CN115508250A - Porous medium gas adsorption capacity evaluation system and method considering water-rock effect - Google Patents
Porous medium gas adsorption capacity evaluation system and method considering water-rock effect Download PDFInfo
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- 239000011435 rock Substances 0.000 title claims abstract description 171
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000011156 evaluation Methods 0.000 title claims abstract description 12
- 230000000694 effects Effects 0.000 title claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000007789 gas Substances 0.000 claims abstract description 117
- 238000005070 sampling Methods 0.000 claims abstract description 92
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 35
- 239000001569 carbon dioxide Substances 0.000 claims description 31
- 239000008398 formation water Substances 0.000 claims description 26
- 238000009792 diffusion process Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 12
- 239000001307 helium Substances 0.000 claims description 12
- 229910052734 helium Inorganic materials 0.000 claims description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
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- 229920006395 saturated elastomer Polymers 0.000 claims description 11
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- 238000005481 NMR spectroscopy Methods 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000006399 behavior Effects 0.000 claims description 6
- 238000010997 low field NMR spectroscopy Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
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- 239000001273 butane Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000010183 spectrum analysis Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 5
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
- G01N7/02—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder
- G01N7/04—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder by absorption or adsorption alone
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
- G01N2013/003—Diffusion; diffusivity between liquids
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Abstract
The invention relates to the technical field of natural gas exploitation, and discloses a porous medium gas adsorption capacity evaluation system and method considering water-rock action. This system includes rock sample holder, the upper reaches of rock sample holder are connected with reference cauldron, middle container group and evacuation subassembly respectively through the six-way valve, be equipped with first manometer between rock sample holder and the six-way valve, rock sample holder low reaches are equipped with second manometer and first sampling point in proper order, refer the cauldron with be equipped with two circuits between the six-way valve, first circuit is in the entry of referring the cauldron is equipped with two three-way valves, two three-way valves with air supply mechanism passes through the pipe connection, and the second circuit is in the entry of referring the cauldron is equipped with first valve, first valve with sample area in the middle of the pipeline constitution between the six-way valve, one of them valve of six-way valve is the second sampling point valve. The invention can realize the detection of the gas adsorption information in the porous medium after the water-rock action.
Description
Technical Field
The invention relates to the technical field of natural gas exploitation, in particular to a porous medium gas adsorption capacity evaluation system and method considering water-rock action.
Background
Natural gas refers to a mixture of hydrocarbon and non-hydrocarbon gases trapped in a formation. After the twenty-first century, the national economy of China has rapidly increased, and the demand for natural gas is gradually increased. At present, unconventional natural gas with commercial value is mainly natural gas in the forms of shale gas, coal bed gas, tight sandstone gas, natural gas hydrate, water-soluble gas, inorganic gas, shallow biogas and the like. Among them, shale gas in China has huge potential, and is one of the energy sources which need to be developed urgently.
Considering that shale has a greater adsorption capacity for carbon dioxide than methane, in the related art, carbon dioxide and methane (CH) are introduced into a shale reservoir 4 ) Occurrence competitionAnd the adsorbed methane in the shale can be replaced by the adsorption.
However, CO 2 Compared with geological fluids such as oil, gas and the like, the active gas is very easy to react with rocks and formation water in surrounding reservoirs when being injected into the underground, the active gas is dissolved in the formation water to form carbonic acid, and the solubility is high under the condition of temperature and pressure of the reservoirs, so that the liquid is strong in acidity and can cause the change of physical conditions and chemical properties of the reservoirs, and therefore, the research of the gas adsorption capacity of the porous medium considering the water-rock effect is an urgent problem to be solved.
Disclosure of Invention
The invention aims to solve the problem that water-rock reaction is not considered when the adsorption capacity of a reservoir to gas is researched in the prior art, and provides a porous medium gas adsorption capacity evaluation system and method considering water-rock action. By reasonably designing the evaluation system, the near-well CO can be realized 2 Research on gas adsorption capacity of porous medium in constant-current and constant-pressure seepage process and far-well CO 2 And (3) researching the gas adsorption capacity of the porous medium in the process of the unsteady pressure free diffusion seepage.
In order to achieve the above object, the present invention provides a porous medium gas adsorption capacity evaluation system considering water and rock effects, which comprises a rock sample holder, wherein a reference kettle, an intermediate container group and a vacuum pumping assembly are respectively connected to the upstream of the rock sample holder through a six-way valve; a first pressure gauge is arranged between the rock sample holder and the six-way valve, and a second pressure gauge and a first sampling point are sequentially arranged at the downstream of the rock sample holder; an air source mechanism and a gas booster pump are sequentially arranged at the upper stream of the reference kettle along the airflow direction, two lines are arranged between the reference kettle and the six-way valve, the first line is provided with two three-way valves at the inlet of the reference kettle, the two three-way valves are connected with the gas booster pump through pipelines, a first valve is arranged at the inlet of the reference kettle in the second line, a pipeline between the first valve and the six-way valve forms an intermediate sampling area, one valve of the six-way valve is a second sampling point valve, and the reference kettle is connected with a third pressure gauge; the middle container group comprises a carbonic acid container, a stratum water container, a natural gas container and a carbon dioxide container, and a plunger pump is arranged at the upstream of the middle container group.
