CN114113440A - System and method for capturing and analyzing volatile hydrocarbon in natural gas hydrate reservoir - Google Patents
System and method for capturing and analyzing volatile hydrocarbon in natural gas hydrate reservoir Download PDFInfo
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Abstract
The invention provides a system and a method for trapping and analyzing volatile hydrocarbon in a natural gas hydrate reservoir, wherein the system comprises a volatilization device, a primary cold trap device, a secondary cold trap device, a temperature control device and a gas chromatography-mass spectrum; the volatilizing device comprises a sealed ball milling tank and a ball milling tank heating body, wherein the ball milling tank heating body is sleeved outside the sealed ball milling tank and used for heating the sealed ball milling tank; the sealed ball milling tank is respectively provided with an inlet and an outlet, and the inlet is communicated with the gas carrying bottle; the primary cold trap device comprises an ice-water bath device and a sample absorption bottle, the sample absorption bottle is filled with dichloromethane, the sample absorption bottle is positioned in the ice-water bath device, and the opening of the sample absorption bottle is communicated with the outlet of the sealed ball milling tank through a transmission pipeline; the secondary cold trap device comprises a liquid nitrogen thermos bottle and a U-shaped absorption tube, wherein an opening at one end of the U-shaped absorption tube is communicated with an opening of the sample absorption bottle; the gas chromatography-mass spectrometry is used for analyzing the composition and content of the trapped volatile hydrocarbon component.
Description
Technical Field
The invention relates to a system and a method for capturing and analyzing volatile hydrocarbon in a natural gas hydrate reservoir, and belongs to the technical field of natural gas hydrate analysis and test.
Background
Natural Gas hydrate (also called combustible ice or hydrate) is an ice-like crystalline substance formed by Natural Gas and water under high pressure and low temperature conditions, and is mainly distributed in sea land frame sediments and land permafrost. The research on the source and the cause of the hydrate gas has important theoretical and practical application values for the exploration of water hydrate resources and has profound significance for knowing the change of the climate environment and the like. The current knowledge of hydrate gas sources and causes is mainly based on CH4Content (such as C)1/(C1+C2) And carbon (hydrogen) isotopes (delta) of natural gas13C and δ D), identifying biogenic, thermogenic and mixed-causative gases. The exploration and research of natural gas hydrates around the marginal hydrocarbon-bearing basins of oceans and continents has recently drawn attention in deep water areas such as the northern slope of the gulf of mexico, the southern foxyland basin of the atlantic, and the trigona of margo canada, where natural gas originates from deep source rocks or reservoirs, being either thermal or mixed-forming. The natural gas hydrate resource in the northern sea area of the south China sea is rich, and the free and bound gas released by the hydrate sample in the deep water area of the southeast Qiong basin is rich in C2+ heavy hydrocarbons (2.3-18.8%) whose carbon isotope values indicate that thermal cause gas contributes.
At present, the understanding of the source and the cause of the hydrate gas is deepened, but as the analysis method and the means are single, most of the analysis methods are focused on the analysis of gas geochemistry, some key scientific problems in the research of hydrate reservoir formation are still difficult to be effectively solved, particularly the effectiveness and the supply size of deep thermal-cause oil gas as a natural gas hydrate reservoir gas source. Studies suggest that deep reservoirs leak or hydrocarbons formed by thermal degradation of mature source rockThe species can migrate over long distances along faults, diapir or gas chimneys, etc. to shallow surfaces where gas and volatile components more readily reach the hydrate stability zone (GHSZ), light hydrocarbons or volatile hydrocarbons (C) in hydrate reservoirs and their adjacent sediments to date5～C15) Have not been successfully extracted and analyzed. The experimental method of separation and extraction from sediments (sedimentary rocks) by Soxhlet extraction often results in the loss of low-boiling volatile fractions, mainly of medium-high boiling hydrocarbons, such as C15+ n-alkanes, stanols, aromatic steroids and terpenes, and Polycyclic Aromatic Hydrocarbons (PAH), etc. Due to the fact that the quantity and types of light hydrocarbon are large, such as n-alkane, cyclane, benzene series, adamantane series, monoterpene and the like, and the analysis on the light hydrocarbon or volatile hydrocarbon in the hydrate and the reservoir thereof is very helpful for exploring and researching the composition, contribution, potential source rock and the like of the natural gas with the thermal origin. Wherein the volatile hydrocarbon can be also called light fraction hydrocarbon or light hydrocarbon, and refers to low boiling point and volatile hydrocarbon component in sediment, sedimentary rock and petroleum, and its carbon number distribution contains C5-C13The boiling point is 30-235 ℃ under normal pressure, the volatile hydrocarbon comprises various types of organic compounds such as normal alkane, isoparaffin, cycloparaffin, aromatic hydrocarbon, adamantane and monoterpene, and the number of the known compounds is more than 450.
