ Raman analysis. And kinetic experiments such as generation/decomposition of the gas hydrate can be realized, and in-situ Raman characterization is carried out. The system comprises a Raman spectrometer, a reaction kettle system, a temperature control system, a sample precooling system, a pressure control gas supply system, a vacuum system, a rapid gas exhaust system and a data acquisition and processing system, wherein the reaction kettle system, the temperature control system, the sample precooling system, the pressure control gas supply system, the vacuum system, the rapid gas exhaust system and the data acquisition and processing system are connected through a connecting. The system can ensure that the hydrate is subjected to in-situ Raman characterization in the reaction kettle, and solves the problems of difficult sampling of the ex-situ Raman characterization, experimental errors caused by sample transfer and the like.
Description
Technical Field
The invention belongs to the field of hydrate experiments, and relates to a gas hydrate generation/decomposition system and a gas hydrate generation/decomposition method for in-situ Raman characterization. In particular to a dynamic experimental research suitable for in-situ high-pressure gas hydrate generation/decomposition.
Background
The gas hydrate is a non-stoichiometric cage crystal with different filling rates, wherein under the conditions of high pressure and low temperature, host molecule water is connected through hydrogen bonds to form a series of holes with different sizes, and guest molecules with proper sizes are filled in the holes through Van der Waals force. Hydrates have three structures, depending on the unit cell structure of the hydrate: is I type, II type and H type respectively. The unit cell of the type I hydrate is a body-centered cubic structure and comprises 46 water molecules, namely 2 water molecules and 5 water molecules12(SC) holes and 6 of 51262(LC) void composition. The unit cell of II type hydrate is face-centered cubic structure, contains 136 water molecules, and consists of 16 molecules and 5 molecules12(SC) holes and 8 51264(LC) void composition. The H-type hydrate unit cell is a simple hexagonal structure and contains 34 water molecules, 3 and 512(SC) Cavity, 2 by 435663(MC) holes and 1 and 51268(LC) holes.
In the growth kinetics of the hydrate, the growth rate of the hydrate is sensitive to local environments such as pressure, composition and the like, so that the research on the guest molecule filling rate and the filling efficiency of the hydrate under different pressure, temperature and composition conditions is the core of the research on the growth kinetics of the hydrate and is the precondition of guiding the application of energy storage engineering. In this respect, the raman spectrometer has an accurate structural analysis result in the growth process of the hydrate, is a nondestructive micro-area measurement means, and is widely applied to characterization of hydrate growth/decomposition kinetics on a molecular level. However, the existing laboratory is limited by the experimental conditions to perform ex-situ raman characterization on the growth of hydrate, for example, patent No. CN101477086BThe patent provides a gas hydrate generation sampling analysis method and a device thereof, which have the defects of difficult sampling, difficult guarantee of sample transfer and the like. While a few devices suitable for in-situ Raman characterization of hydrates, such as the CN103278374B patent, propose an in-situ Raman analysis and hydrate characterization device and an in-situ Raman analysis method of hydrate samples, wherein the gas phase peak is used for carrying out quantitative analysis on the hydrates 512Peak coverage of the cage, resulting in failure to analyze hydrate 512The disadvantages of cages.
With the progress of experimental research, in order to better meet experimental requirements and improve experimental precision, a set of comprehensive hydrate experimental system suitable for in-situ Raman characterization is urgently needed to meet the microscopic characterization of a hydrate structure.
Disclosure of Invention
In response to the deficiencies of the prior art, the present invention provides a system and method for hydrate formation/decomposition suitable for in situ raman characterization. The method can realize the experiments such as generation/decomposition of the gas hydrate and the like, and carry out in-situ Raman characterization.