Preferably, a first flow control device is arranged between the rock sample holder and the first pressure gauge, and a second flow control device is arranged between the second pressure gauge and the first sampling point.
Preferably, a gas-liquid separation device is arranged between the second pressure gauge and the second flow control device.
Preferably, a third valve and a fourth valve are provided between the second flow control device and the first sampling point, the third valve being open for exhaust and the fourth valve being open for sampling.
Preferably, a fourth pressure gauge is arranged between the intermediate container group and the six-way valve.
Preferably, the carbonic acid container, the stratum water container, the natural gas container and the carbon dioxide container are connected in parallel, and the outlets and inlets of the carbonic acid container, the stratum water container, the natural gas container and the carbon dioxide container are all provided with switch valves.
Preferably, the reference tank and the intermediate tank group are both arranged in a thermostatic control device.
Preferably, the rock sample holder is arranged in a low-field nuclear magnetic resonance instrument, and the low-field nuclear magnetic resonance instrument is connected with a first industrial control computer.
Preferably, the first pressure gauge and the second pressure gauge are both connected with the first industrial control computer.
Preferably, the gas source mechanism comprises a natural gas supply unit, a carbon dioxide supply unit and a helium supply unit, and the tops of the natural gas supply unit, the carbon dioxide supply unit and the helium supply unit are all provided with switch valves.
Preferably, the third pressure gauge is connected with a second industrial control computer.
In a second aspect, the invention provides a method for evaluating the gas adsorption capacity of a porous medium in consideration of the effect of water and rock, which is implemented in the system described above,
the method comprises the following steps:
s1, placing a porous medium in the rock sample holder, vacuumizing the system, and measuring the volume of a free space in the rock sample holder;
s2, vacuumizing the system, injecting natural gas into the porous medium through the plunger pump, performing saturated adsorption, and then injecting CO at constant pressure and constant flow 2 Collecting gas at the outlet end of the rock sample holder at different moments for component analysis, and recording gas pressure, instantaneous flow and accumulated flow at two ends of the rock sample holder in real time;
s3, saturation adsorption of CO by porous medium 2 Post stop CO injection 2 Calculating the porous Medium CO according to formula (I) 2 The adsorption capacity of the adsorbent is improved,
wherein, P in 、P i And P p Respectively CO at the inlet end of the rock sample holder 2 The unit of the injection pressure, the instantaneous pressure at the outlet end of the rock sample holder when collecting and sampling at different moments and the free space pressure in the porous medium is MPa; z is a linear or branched member in 、Z i 、Z p Respectively corresponding to pressure P in 、P i And P p The gas compression factor of (a); v in And V i Respectively CO at the inlet end of the rock sample holder 2 The unit of the injection amount and the collection amount at the outlet end in the process of collecting and sampling at different moments is mL; v p The volume of the free space of the rock sample holder is mL; x is the number of i Collecting CO in gas at outlet end of rock sample holder for sampling at different times 2 The volume ratio is expressed in%; i is the sampling frequency; n is Adsorption The unit of (A) is mol;
s4, carrying out vacuum pumping to desorb the porous medium, injecting formation water into the porous medium to saturation through the plunger pump, and then injecting carbonic acid into the porous medium through the plunger pump to carry out water-rock reaction;
s5, repeating the step S1 to the step S3, and measuring the porous medium CO after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
In a third aspect, the invention provides a method for evaluating the gas adsorption capacity of a porous medium in consideration of the effect of water and rock, which is implemented in the system described above,
the method comprises the following steps:
1) Placing a porous medium in the rock sample holder, then evacuating the system, and determining the volume of free space in the rock sample holder;
2) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 Preparation of Natural gas and CO 2 Pressure ratio of K 1 The reference kettle and the rock sample holder are communicated, and the mixed gas is introduced into a porous medium to be adsorbed stably, so that the pretreatment of the porous medium is completed;
3) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 Preparation of Natural gas and CO 2 Pressure ratio of K 2 Mixed gas of (2), K 2 And K 1 The same or different;
4) Communicating the reference kettle and the rock sample holder to diffuse the mixed gas into the porous medium, closing the first valve after the intermediate sampling area has diffusion pressure until the porous medium is stably adsorbed, then closing the six-way valve, opening the second sampling point valve to sample from the intermediate sampling area for gas component analysis, and measuring the balance pressure of the sampling area at the moment through the first pressure gauge;
5) Repeating the step 4), wherein the diffusion pressure of the middle sampling area is different when the operation is repeated each time, and calculating the porous medium CO under different diffusion pressures according to the formula (II) 2 The capability of adsorption,
wherein M is i And N i Respectively the equilibrium pressure of the reference kettle and the equilibrium pressure of the sampling area during each sampling, and the unit is MPa; a is i And b i Respectively the CO in the reference kettle gas at each sampling 2 The volume ratio is expressed in%; s L And S p Respectively the volume of the middle sampling area and the volume of the free space of the rock sample holder, wherein the unit is mL; t is i To correspond to the pressure N i The gas compression factor of (a); i is the sampling frequency; m is a unit of Adsorption The unit of (A) is mol;
6) Vacuumizing to desorb the porous medium, injecting formation water into the porous medium through the plunger pump until the formation water is saturated, and then injecting carbonic acid into the porous medium through the plunger pump to perform water-rock reaction;
7) Repeating the steps 1) to 6), and measuring the porous medium CO under different diffusion pressures after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
Preferably, the method further comprises measuring T of the porous medium by the low-field NMR spectrometer 2 And (4) spectrum analysis is carried out on the peak area change of the spectrogram and the gas adsorption-desorption behaviors in the pores of different porous media.