Prior art relating to the invention
The technical scheme of the prior art I is as follows:
chinese patent CN101900713A discloses an online analysis device for closed ball milling, crushing, heating, desorption, helium purging, and cold trap trapping for chromatography and chromatography-mass spectrometry, which comprises the following steps: putting a massive rock sample into a liquid nitrogen cup for cooling, taking out, knocking one piece of rock sample, weighing, putting the rock sample into a clean sealed tank, vacuumizing the sealed tank to 1Pa, heating the sealed tank and a transmission line to 300 ℃, wherein two ends of the transmission line are sample injection needles for chromatography, respectively inserting the transmission line into a high-temperature-resistant silica gel pad of the sealed tank and a high-temperature-resistant silica gel pad of a chromatography vaporization chamber, setting the flow rate of gaseous hydrocarbon entering the chromatography through the transmission line by using a mass flow controller, adjusting a pressure stabilizing valve to control the flow rate and pressure of helium entering the sealed tank, carrying the heated and vaporized gaseous hydrocarbon in the sealed tank into a chromatograph by the helium, dividing the gaseous hydrocarbon into liquid nitrogen cold traps in the chromatograph box, trapping the sample at the front section condensation part of the chromatographic column, removing the cup after the gaseous hydrocarbon in the tank is fully carried into the cold traps, closing a furnace door, and starting a chromatographic liquid nitrogen program to increase the temperature for analysis.
The first prior art has the following defects:
(1) because the natural gas hydrate is distributed at the depth of 0-200m at a submarine sediment/water interface and is in the early stage of diagenesis, a sample has the characteristics of high water content, weak soil and the like, and the prior art can not carry out effective moisture removal and light hydrocarbon enrichment analysis;
(2) in the heating process of the sample, the generated water vapor is condensed in the transmission pipeline, so that the transmission pipeline is easy to block, and the success rate of online analysis is not high.
Therefore, it is a technical problem to be solved in the art to provide a novel system and method for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir.
Disclosure of Invention
To address the above-described shortcomings and drawbacks, it is an object of the present invention to provide a system for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir.
The invention also aims to provide a method for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir. The method provided by the invention can be used for analyzing the volatile hydrocarbon in the deep-sea natural gas hydrate for the first time, is beneficial to understanding and understanding the formation and distribution mechanism of the natural gas hydrate, and provides a new idea and method for finding clean alternative energy and paying attention to the climate environment effect.
In order to achieve the above objects, in one aspect, the present invention provides a system for trapping and analyzing volatile hydrocarbons in a natural gas hydrate reservoir, wherein the system includes a volatilization device, a primary cold trap device, a secondary cold trap device, a temperature control device, and a gas chromatography-mass spectrometer;
the volatilization device comprises a sealed ball milling tank and a ball milling tank heating body, wherein the ball milling tank heating body is sleeved outside the sealed ball milling tank and used for heating the sealed ball milling tank; the sealed ball milling tank is respectively provided with an inlet and an outlet, and the inlet is communicated with the gas carrying bottle;
the primary cold trap device comprises an ice-water bath device and a sample absorption bottle, the sample absorption bottle is filled with dichloromethane, the sample absorption bottle is positioned in the ice-water bath device, and an opening of the sample absorption bottle is communicated with an outlet of the sealed ball milling tank through a transmission pipeline;
the secondary cold trap device comprises a liquid nitrogen thermos bottle and a U-shaped absorption tube, wherein an opening at one end of the U-shaped absorption tube is communicated with an opening of the sample absorption bottle;
the gas chromatography-mass spectrometry is used for analyzing the composition and the content of the trapped volatile hydrocarbon component;
the temperature control device is used for carrying out temperature programming on the sealed ball milling tank through a heating body of the ball milling tank, controlling the temperature of the transmission pipeline and controlling the temperature of the ice-water bath device.