The invention provides a gas hydrate generation/decomposition system for in-situ Raman analysis, which comprises a Raman spectrometer, a reaction kettle system, a sample precooling system, a pressure control and gas supply system, a pressure maintaining system, a vacuum system and a data acquisition and processing system, wherein the reaction kettle system is arranged on an XY operating platform of the Raman spectrometer;
the reaction kettle system comprises a visual hydrate reaction kettle, a temperature sensor and a liquid nitrogen temperature control component; the sapphire window is arranged on the top surface of the reaction kettle, and the Raman peak position of the sapphire is sharp and is easy to be separated from a gas hydrate signal, so that errors caused by window materials can be avoided. The side surface is provided with a liquid nitrogen inlet/outlet for controlling the temperature, the temperature range is-196 ℃ to 600 ℃, and the pressure-bearing range is-0.1 MPa to 10 MPa; temperature sensor sets up the sample bench in reation kettle, and the outer protective cover of reation kettle is equipped with liquid nitrogen and sweeps the device and be used for the temperature extrinsic cycle and prevent that the window from frosting and the signal weakens, is furnished with liquid nitrogen in the shell and sweeps the pipeline in order to maintain the whole low temperature state of reation kettle, prevents that visual window from frosting to hinder the measurement.
The pressure control gas supply system comprises a pressure regulating valve and a gas cylinder capable of forming hydrate, wherein the pressure regulating valve is used for opening and closing a pipeline and regulating the pressure of the pipeline according to target pressure so as to provide stable gas to generate initial hydrate.
The pressure maintaining system comprises a plunger pump 6 filled with isotope gas, wherein the isotope gas is used for maintaining the pressure after discharging initial gas for forming hydrate, and the gas phase peak and the hydrate phase 5 of the gas hydrate12Coincidence of cage peak positions results in failure to analyze hydrate 512Filling the cage, wherein the difference between the Raman peak position of the isotope gas and the Raman peak position of the common gas is 800cm-1On the left and right sides, and because of the allotrope, the physical properties are similar, so the problem that the gas phase peak covers the target peak position in the single gas hydrate in-situ experiment can be solved by using the isotope gas to maintain the confining pressure of the gas hydrate, and the quantitative analysis of the occupancy condition of the hydrate cage is realized.
The sample precooling system comprises a water bath and an auxiliary temperature control unit, the inlet end of the sample precooling system is connected with a pressure maintaining system and a pressure control gas supply system which are connected in parallel, gas provided by the pressure control gas supply system or the pressure maintaining system is precooled, decomposition of a hydrate sample caused by heat carried by the gas during gas injection is prevented, the outlet end of the sample precooling system is connected with a reaction kettle system, and the precooled gas is sent into the reaction kettle.
The vacuum system comprises a vacuum pump connected to a pipeline through a tee joint and is used for vacuumizing the visual hydrate reaction kettle before reaction, eliminating the influence of impurity gases in the reaction kettle on Raman analysis and quickly exhausting after the reaction is finished.
The data acquisition and processing system is used for acquiring the temperature of the temperature sensor and various data of Raman spectrum of a sample for analysis, and can perform visual observation with the maximum magnification of 100 times and the precision of 0.1cm-1And (4) performing Raman spectrometry analysis.
The method adopting the gas hydrate generation/decomposition system for in-situ Raman analysis comprises the following steps:
step 1: adding deionized water into the reaction kettle, and reducing the temperature of the reaction kettle to be below 0 ℃ by using a temperature sensor and a liquid nitrogen temperature control component to freeze the deionized water so as to prevent water from being pumped out of the reaction kettle due to vacuum; and (4) opening the vacuum pump and the valve after the sample is frozen, and closing the vacuum pump and the valve after the reaction kettle is vacuumized.
Step 2: and closing a needle valve at the joint of the precooling system and the reaction kettle, unscrewing a gas cylinder knob in the pressure control gas supply system and adjusting a pressure regulating valve to enable the gas pressure in the pipeline to be target pressure, standing until a digital pressure gauge displays stable pressure, precooling the displaced gas to a target temperature, opening a needle valve of a precooling device to introduce the precooled gas into the reaction kettle, simultaneously raising the reaction temperature to the target temperature, and seeing that the hydrate is quickly formed when the temperature is close to the target temperature.