Preferably, the natural gas contains one or more of methane, ethane, propane, butane and hydrogen.
Preferably, the porous medium is shale, coal, activated carbon, sandstone or carbonate.
By adopting the system provided by the invention to be matched with a specific method, near-well CO can be explored 2 Difference of adsorption capacity of porous medium before and after water-rock action in constant-current constant-pressure seepage process, and far-well CO 2 The difference of the adsorption capacity of the porous medium before and after the water-rock action in the free diffusion seepage process realizes the detection of gas adsorption information in the porous medium after the water-rock action, thereby reasonably guiding the efficient exploitation of shale gas and the carbon sequestration of a shale reservoir.
Drawings
FIG. 1 is a gas adsorption capacity evaluation system for porous media considering the effect of water and rock according to the present invention.
FIG. 2 is a graph showing the change in the adsorption amount before and after the action of the water rock in example 1.
FIG. 3 is a graph showing the change in the adsorption amount before and after the action of the hydrorocks in example 2.
FIG. 4 is a graph showing the change of the T2 curve before and after the water-rock interaction in example 2.
Description of the reference numerals
1 a rock sample holder; 2, a reference kettle; 3 middle container group; 31 a carbonic acid container; 32 formation water containers; 33 a natural gas container; 34 a carbon dioxide container; 35 a plunger pump; 4, a vacuum pumping assembly; 5, a first pressure gauge; 6 a second pressure gauge; 7 a first sampling point; 8, an air source mechanism; 81 natural gas supply units; 82 a carbon dioxide supply unit; 83 a helium gas supply unit; 9 a three-way valve; 10 a first valve; 12 a second sample point valve; 13 a third pressure gauge; 14 a first flow control device; 15 a second flow control device; 16 gas-liquid separation device; 17 a third valve; 18 a fourth valve; 19 a fourth pressure gauge; 20 a first industrial control computer; 21 a second industrial control computer; a six-way valve; b, a booster pump; c, a constant temperature control device; 101 low field nuclear magnetic resonance apparatus.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the "upstream" refers to the direction of the source of the gas and the "downstream" refers to the direction of the destination of the gas, and in fig. 1, the left side is "upstream" and the right side is "downstream".
The invention provides a porous medium gas adsorption capacity evaluation system considering water and rock effects, as shown in figure 1, the system comprises a rock sample holder 1, wherein the upstream of the rock sample holder 1 is respectively connected with a reference kettle 2, an intermediate container group 3 and a vacuumizing assembly 4 through a six-way valve A; a first pressure gauge 5 is arranged between the rock sample holder 1 and the six-way valve A, and a second pressure gauge 6 and a first sampling point 7 are sequentially arranged at the downstream of the rock sample holder 1; an air source mechanism 8 and a gas booster pump B are sequentially arranged at the upstream of the reference kettle 3 along the air flow direction, two lines are arranged between the reference kettle 3 and the six-way valve A, the first line is provided with two three-way valves 9 at the inlet of the reference kettle 3, the two three-way valves 9 are connected with the gas booster pump B through pipelines, the second line is provided with a first valve 10 at the inlet of the reference kettle 3, the pipeline between the first valve 10 and the six-way valve A forms an intermediate sampling area 11, one valve of the six-way valve A is a second sampling point valve 12, and the reference kettle is connected with a third pressure gauge 13; the intermediate container group 3 comprises a carbonic acid container 31, a formation water container 32, a natural gas container 33 and a carbon dioxide container 34, and a plunger pump 35 is arranged at the upstream of the intermediate container group 3.