As a specific embodiment of the above system of the present invention, the gas carrying cylinder is sequentially communicated with the inlet of the sealed ball milling tank through a pressure gauge and a mass flow meter via a pipeline.
In an embodiment of the above system, the pipeline heating insulator is coated outside the transmission pipeline.
As a specific embodiment of the system according to the present invention, the opening of the sample absorption bottle is provided with a reducing tee for communicating the outlet of the sealed ball milling jar and the opening of one end of the U-shaped absorption tube with the opening of the sample absorption bottle.
In an embodiment of the system according to the present invention, an opening of one end of the U-shaped absorption tube is provided with a variable diameter two-way for communicating the opening of the sample absorption bottle with the opening of one end of the U-shaped absorption tube.
In the invention, the sealed ball milling tank, the ball milling tank heating body, the pipeline heating heat insulator, the gas carrying bottle, the ice water bath device, the sample absorption bottle, the liquid nitrogen vacuum bottle, the temperature control device, the gas chromatography-mass spectrometry and other equipment and the parts such as the reducing tee joint, the reducing two-way pressure gauge, the mass flowmeter, the transmission pipeline and other parts are all conventional equipment or parts in the field. For example, in some embodiments of the present invention, the ball mill pot heater may be a heating furnace and the pipeline heating insulation may be resistance heating wire.
On the other hand, the invention also provides a method for capturing and analyzing volatile hydrocarbon in a natural gas hydrate reservoir, wherein the method is realized by adopting the system for capturing and analyzing volatile hydrocarbon in the natural gas hydrate reservoir, and the method comprises the following steps:
(1) filling a hydrate sediment sample into a sealed ball milling tank, sealing and vacuumizing, performing temperature programming on the sealed ball milling tank by using a heating body of the ball milling tank, and opening a gas carrying bottle;
(2) in the temperature programming process, light hydrocarbon components and water vapor are separated and carried by carrier gas to enter a sample absorption bottle, the light hydrocarbon components in the sample absorption bottle are absorbed by dichloromethane, and the temperature of the dichloromethane is always kept at 0 ℃ in the absorption process;
(3) light hydrocarbon components which are not absorbed by the dichloromethane enter the U-shaped absorption tube, and are condensed in liquid nitrogen;
(4) and light hydrocarbon components captured by the sample absorption bottle and light hydrocarbon components captured by the U-shaped absorption tube are respectively collected, and then are mixed and sent to a gas chromatography-mass spectrometer for composition and content analysis.
As a specific embodiment of the above method of the present invention, in step (1), the temperature programming includes:
firstly, heating to 110-150 ℃ at a heating rate of 2-5 ℃/min, fully evaporating and separating water and part of low-boiling light hydrocarbon components, and heating to 300 ℃ at a heating rate of 5-10 ℃/min, wherein a large amount of light hydrocarbon components are volatilized and separated.
As a specific embodiment of the above method of the present invention, in step (1), the temperature programming includes:
firstly, heating to 150 ℃ at a heating rate of 3 ℃/min, fully evaporating and separating water and part of light hydrocarbon components with low boiling points, and then heating to 300 ℃ at a heating rate of 5 ℃/min, wherein a large amount of light hydrocarbon components are volatilized and separated.
In an embodiment of the above method of the present invention, the carrier gas is nitrogen.
As a specific embodiment of the above method of the present invention, in the step (2), the light hydrocarbon component and the water vapor are separated and carried by the carrier gas to enter the sample absorption bottle through the transmission pipeline, and in the process, the pipeline heating insulator is used to heat the transmission pipeline and maintain the temperature at 120-150 ℃.
In a specific embodiment of the above method of the present invention, the hydrate deposit sample is taken from 1 to 200m below the interface of water/deposit in the deep sea bottom.