And step 3: the generation condition of the hydrate is determined by Raman spectrum, when the Raman spectrum of the hydrate is measured, the temperature of the reaction kettle is reduced to be lower than minus 80 ℃ by a liquid nitrogen temperature control component, and the experimental result shows that the hydrate is extremely slowly decomposed at minus 80 ℃, and the hydrate is decomposed less than 0.1% in the process of replacing for 1 hour. And opening a vacuum pump to pump vacuum after the temperature is stable, closing the vacuum pump, a pressure control gas supply system and a needle valve of a precooling system after the vacuum pumping, opening a plunger pump 6 to inject isotope gas into the pipeline, precooling the isotope gas in the precooling system to prevent the hydrate sample from being decomposed by heat carried by the gas during gas injection, and then opening the needle valve of the precooling system to introduce the precooled isotope gas into the reaction kettle to maintain the pressure.
And 4, step 4: and acquiring primary spectrum data by using a Raman spectrometer to obtain the generation condition and the filling rate change of the hydrate in the reaction kettle.
And 5: and after the collection is finished, opening a vacuum pump to vacuumize the gas, then closing a valve of the vacuum pump, quickly opening a gas cylinder of the gas used by the gas hydrate, inflating the reaction kettle to a target pressure, raising the temperature to a target temperature after the pressure is stabilized, and continuing the generation process of the hydrate.
And (5) reducing the pressure to be under the phase equilibrium pressure when the hydrate is decomposed, and repeating the step 3-5.
The invention has the beneficial effects that: the method is suitable for in-situ characterization of hydrate growth by a Raman spectrometer, eliminates experimental errors caused by transfer of test samples, and is suitable for continuous growth kinetic study of the hydrate for a long time scale. Is an essential device for researching the micro mechanism of the growth dynamics of the hydrate.
Drawings
FIG. 1 is a schematic diagram of a gas hydrate generation/decomposition system for in situ Raman analysis of the present invention.
In the figure: 1, a computer; 2, a reaction kettle; 3, constant temperature water bath; 4 precooling the spiral pipeline; 5, a vacuum pump; 6 plunger pump; 7 gas cylinders; 8, a Raman spectrometer; 9 a pressure regulating valve.
Fig. 2 is a raman spectrum of a deuteromethane gas maintenance methane hydrate formation/decomposition experiment.
Detailed Description
Example 1:
the embodiment is a gas hydrate generation/decomposition system for in-situ raman analysis, taking a methane hydrate generation/decomposition experiment as an example, and combining fig. 1, the generation experiment process is as follows:
the gas cylinder 7 is filled with high-purity methane gas with the purity of 99.99 percent, and the plunger pump 6 is filled with scientific research grade deuterated methane gas with the purity of 99.98 percent;
deionized water is added into the reaction kettle 2, the temperature of the reaction kettle 2 is reduced to below 0 ℃ by utilizing a temperature sensor and a liquid nitrogen temperature control component, so that the deionized water is frozen, and the water is prevented from being pumped out of the reaction kettle 2 due to vacuum; after the sample is frozen, opening the vacuum pump 5 and the valve, vacuumizing the reaction kettle 2, and then closing the vacuum pump 5 and the valve;
closing a needle valve at the joint of the precooling device and the reaction kettle 2, unscrewing a knob of a methane gas cylinder 7 and adjusting a pressure regulating valve to enable the gas pressure in the pipeline to be target pressure, standing until a digital pressure gauge displays stable pressure, precooling methane to a target temperature, opening the needle valve of the precooling device to introduce precooled gas into the reaction kettle 2, simultaneously raising the reaction temperature to the target temperature, and seeing that hydrates are rapidly formed when the temperature is close to the target temperature;
the generation condition of the hydrate is determined through the Raman spectrum 8, when the Raman spectrum of the hydrate is measured, the temperature of the reaction kettle is reduced to be lower than minus 80 ℃ through a liquid nitrogen temperature control component, and the experimental result shows that the hydrate is extremely slowly decomposed at minus 80 ℃, and the hydrate is decomposed less than 0.1% in the process of replacing for 1 hour. After the temperature is stable, opening a vacuum pump 5 for vacuumizing, closing the vacuum pump 5, a methane gas cylinder 7 and a needle valve of a precooling system 4 after vacuumizing, opening a needle valve of a plunger pump 6 and adjusting the pressure in a pipeline to be a target pressure, precooling the deuterated methane in the precooling system 4 to prevent the heat carried by the deuterated methane from decomposing a hydrate sample during gas injection, and then opening the needle valve between the precooling system 4 and a reaction kettle 2 to introduce the precooled deuterated methane into the reaction kettle 2 to maintain the pressure;
acquiring primary spectrum data by a Raman spectrometer to obtain the generation condition and the filling rate change of the hydrate in the reaction kettle;
and after the collection is finished, opening the vacuum pump 5 to vacuumize the gas, then closing a valve of the vacuum pump 5, quickly opening the methane gas bottle 7, inflating the reaction kettle 2 to the target pressure, raising the temperature to the target temperature after the pressure is stabilized, and continuing the hydrate generation process.