In the system of the invention, the gas provided by the gas source mechanism 8 can directly reach the six-way valve A through a first line without entering the reference kettle 3 by controlling the switches of the two three-way valves 9, then the six-way valve A is controlled to enable the gas to respectively enter the natural gas container 33 and the carbon dioxide container 34 in the intermediate container group 3, the liquids in the carbonic acid container 31 and the formation water container 32 can be prepared in advance and directly filled, and then the natural gas, the carbon dioxide, the carbonic acid or the formation water in the natural gas container 33, the carbon dioxide container 34, the carbonic acid container 31 or the formation water container 32 enters the rock sample holder 1 through the six-way valve A by the plunger pump 35. In the system of the invention, the gas provided by the gas source mechanism 8 can enter the reference kettle 3 through the second line to the six-way valve a by controlling the switches of the two three-way valves 9, and then the six-way valve a is controlled to directly enter the rock sample holder 1. After natural gas and carbon dioxide are fed into the reference kettle 3, the reference kettle 3 can be used for preparing natural gas and carbon dioxide mixed gas in different proportions. The vacuum pumping assembly 4 is used for pumping vacuum for the whole system. The gas booster pump B is used for pumping out the gas provided by the gas source mechanism 8 and then pumping the gas with the specified pressure into the reference kettle 3 or pumping the gas with the specified pressure into the six-way valve A.
In a specific embodiment, the rock sample holder 1 is further connected with a device for generating confining pressure and high temperature and high pressure in the rock sample holder 1 through a connecting pipeline, and the device is used for providing temperature and pressure conditions similar to the formation environment for a sample in the rock sample holder 1.
In a preferred embodiment, a first flow control device 14 is arranged between the rock sample holder 1 and the first pressure gauge 5, and a second flow control device 15 is arranged between the second pressure gauge 6 and the first sampling point 7. The first and second flow control devices 14, 15 may be used to control the flow of gas through a porous medium placed within the rock sample holder 1.
In a preferred embodiment, a gas-liquid separation device 16 is arranged between the second pressure gauge 6 and the second flow control device 15. During the evaluation method, after stratum water and carbonate water are added for action, the outlet end of the rock sample holder 1 can produce liquid, and a gas-liquid separation device 16 is needed for separation so as to collect a gas sample.
In a preferred embodiment, a third valve 17 and a fourth valve 18 are provided between the second flow control device 15 and the first sampling point 7, the third valve 17 being open for exhaust and the fourth valve 18 being open for sampling.
In a preferred embodiment, a fourth pressure gauge 19 is provided between the intermediate container group 3 and the six-way valve a. The function of the fourth pressure gauge 19 is to determine the pressure of the gas introduced into the intermediate container group 3.
In a preferred embodiment, the carbonic acid container 31, the formation water container 32, the natural gas container 33 and the carbon dioxide container 34 are connected in parallel, and the outlets and inlets of the carbonic acid container 31, the formation water container 32, the natural gas container 33 and the carbon dioxide container 34 are provided with on-off valves. In actual operation, the independent use of each carbonic acid, formation water, natural gas and carbon dioxide can be realized by controlling the switch valve of each container.
In a preferred embodiment, the reference kettle 2 and the intermediate container group 3 are both arranged in a thermostatic control device C, so that the temperature of the gas entering the reference kettle and the gas and the liquid in the intermediate container group 3 are consistent with the temperature of the porous medium arranged in the rock sample holder 1, and the formation environment is simulated.
In a preferred embodiment, the rock sample holder 1 is placed in a low-field nmr 101, and the low-field nmr 101 is connected to a first industrial control computer 20. The low field nmr 2 can measure the transverse relaxation time of the natural gas and display the result by the first industrial computer 20.
In a preferred embodiment, the first pressure gauge 5 and the second pressure gauge 6 are both connected to the first industrial control computer 20. The first industrial control computer 20 can record the pressure change data of the inlet and outlet of the rock sample holder 1 in real time.
In a preferred embodiment, the gas source mechanism 8 comprises a natural gas supply unit 81, a carbon dioxide supply unit 82 and a helium supply unit 83, and the tops of the natural gas supply unit 81, the carbon dioxide supply unit 82 and the helium supply unit 83 are all provided with a switch valve. The natural gas, carbon dioxide and helium provided from the natural gas supply unit 81, the carbon dioxide supply unit 82 and the helium supply unit 83 may be used individually or simultaneously. The helium gas can be used to determine the free space volume of the rock sample holder 1.
In a preferred embodiment, the third pressure gauge 13 is connected to a second industrial control computer 21. The second industrial control computer 21 can be used to record the pressure in the reference tank 3 in real time.