Unlike the existing method for extracting and analyzing light hydrocarbon from a hydrocarbon source rock or rock sample, the natural gas hydrate sample, namely the hydrate sediment sample, which is aimed by the invention, has large water content and presents a soft mud shape, and volatile hydrocarbon in the natural gas hydrate sample is analyzed, the water in the volatile hydrocarbon must be removed or separated, so that the removal or separation of the water is very critical, but the boiling point of the water (100 ℃ at normal pressure) is just in the range of the boiling point of the light hydrocarbon component, namely the volatile hydrocarbon component (30 ℃ to 300 ℃), and when the sample is heated, the water in the sample can be simultaneously separated along with the light hydrocarbon component. Therefore, when the light hydrocarbon component is extracted, the water contained in the light hydrocarbon component needs to be removed and separated at the same time, and the basic flow comprises the following steps: heating a certain amount of hydrate sediment sample to 300 ℃ in a ball milling tank through programmed heating, volatilizing water and light hydrocarbon components from the ball milling tank, then enabling the water and the light hydrocarbon components to enter a transmission pipeline, absorbing the light hydrocarbon components in a sample absorption bottle by dichloromethane, condensing the water, enabling the light hydrocarbon components which are not absorbed by the dichloromethane to enter a U-shaped absorption tube, condensing the light hydrocarbon components in liquid nitrogen, respectively collecting the light hydrocarbon components captured by the sample absorption bottle and the light hydrocarbon components captured by the U-shaped absorption tube, mixing the light hydrocarbon components and the light hydrocarbon components, and sending the mixture into a gas chromatography-mass spectrometry for analysis.
In conclusion, the system and the method for trapping and analyzing the volatile hydrocarbon in the natural gas hydrate reservoir provided by the invention adopt the two-stage cold trap to separate and trap the light hydrocarbon components, can effectively separate the water contained in the hydrate sediment sample, and reduce the loss of the light hydrocarbon; meanwhile, the ball milling tank is heated and sealed by adopting temperature programming, so that the blockage of a transmission pipeline can be effectively prevented, and the analysis efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a system for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir provided in embodiment 1 of the present invention.
Fig. 2 is a comparison graph of a gas chromatogram obtained in a blank experiment and a gas chromatogram of a hydrate deposit sample in experimental example 2 of the present invention.
Fig. 3 is a total ion flow diagram of light hydrocarbon components in a hydrate sediment sample obtained in example 2 of the present invention.
Figure 4a is a mass spectrum of adamantane in light hydrocarbon components contained in the sample of the hydrate deposit obtained in example 2 of the invention.
Figure 4b is a mass spectrum of diamantane in the light hydrocarbon component of the sample of the hydrate deposit obtained in example 2 of the present invention in the study area.
Figure 4c is a mass spectrum of triamantane in the light hydrocarbon component contained in the sample of the hydrate deposit from the study area obtained in example 2 of the present invention.
FIG. 5a is a total ion flow diagram of light hydrocarbon obtained in comparative example 1 under constant temperature (300 ℃ C.).
Fig. 5b is a total ion flow diagram of light hydrocarbons obtained under temperature programmed conditions in example 2 of the present invention.
FIGS. 5c to 5d are graphs showing the results of analysis of adamantane compounds (m/z 135) obtained under the temperature-programmed condition in example 2 of the present invention and the results of analysis of adamantane compounds (m/z 135) obtained under the constant temperature (300 ℃ C.) in comparative example 1, respectively.
FIGS. 5e to 5f are graphs showing the results of analysis of adamantane compound (m/z 149) obtained under the temperature-programmed condition in example 2 of the present invention and the results of analysis of adamantane compound (m/z 149) obtained under the constant temperature (300 ℃ C.) in comparative example 1, respectively.
FIGS. 5g to 5h are graphs showing the results of analysis of adamantane compounds (m/z 163) obtained under the temperature-programmed conditions in example 2 of the present invention and the results of analysis of adamantane compounds (m/z 163) obtained under the constant temperature (300 ℃ C.) in comparative example 1, respectively.
The main reference numbers illustrate:
1. a pressure gauge;
2.a mass flow meter;
3. ball milling pot heating body/temperature control heating body;
4. sealing the ball milling tank;
5-1, an inlet;
5-2, an outlet;
6. grinding balls;
7. a pipeline heating insulator;
8. a reducing tee joint;
9. a sample absorption bottle;
10. an ice-water bath device;
11. the diameter-variable two-way pipe is connected;
12. a liquid nitrogen vacuum flask;
13. a U-shaped absorption tube;
14. a temperature control device.
Detailed Description
It should be noted that the term "comprises/comprising" and any variations thereof in the description and claims of this invention and the above-described drawings is intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present invention, the terms "upper", "lower", "inner", "outer", "middle", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings. These terms are used primarily to better describe the invention and its embodiments and are not intended to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meanings of these terms in the present invention can be understood by those skilled in the art as appropriate.