The decomposition experiment procedure was as follows:
slowly opening a valve of the vacuum pump 5 to discharge gas below the phase equilibrium pressure, and simultaneously observing the interface change condition of the hydrate by the Raman spectrometer 8;
when the methane hydrate is measured, the hydrate is quickly cooled to-80 ℃, after the temperature is stabilized, the plunger pump 6 is started to inject the deuterated methane gas to be below the phase equilibrium pressure, and at the moment, the Raman spectrum is collected to obtain the cage occupancy condition of the current methane hydrate, namely the kinetic information of the methane hydrate decomposition at the moment;
and after the collection is finished, opening the vacuum pump 5 to vacuumize the gas, then closing a valve of the vacuum pump 5, quickly opening the methane gas bottle 7, inflating the reaction kettle 2 to the target pressure, raising the temperature to the target temperature after the pressure is stabilized, and continuing the hydrate generation process.
The experimental result shows that the deuterated methane gas can maintain the methane hydrate for 3h without decomposition, so that an accurate Raman spectrogram of the in-situ methane hydrate can be obtained. And realizing the in-situ Raman quantitative analysis of the high-pressure gas hydrate.
Example 2:
taking ethane hydrate generation/decomposition experiment as an example, and combining fig. 1, the generation experiment process is as follows:
the gas cylinder 7 is filled with 95 percent of high-purity methane gas, 5 percent of ethane and propane mixed gas in any proportion, and the plunger pump 6 is filled with 95 percent of high-purity methane gas and 5 percent of ethane and propane gas which are completely deuterated;
the procedure was exactly the same as in example 1.
Although the patented technology has been described with reference to the drawings, the patented technology is not limited to the above-described embodiments, and the above-described manner of use is illustrative only and not intended to be limiting, and it will be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles of the invention, and the scope of the invention is to be defined by the claims.