In a second aspect, the invention provides a method for evaluating the gas adsorption capacity of a porous medium in consideration of the effect of water and rock, which is implemented in the system described above,
the method comprises the following steps:
s1, placing a porous medium in the rock sample holder 1, vacuumizing the system, and measuring the volume of a free space in the rock sample holder 1;
s2, vacuumizing the system, injecting natural gas into the porous medium through the plunger pump 35, performing saturated adsorption, and then injecting CO at constant pressure and constant flow 2 Collecting gas at the outlet end of the rock sample holder 1 at different moments for component analysis, and recording gas pressure, instantaneous flow and accumulated flow at two ends of the rock sample holder 1 in real time;
s3, adsorbing CO by porous medium in a saturated way 2 Post stop CO injection 2 Calculating the porous Medium CO according to formula (I) 2 The capability of adsorption,
wherein, P in 、P i And P p Respectively CO at the inlet end of the rock sample holder 1 2 The unit of the injection pressure, the instantaneous pressure at the outlet end of the rock sample holder 1 when collecting and sampling at different moments and the free space pressure in the porous medium is MPa; z in 、Z i 、Z p Respectively corresponding to pressure P in 、P i And P p The gas compression factor of (a); v in And V i CO at the inlet end of the rock sample holder 1 2 The unit of the injection amount and the collection amount at the outlet end in the process of collecting and sampling at different moments is mL; v p The volume of the free space of the rock sample holder 1 is in mL; x is the number of i Collecting CO in gas at the outlet end of the rock sample holder 1 for sampling at different moments 2 The volume ratio is expressed in%; i is the sampling times; n is Adsorption The unit of (A) is mol;
s4, carrying out vacuum pumping to desorb the porous medium, injecting formation water into the porous medium through the plunger pump 35 until the porous medium is saturated, and then injecting carbonic acid into the porous medium through the plunger pump 35 to carry out water-rock reaction;
s5, repeating the step S1 to the step S3, and measuring the porous medium CO after the water rock reaction 2 The adsorption capacity of the adsorbent is improved,and evaluating the influence of the water rock reaction on the adsorption capacity of the porous medium.
The method provided by the second aspect of the invention can be used for exploring near-well CO 2 And the difference of the adsorption capacity of the porous medium before and after the water-rock action in the constant-current constant-pressure seepage process. The method comprises the following specific operation processes: after the system is installed and the experimental sample is installed, namely after the preparation work is done, the system is vacuumized, the free space volume in the rock sample holder 1 is measured, then natural gas is injected into the porous medium through the plunger pump 35 and is subjected to saturated adsorption, the original natural gas adsorption behavior in the reservoir is simulated, and then CO is injected into the porous medium at constant pressure and constant current 2 Displacing natural gas by competitive adsorption and evaluating it for CO 2 Adsorption capacity of the CO 2 Is monitored by means of a first pressure gauge 5 and a first flow control device 14, the gas at the outlet end of the rock sample holder 1 is collected from a first sampling point 7 at intervals for composition analysis, and the porous medium CO is calculated according to formula (I) 2 Adsorbing capacity, then vacuumizing to desorb the porous medium, injecting formation water into the porous medium to saturation through the plunger pump 35, then injecting carbonic acid into the porous medium through the plunger pump 35 to perform water-rock reaction, and simulating CO 2 Injection into the reservoir, CO 2 The step S1 to the step S3 are repeated under the condition of reacting with rocks and formation water in the surrounding reservoir, and the porous medium CO after the water-rock reaction is measured 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
In a third aspect, the invention provides a method for evaluating the gas adsorption capacity of a porous medium by considering the water-rock effect, which is implemented in the system,
the method comprises the following steps:
1) Placing a porous medium in the rock sample holder 1, then evacuating the system and determining the volume of free space in the rock sample holder 1;
2) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 1 The reference kettle 2 and the rock sample holder 1 are communicated, and the mixed gas is introduced into a porous medium to be adsorbed to be stable, so that the pretreatment of the porous medium is completed;
3) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 2 Mixed gas of (2), K 2 And K 1 The same or different;
4) Communicating the reference kettle 2 with the rock sample holder 1 to diffuse the mixed gas into a porous medium, closing the first valve 10 after the intermediate sampling area 11 has diffusion pressure until the porous medium is stably adsorbed, then closing the six-way valve A, opening the second sampling point valve 12 to sample from the intermediate sampling area 11 for gas component analysis, and measuring the balance pressure of the sampling area 11 at the moment through the first pressure gauge 5;
5) Repeating the step 4), wherein the intermediate sampling region 11 has different diffusion pressures each time the operation is repeated, and calculating the porous medium CO at different diffusion pressures according to the formula (II) 2 The adsorption capacity of the adsorbent is improved,
wherein M is i And N i The balance pressure of the reference kettle 2 and the balance pressure of the sampling area 11 are respectively obtained in MPa during each sampling; a is i And b i Respectively, the CO in the gas of the reference kettle 2 during each sampling 2 The volume ratio is expressed in%; s L And S p Respectively the volume of the middle sampling area 11 and the free space volume of the rock sample holder 1, and the unit is mL; t is i To correspond to the pressure N i The gas compression factor of (a); i is the sampling frequency; m is a unit of Adsorption The unit of (A) is mol;
6) Vacuumizing to desorb the porous medium, injecting formation water into the porous medium to saturation through the plunger pump 35, and then injecting carbonic acid into the porous medium through the plunger pump 35 to perform water-rock reaction;
7) Repeating the steps 1) to 6), and measuring the porous medium CO under different diffusion pressures after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