Furthermore, the terms "disposed" and "connected" should be interpreted broadly. For example, "connected" may be a fixed connection, a detachable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meanings of the above terms in the present invention can be understood by those of ordinary skill in the art according to specific situations.
The "ranges" disclosed herein are given as lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges defined in this manner are combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60 to 120 and 80 to 110 are listed for particular parameters, with the understanding that ranges of 60 to 110 and 80 to 120 are also contemplated. Further, if the minimum range values listed are 1 and 2 and the maximum range values listed are 3, 4, and 5, then the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed in the present invention, and "0 to 5" is only a shorthand representation of the combination of these numerical values.
In the present invention, all the embodiments and preferred embodiments mentioned in the present invention may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned in the present invention and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides a system for trapping and analyzing volatile hydrocarbons in a natural gas hydrate reservoir, which is shown in fig. 1, and as can be seen from fig. 1, the system comprises a volatilization device, a primary cold trap device, a secondary cold trap device and a gas chromatography-mass spectrometry;
the volatilization device comprises a sealed ball milling tank 4 containing grinding balls 6 and a ball milling tank heating body/temperature control heating body 3, wherein the ball milling tank heating body/temperature control heating body 3 is sleeved outside the sealed ball milling tank 4 and is used for heating the sealed ball milling tank 4; the sealed ball milling tank 4 is respectively provided with an inlet 5-1 and an outlet 5-2, and a gas carrying bottle (not shown in the figure) is communicated with the inlet 5-1 of the sealed ball milling tank 4 through a pressure gauge 1 and a mass flow meter 2 in sequence by pipelines;
the primary cold trap device comprises an ice-water bath device 10 and a sample absorption bottle 9, the sample absorption bottle 9 contains dichloromethane, the sample absorption bottle 9 is positioned in the ice-water bath device 10, and the opening of the sample absorption bottle is communicated with an outlet 5-1 of the sealed ball milling tank 4 through a transmission pipeline; the outside of the transmission pipeline is coated with a pipeline heating heat-insulating body 7;
the secondary cold trap device comprises a liquid nitrogen vacuum flask 12 and a U-shaped absorption tube 13, wherein an opening at one end of the U-shaped absorption tube 13 is communicated with an opening of the sample absorption bottle 9;
the gas chromatography-mass spectrometry is used for analyzing the composition and content of the trapped volatile hydrocarbon components.
In this embodiment, the opening of the sample absorption bottle 9 is provided with a reducing tee 8 for communicating the outlet 5-2 of the sealed ball milling tank 4 and an opening at one end of the U-shaped absorption tube 13 with the opening of the sample absorption bottle 9.
In this embodiment, the openings at the two ends of the U-shaped absorption tube 13 are both provided with two reducing ports 11, wherein the two reducing ports 11 provided at the opening at one end are used for communicating the opening of the sample absorption bottle 9 with the opening at the end of the U-shaped absorption tube 13, and the two reducing ports 11 provided at the opening at the other end of the U-shaped absorption tube 13 are used for communicating with an external pipeline to discharge light hydrocarbon components condensed in the U-shaped absorption tube 13;
in this embodiment, the system further includes a temperature control device 14, configured to perform temperature programming on the sealed ball milling tank 4 through the ball milling tank heating body/temperature control heating body 3, and further configured to control the temperature of the transmission pipeline and the temperature of the ice-water bath device 10 through the pipeline heating heat insulator 7.