Claims (2)
1. The method for the gas hydrate generation/decomposition system for the in-situ Raman analysis is characterized in that the gas hydrate generation/decomposition system for the in-situ Raman analysis comprises a Raman spectrometer, a reaction kettle system, a temperature control system, a sample precooling system, a pressure control gas supply system, a pressure maintaining system, a vacuum system, a quick exhaust system and a data acquisition and processing system, wherein the reaction kettle is arranged on an XY sample table of the Raman spectrometer;
the reaction kettle system comprises a visual hydrate reaction kettle, a temperature sensor and a liquid nitrogen temperature control component; a sapphire window is arranged on the top surface of the reaction kettle, and a liquid nitrogen inlet/outlet is arranged on the side surface of the reaction kettle for controlling the temperature; the temperature sensor is arranged on a sample table in the reaction kettle, the reaction kettle is sleeved with a plastic heat-insulating shell, and a liquid nitrogen purging pipeline is arranged in the shell to maintain the integral low-temperature state of the reaction kettle, so that a visible window is prevented from frosting to obstruct measurement;
the pressure control gas supply system comprises a pressure regulating valve and a generated gas cylinder connected through a pipeline and is used for forming gas hydrate;
the pressure maintaining system comprises a plunger pump filled with isotope gas, and the isotope gas is used for maintaining the pressure of the gas hydrate after the gas of the gas hydrate is discharged;
the sample precooling system comprises a water bath and an auxiliary temperature control unit, the inlet end of the sample precooling system is connected with a pressure maintaining system and a pressure control gas supply system which are connected in parallel, gas provided by the pressure control gas supply system or the pressure maintaining system is precooled, the outlet end of the sample precooling system is connected with the reaction kettle system, and the precooled gas is sent to the reaction kettle;
the vacuum system comprises a vacuum pump connected to a pipeline through a tee joint and is used for vacuumizing the visual hydrate reaction kettle before reaction, eliminating the influence of impurity gases in the reaction kettle and quickly exhausting after the reaction is finished;
the data acquisition and processing system is used for acquiring the temperature of the temperature sensor and various data of the Raman spectrum of the sample for analysis;
the method comprises the following steps:
step 1: adding deionized water into a reaction kettle, reducing the temperature of the reaction kettle to be below 0 ℃ by using a temperature sensor and a liquid nitrogen temperature control component, starting a vacuum pump and a valve after the temperature is stable, vacuumizing the reaction kettle, and closing the vacuum pump and the valve;
step 2: closing a needle valve at the joint of the precooling device and the reaction kettle, unscrewing a knob of a displaced gas cylinder in a pressure-controlled gas supply system and adjusting a pressure regulating valve to enable the gas pressure in a pipeline to be target pressure, standing until a digital pressure gauge displays stable pressure, ending precooling of displaced gas, opening the needle valve of the precooling device to send initial gas into the reaction kettle, and simultaneously raising the reaction temperature to the required temperature;
and step 3: determining the generation condition of the hydrate through a Raman spectrum, when measuring the Raman spectrum of the hydrate, reducing the temperature of a reaction kettle to be lower than minus 80 ℃ through a liquid nitrogen temperature control component, starting a vacuum pump to pump vacuum after the temperature is stable, closing a vacuum pump, a pressure control gas supply system and a needle valve of a precooling system after the vacuum pumping, opening the needle valve of a plunger pump to inject isotope gas into a pipeline, adjusting the pressure in the pipeline to be a target pressure, precooling the isotope gas in the precooling system, and then opening the needle valve of the precooling system to introduce the precooled isotope gas into the reaction kettle to maintain the pressure;
and 4, step 4: acquiring primary spectrum data by a Raman spectrometer to obtain the generation condition and the filling rate change of the hydrate in the reaction kettle;
and 5: after the collection is finished, opening a vacuum pump to vacuumize the gas, then closing a valve of the vacuum pump, quickly opening a gas cylinder of the gas used by the gas hydrate, inflating the reaction kettle to a target pressure, raising the temperature to a target temperature after the pressure is stabilized, and continuing the generation process of the hydrate;
and (5) reducing the pressure to be under the phase equilibrium pressure when the hydrate is decomposed, and repeating the step 3-5.
2. The method as claimed in claim 1, wherein the gas is one or a mixture of two or more of methane, ethane, propane and xenon.
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| CN112345418B (en) * | 2020-10-23 | 2022-07-05 | 大连理工大学 | Nano bubble generation method based on gas hydrate |
| CN112697768A (en) * | 2020-12-03 | 2021-04-23 | 重庆大学 | Component competition analysis method for coal bed gas purification process |
| CN113433069A (en) * | 2021-07-09 | 2021-09-24 | 齐鲁工业大学 | Device for in-situ monitoring gas hydrate generation and decomposition process by online infrared spectrometer on molecular level and use method thereof |
| CN114088683A (en) * | 2021-11-05 | 2022-02-25 | 青岛海洋地质研究所 | Hydrate multi-process simulation device and method for in-situ Raman test |
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