The third aspect of the invention provides a method for studying off-hole CO 2 And the difference of the adsorption capacity of the porous medium before and after the water-rock action in the free diffusion seepage process. The method comprises the following specific operations: after the system is installed and the experimental sample is installed, namely after the preparation work is done, the system is vacuumized, the free space volume in the rock sample holder 1 is measured, and then natural gas and CO are introduced into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 1 The reference kettle 2 and the rock sample holder 1 are communicated, the mixed gas is introduced into a porous medium to be adsorbed stably, and the pretreatment of the porous medium is completed, wherein the purpose of the pretreatment is to simulate natural gas and CO with different proportions 2 Initial adsorption state in natural gas reservoir, then vacuumizing again, and introducing natural gas and CO into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 2 Mixed gas of (2), K 2 And K 1 The reference kettle 2 and the rock sample holder 1 are communicated to diffuse the mixed gas into the porous medium, the first valve 10 is closed after the middle sampling area 11 has a certain diffusion pressure until the porous medium is stably adsorbed, then the six-way valve A is closed, the second sampling point valve 12 is opened to sample from the middle sampling area 11 for gas component analysis, the balance pressure of the sampling area 11 at the moment is measured through the first pressure gauge 5, the operation is repeated, the difference is that the reference kettle 2 and the rock sample holder 1 are communicated each time to diffuse the mixed gas into the porous medium, the diffusion pressure of the middle sampling area 11 is different, and then the porous medium CO under different diffusion pressures is calculated according to the formula (II) 2 Adsorbing capacity, then vacuumizing to desorb the porous medium, injecting formation water into the porous medium to saturation through the plunger pump 35, then injecting carbonic acid into the porous medium through the plunger pump 35 to perform water-rock reaction, and simulating CO 2 Is injected intoIn the reservoir, CO 2 And (3) under the condition of reacting with rocks and formation water in a surrounding reservoir, repeating the steps 1) to 6), and measuring the porous medium CO under different diffusion pressures after the reaction of the rocks 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
The method according to the second and third aspects of the invention further comprises measuring T of the porous medium by means of the low-field NMR spectrometer 101 2 And (4) spectrum analysis is carried out on the peak area change of the spectrogram and the gas adsorption-desorption behaviors in the pores of different porous media. In particular, T 2 The spectrum can obtain the adsorption characteristics of natural gas in pores with different sizes, and the injected CO is analyzed 2 Competitive adsorption in pores and influence on natural gas desorption behavior, comparing natural gas and CO before and after water-rock reaction 2 Competitive adsorption behavior change characteristics.
The second and third aspects of the invention provide processes wherein the natural gas comprises one or more of methane, ethane, propane, butane and hydrogen.
In the method provided by the second and third aspects of the invention, the porous medium is shale, coal, activated carbon, sandstone or carbonate.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The following embodiments are implemented in a porous medium gas adsorption capacity evaluation system considering water and rock action as shown in fig. 1, the system comprises a rock sample holder 1, the upstream of the rock sample holder 1 is respectively connected with a reference kettle 2, an intermediate container group 3 and a vacuumizing assembly 4 through a six-way valve a, a first pressure gauge 5 is arranged between the rock sample holder 1 and the six-way valve a, the downstream of the rock sample holder 1 is sequentially provided with a second pressure gauge 6 and a first sampling point 7, the upstream of the reference 3 is sequentially provided with a gas source mechanism 8 and a gas booster pump B along the gas flow direction, two lines are arranged between the reference kettle 3 and the six-way valve a, the first line is provided with two three-way valves 9 at the inlet of the reference kettle 3, the two three-way valves 9 are connected with the gas booster pump B through pipelines, the second line is provided with a first valve 10 at the inlet of the reference kettle 3, a pipeline between the first valve 10 and the six-way valve A forms an intermediate sampling area 11, one valve of the six-way valve A is a second sampling point valve 12, the reference kettle is connected with a third pressure gauge 13, the intermediate container group 3 comprises a carbonic acid container 31, a stratum water container 32, a natural gas container 33 and a carbon dioxide container 34, a plunger pump 35 is arranged at the upstream of the intermediate container group 3, a first flow control device 14 is arranged between the rock sample holder 1 and the first pressure gauge 5, a second flow control device 15 is arranged between the second pressure gauge 6 and the first sampling point 7, a gas-liquid separation device 16 is arranged between the second pressure gauge 6 and the second flow control device 15, a third valve 17 and a fourth valve 18 are arranged between the second flow control device 15 and the first sampling point 7, the third valve 17 is opened for exhausting gas, the fourth valve 18 is opened for sampling, a third valve 17 and a fourth valve 18 are arranged between the second flow control device 15 and the first sampling point 7, the third valve 17 is opened for exhausting gas, the fourth valve 18 is opened for sampling, a fourth pressure gauge 19 is arranged between the intermediate container group 3 and the six-way valve a, the carbonated container 31, the formation water container 32, the natural gas container 33 and the carbon dioxide container 34 are connected in parallel, the carbonated container 31, the formation water container 32, the natural gas container 33 and the carbon dioxide container 34 are provided with switch valves at the outlet and inlet, the reference kettle 2 and the intermediate container group 3 are arranged in a thermostatic control device C, the rock sample holder 1 is arranged in the low-field nuclear magnetic resonance instrument 101, the low-field nuclear magnetic resonance instrument 101 is connected with a first industrial control computer 20, the first industrial control computer 5 and the second industrial control computer 6 are connected with the first industrial control computer 20, the gas source mechanism 8 comprises a natural gas supply unit 81, a carbon dioxide supply unit 82 and a supply unit 83, the natural gas supply unit 81 and the helium supply unit 21 and the second industrial control computer 13 is connected with a helium supply unit.