Example 2
The embodiment provides a method for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir, which is realized by using the system for capturing and analyzing volatile hydrocarbons in the natural gas hydrate reservoir provided by the embodiment, and the method comprises the following specific steps:
1) weighing 15-20 g of hydrate sediment sample collected from 3-170 m below a water/sediment interface, filling the hydrate sediment sample into a sealed ball milling tank, sealing and vacuumizing, and filling the sealed ball milling tank into a heating body of the ball milling tank;
2) connecting a gas carrying bottle, wherein the gas carrying bottle uses nitrogen, the mass flow meter controls the gas carrying bottle, and one end of a pipeline connected with the outlet of the gas carrying bottle is inserted into an injection port (inlet) at one side of the ball milling tank by a phi 1 needle;
3) inserting one end of a transmission pipeline into an injection port (outlet) of the ball milling tank, inserting the other end of the transmission pipeline into the bottom of a sample absorption bottle filled with a certain amount of dichloromethane samples, and placing the sample absorption bottle in an ice-water bath device;
4) connecting the sample absorption bottle with an opening at one end of the U-shaped absorption tube, and placing the U-shaped absorption tube in a liquid nitrogen thermos bottle for freezing;
5) and (3) carrying out temperature programming on the ball milling tank in a heating body of the ball milling tank, opening a nitrogen bottle when the ball milling tank is placed in the heating body of the ball milling tank, and setting the mass flow meter to be 10 ml/min. In the temperature programming process, light hydrocarbon components and water vapor are separated and carried by carrier gas through a transmission pipeline to enter a sample absorption bottle, wherein the transmission pipeline is heated by a pipeline heating heat preservation body and keeps the temperature at 120-150 ℃ to prevent the water and the light hydrocarbon components from condensing;
the temperature programming process comprises the following steps: firstly, heating to 150 ℃ at a heating rate of 3 ℃/min, wherein water and part of low-boiling light hydrocarbon components are fully evaporated and separated out; then the temperature is increased to 300 ℃ at the heating rate of 5 ℃/min, and a large amount of light hydrocarbon components are volatilized and separated out. The water and the light hydrocarbon components enter the sample absorption bottle through the insulated transmission pipeline. Because the heat value of the sample and water is very high, the dichloromethane can be gasified, so that the temperature of the dichloromethane in the process must be kept at 0 ℃ or below 0 ℃, and the dichloromethane is convenient for the dichloromethane to dissolve and absorb light hydrocarbon components;
6) because the flow rate is fast, the retention time of the product in the sample absorption bottle is short, and the light hydrocarbon product which is not absorbed by the dichloromethane solution enters the U-shaped absorption tube and is subjected to secondary condensation and collection in the liquid nitrogen vacuum flask;
7) after extraction, cleaning a pipeline, filtering and separating dichloromethane absorption liquid in a sample absorption bottle from water, concentrating by using a nitrogen-blowing method, mixing the obtained light hydrocarbon component with the light hydrocarbon component captured in the U-shaped absorption tube, and analyzing the composition and the content by using gas chromatography-mass spectrometry (GC-MS);
wherein the analysis equipment and analysis conditions used for the gas chromatography-mass spectrometry (GC-MS) analysis comprise:
the gas chromatography-mass spectrometry (GC-MS) adopts Agilent 6890GC-Agilent 5975i MS gas chromatography-mass spectrometry combined instrument and is provided with a DB-5 type capillary chromatographic column (60m multiplied by 0.25mm multiplied by 0.25 mu m);
gas chromatography conditions: the initial temperature of the non-heating program is 100 ℃, the temperature is raised to 320 ℃ at the heating rate of 4 ℃/min, the temperature is maintained for 20min, the carrier gas is high-purity helium, and the split ratio is 20: 1;
the mass spectrometry adopts a full scan mode, an EI ion source is adopted, the electron bombardment energy is 70eV, and the mass number is 50-500 aum.
Samples of hydrate deposits were repeated 3 times according to the procedure, i.e. the procedure shown in steps 1) to 7) above, and the results were analysed for parallelism and a blank test was carried out. The blank control experiment differs from example 2 only in that step 1) was not carried out, i.e. no hydrate sediment sample was added.
A comparison of the gas chromatogram obtained in the blank experiment with the gas chromatogram of the hydrate deposit sample is shown in fig. 2.
Wherein, the total ion flow diagram of the light hydrocarbon components in the hydrate sediment sample obtained by the gas chromatography-mass spectrometry is shown in fig. 3, and as can be seen from fig. 3, through the extraction of the light hydrocarbon components contained in the hydrate sediment sample in the research area, the extracted light hydrocarbon components are mainly C8-C15Hydrocarbon component in the range including the normal alkane series (C)8～C15) Toluene, xylene, trimethylbenzene and naphthalene series (C)0～C3) Etc., and is particularly rich in adamantane series compounds.
The mass spectrograms of the adamantane series compounds in the light hydrocarbon components contained in the hydrate sediment sample in the research area are shown in fig. 4 a-4 c, wherein fig. 4a is the mass spectrogram of adamantane in the light hydrocarbon components contained in the hydrate sediment sample in the research area, fig. 4b is the mass spectrogram of diamantane, and fig. 4c is the mass spectrogram of triamantane.
The specific composition information of the adamantane series compounds in the light hydrocarbon components contained in the hydrate deposit samples obtained from fig. 4a to 4c in the study area is shown in table 1 below.
TABLE 1 analysis and identification table for adamantane series compounds in light hydrocarbon components contained in hydrate sediment samples
As can be seen from fig. 4 a-4 c and table 1, the adamantane series of compounds in the light hydrocarbon component contained in the hydrate deposit samples in the research area included adamantane, diamantane and triamantane, and the adamantane content was predominant.
Based on the analysis of three parallel experiments, the parameters of four main types of compounds, such as methyl adamantane, dimethyl adamantane, methyl naphthalene and dimethyl naphthalene, were calculated, and the results are shown in table 2 below.
Table 2 table for calculating parameters of three experimental results of hydrate deposit samples
Note: the parameters shown in Table 2 include adamantane parameters such as MAI, EAI and DMAI and naphthalene parameters such as DNR-1, MNR and ENR, and specific meanings of these parameters and their calculation formulas are shown in documents [1] and [2 ].
Document [1] Zhibin Wei, J.M.Moldown, Shuichang Zhang, et al, 2007.Diamondoid hydrocarbons as a molecular proxy for thermal mapping and oil cropping, Geochemical models from hydro us virosis. organic Geochemistry 38,227 and 249.
Document [2] Radke, M., Willsch, H.and Leythaeuseer, D.,1982.Aromatic components of mutual: relationship of distribution pattern to rank.Geochimica et Cosmothimic Acta,46,1831-48.
As can be seen from table 2, generally the more abundant compounds are more parallel, with the relative standard deviation RSD of adamantane being substantially less than 5% and the relative standard deviation RSD of naphthalene series compounds being less than 10%.
Comparative example 1
This comparative example provides a method for capturing and analyzing volatile hydrocarbons in a gas hydrate reservoir, which differs from example 2 only in that: in the step 5), the ball milling tank is kept at the constant temperature (300 ℃) in a heating body of the ball milling tank instead of temperature programming.
The total ion flow diagram of light hydrocarbon obtained under the constant temperature (300 ℃) condition in the comparative example 1 and the total ion flow diagram of light hydrocarbon obtained under the temperature programming condition in the embodiment 2 of the present invention are respectively shown in fig. 5a and 5 b.
FIGS. 5c to 5h show the graphs of the analysis results of different adamantane compounds obtained under the temperature-programmed condition in example 2 of the present invention and the graphs of the analysis results of different adamantane compounds obtained under the constant temperature (300 ℃ C.) in comparative example 1, respectively.
Comparing fig. 5a and 5b, fig. 5c and 5d, fig. 5e and 5f, and fig. 5g and 5h, it can be seen that higher light hydrocarbon yield can be obtained by using temperature programming in example 2 of the present invention.
In the embodiment of the invention, when light hydrocarbon components are extracted, water contained in the light hydrocarbon components needs to be removed and separated simultaneously, and the basic flow comprises the following steps: heating a certain amount of hydrate sediment sample to 300 ℃ in a ball milling tank through programmed heating, volatilizing water and light hydrocarbon components from the ball milling tank, then enabling the water and the light hydrocarbon components to enter a transmission pipeline, absorbing the light hydrocarbon components in a sample absorption bottle by dichloromethane, condensing the water, enabling the light hydrocarbon components which are not absorbed by the dichloromethane to enter a U-shaped absorption tube, condensing the light hydrocarbon components in liquid nitrogen, respectively collecting the light hydrocarbon components captured by the sample absorption bottle and the light hydrocarbon components captured by the U-shaped absorption tube, mixing the light hydrocarbon components and the light hydrocarbon components, and sending the mixture into a gas chromatography-mass spectrometry for analysis.
In summary, the system and the method for trapping and analyzing volatile hydrocarbon in the natural gas hydrate reservoir provided by the embodiment of the invention adopt the two-stage cold trap to separate and trap light hydrocarbon components, can effectively separate water contained in a hydrate sediment sample, and reduce the loss of light hydrocarbon; meanwhile, the ball milling tank is heated and sealed by adopting temperature programming, so that the blockage of a transmission pipeline can be effectively prevented, and the analysis efficiency is improved.