The natural gas used in examples 1 and 2 had a methane component.
Examples1 for exploring near-well CO 2 And (3) the difference of the adsorption capacity of the shale before and after the action of water and rock in the constant-current constant-pressure seepage process.
The method comprises the following steps:
s1, placing shale into the rock sample holder 1, vacuumizing the system, and measuring the volume of a free space in the rock sample holder 1;
s2, vacuumizing the system, injecting natural gas into the shale through the plunger pump 35, performing saturated adsorption, and then injecting CO at constant pressure and constant flow 2 Collecting gas at the outlet end of the rock sample holder 1 at different moments for component analysis, and recording gas pressure, instantaneous flow and accumulated flow at two ends of the rock sample holder 1 in real time;
s3, shale saturation adsorption of CO 2 Post stop CO injection 2 Calculating shale CO according to formula (I) 2 The adsorption capacity of the adsorbent is improved,
wherein, P in 、P i And P p CO at the inlet end of the rock sample holder 1 2 The unit of the instantaneous pressure at the outlet end of the rock sample holder 1 and the free space pressure in the shale is MPa when the injection pressure, the collection and sampling at different moments are carried out; z in 、Z i 、Z p Respectively corresponding to pressure P in 、P i And P p The gas compression factor of (a); v in And V i CO at the inlet end of the rock sample holder 1 2 The unit of the injection amount and the collection amount at the outlet end in the process of collecting and sampling at different moments is mL; v p The volume of the free space of the rock sample holder 1 is in mL; x is the number of i Collecting CO in gas at the outlet end of the rock sample holder 1 for sampling at different moments 2 The occupied volume ratio is in unit; i is the sampling times;
s4, desorbing the shale by vacuumizing, injecting formation water into the shale to saturation through the plunger pump 35, and then injecting carbonic acid into the porous medium through the plunger pump 35 to perform water-rock reaction;
s5, repeating the step S1 to the step S3, and measuring the shale CO after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the shale adsorption capacity.
The change of the adsorption amount before and after the action of the water rock in this example is shown in FIG. 2. As can be seen from fig. 2, the CO2 adsorption rate after the water-rock reaction becomes faster, i.e., the saturated adsorption state is reached more quickly, but the total adsorption amount is reduced.
Example 2 exploration of far-well CO 2 And the difference of the adsorption capacity of the porous medium before and after the water-rock action in the free diffusion seepage process.
The method comprises the following steps:
1) Placing shale into the rock sample holder 1, then evacuating the system and determining the volume of free space in the rock sample holder 1;
2) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 1 (K 1 The mixed gas of 5) is communicated with the reference kettle 2 and the rock sample holder 1, and the mixed gas is introduced into shale to be adsorbed stably, so that the pretreatment of the porous medium is completed;
3) Vacuumizing the system, and introducing natural gas and CO into the reference kettle 2 2 Preparation of Natural gas and CO 2 Pressure ratio of K 2 (K 2 0.5) of mixed gas;
4) Communicating the reference kettle 2 and the rock sample holder 1 to diffuse the mixed gas into shale, closing the first valve 10 after the middle sampling area 11 has a certain diffusion pressure until the shale is stably adsorbed, then closing the six-way valve A, opening the second sampling point valve 12 to sample from the middle sampling area 11 for gas component analysis, and measuring the balance pressure of the sampling area 11 at the moment through the first pressure gauge 5;
5) Repeating the step 4), wherein the diffusion pressure of the middle sampling area 11 is different when the operation is repeated each time, and calculating the shale CO under different diffusion pressures according to the formula (II) 2 The adsorption capacity of the adsorbent is improved,
wherein, M i And N i The equilibrium pressure of the reference kettle 2 and the equilibrium pressure of the sampling area 11 are respectively obtained in MPa in each sampling; a is a i And b i Respectively, the CO in the gas of the reference kettle 2 during each sampling 2 The volume ratio is expressed in%; s L And S p Respectively the volume of the middle sampling area 11 and the free space volume of the rock sample holder 1, and the unit is mL; t is i To correspond to the pressure N i The gas compression factor of (a); i is the number of samples.