The above description is only exemplary of the invention and should not be taken as limiting the scope of the invention, so that the invention is intended to cover all modifications and equivalents of the embodiments described herein. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (10)
1. The system for trapping and analyzing the volatile hydrocarbon in the natural gas hydrate reservoir is characterized by comprising a volatilization device, a primary cold trap device, a secondary cold trap device, a temperature control device and a gas chromatography-mass spectrum;
the volatilization device comprises a sealed ball milling tank and a ball milling tank heating body, wherein the ball milling tank heating body is sleeved outside the sealed ball milling tank and used for heating the sealed ball milling tank; the sealed ball milling tank is respectively provided with an inlet and an outlet, and the inlet is communicated with the gas carrying bottle;
the primary cold trap device comprises an ice-water bath device and a sample absorption bottle, the sample absorption bottle is filled with dichloromethane, the sample absorption bottle is positioned in the ice-water bath device, and an opening of the sample absorption bottle is communicated with an outlet of the sealed ball milling tank through a transmission pipeline;
the secondary cold trap device comprises a liquid nitrogen thermos bottle and a U-shaped absorption tube, wherein an opening at one end of the U-shaped absorption tube is communicated with an opening of the sample absorption bottle;
the gas chromatography-mass spectrometry is used for analyzing the composition and the content of the trapped volatile hydrocarbon component;
the temperature control device is used for carrying out temperature programming on the sealed ball milling tank through a heating body of the ball milling tank, controlling the temperature of the transmission pipeline and controlling the temperature of the ice-water bath device.
2. The system of claim 1, wherein the gas carrying bottle is communicated with an inlet of the sealed ball milling tank through a pressure gauge and a mass flow meter in sequence through pipelines.
3. The system of claim 1 or 2, wherein the transfer line is coated with a line heating insulation.
4. The system as claimed in claim 1 or 2, wherein the opening of the sample absorption bottle is provided with a reducing tee for communicating the outlet of the sealed ball milling jar and the opening of one end of the U-shaped absorption tube with the opening of the sample absorption bottle.
5. The system as claimed in claim 1 or 2, wherein the one end opening of the U-shaped absorption tube is provided with a reducing two-way for communicating the opening of the sample absorption bottle with the one end opening of the U-shaped absorption tube.
6. A method for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir, which is implemented by using the system for capturing and analyzing volatile hydrocarbons in a natural gas hydrate reservoir according to any one of claims 1 to 5, and comprises the following steps:
(1) filling a hydrate sediment sample into a sealed ball milling tank, sealing and vacuumizing, performing temperature programming on the sealed ball milling tank by using a heating body of the ball milling tank, and opening a gas carrying bottle;
(2) in the temperature programming process, light hydrocarbon components and water vapor are separated and carried by carrier gas to enter a sample absorption bottle, the light hydrocarbon components in the sample absorption bottle are absorbed by dichloromethane, and the temperature of the dichloromethane is always kept at 0 ℃ in the absorption process;
(3) light hydrocarbon components which are not absorbed by the dichloromethane enter the U-shaped absorption tube, and are condensed in liquid nitrogen;
(4) and light hydrocarbon components captured by the sample absorption bottle and light hydrocarbon components captured by the U-shaped absorption tube are respectively collected, and then are mixed and sent to a gas chromatography-mass spectrometer for composition and content analysis.
7. The method of claim 6, wherein in step (1), the temperature programming comprises:
firstly, heating to 110-150 ℃ at a heating rate of 2-5 ℃/min, fully evaporating and separating water and part of low-boiling light hydrocarbon components, and heating to 300 ℃ at a heating rate of 5-10 ℃/min, wherein a large amount of light hydrocarbon components are volatilized and separated.
8. The method according to claim 6 or 7, wherein the carrier gas is nitrogen.
9. The method of claim 6 or 7, wherein in step (2), the light hydrocarbon components and the water vapor are separated and carried by the carrier gas through the transport line into the sample absorption bottle, and the transport line is heated by the pipeline heating insulator and maintained at 120-150 ℃.
10. The method of claim 6 or 7, wherein the hydrate deposit sample is taken from the deep sea floor 1 to 200m below the water/deposit interface.
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