6) Vacuumizing to desorb the shale, injecting formation water into the porous medium through the plunger pump 35 until the formation water is saturated, and then injecting carbonic acid into the porous medium through the plunger pump 35 to perform water-rock reaction;
7) Repeating the steps 1) to 6), and measuring shale CO under different diffusion pressures after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the shale adsorption capacity.
The change of the adsorption amount before and after the water rock action in this example is shown in fig. 3, and the abscissa of fig. 3 represents the equilibrium pressure of the sampling area 11 at each sampling analysis. As can be seen from fig. 3, after the water-rock reaction, the amount of CO2 adsorbed increases at a low pressure value, and the pressure value required to reach saturation adsorption decreases, but the total amount of adsorbed decreases.
The change of the T2 curve before and after the water-rock action of the embodiment is shown in FIG. 4. As can be seen from fig. 4, before and after the water-rock action, the curve area is reduced after CO2 is injected, which indicates that before and after the water-rock action, CO2 can well displace natural gas, but the amount of saturated natural gas is reduced after the water-rock action, which indicates that the pore structure is changed, the pore size is partially increased, and the reduction of the specific surface area leads to the reduction of the total adsorption amount.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A porous medium gas adsorption capacity evaluation system considering water and rock action is characterized by comprising a rock sample holder (1), wherein the upstream of the rock sample holder (1) is respectively connected with a reference kettle (2), an intermediate container group (3) and a vacuumizing assembly (4) through a six-way valve (A),
a first pressure gauge (5) is arranged between the rock sample holder (1) and the six-way valve (A), a second pressure gauge (6) and a first sampling point (7) are sequentially arranged at the downstream of the rock sample holder (1),
the upper reaches of reference cauldron (3) are equipped with air supply mechanism (8) and gas booster pump (B) along the air current direction in proper order, reference cauldron (3) with be equipped with two circuits between six-way valve (A), the first circuit is in the entry of reference cauldron (3) is equipped with two three-way valves (9), two three-way valves (9) with gas booster pump (B) pass through the pipe connection, the second circuit is in the entry of reference cauldron (3) is equipped with first valve (10), pipeline between first valve (10) and six-way valve (A) constitutes middle sample area (11), one of them valve of six-way valve (A) is second sampling point valve (12), the reference cauldron is connected with third manometer (13),
the middle container group (3) comprises a carbonic acid container (31), a stratum water container (32), a natural gas container (33) and a carbon dioxide container (34), and a plunger pump (35) is arranged on the upstream of the middle container group (3).
2. A system according to claim 1, characterized in that a first flow control device (14) is arranged between the rock sample holder (1) and the first pressure gauge (5), and a second flow control device (15) is arranged between the second pressure gauge (6) and the first sampling point (7);
preferably, a gas-liquid separation device (16) is arranged between the second pressure gauge (6) and the second flow control device (15);
preferably, a third valve (17) and a fourth valve (18) are arranged between the second flow control device (15) and the first sampling point (7), the third valve (17) being open for exhaust gas and the fourth valve (18) being open for sampling.
3. System according to claim 1 or 2, characterized in that a fourth pressure gauge (19) is provided between the intermediate group of containers (3) and the six-way valve (a);
preferably, the carbonic acid container (31), the stratum water container (32), the natural gas container (33) and the carbon dioxide container (34) are connected in parallel, and the outlet and the inlet of the carbonic acid container (31), the stratum water container (32), the natural gas container (33) and the carbon dioxide container (34) are provided with switch valves;
preferably, the reference tank (2) and the intermediate container group (3) are both placed in a thermostatic control device (C).
4. The system according to claim 1, characterized in that the rock sample holder (1) is placed in a low-field nuclear magnetic resonance instrument (101), the low-field nuclear magnetic resonance instrument (101) being connected to a first industrial control computer (20);
preferably, the first pressure gauge (5) and the second pressure gauge (6) are both connected with the first industrial control computer (20).
5. The system according to claim 1, wherein the gas source mechanism (8) comprises a natural gas supply unit (81), a carbon dioxide supply unit (82) and a helium supply unit (83), and the tops of the natural gas supply unit (81), the carbon dioxide supply unit (82) and the helium supply unit (83) are provided with switch valves;
preferably, the third pressure gauge (13) is connected with a second industrial control computer (21).
6. A method for evaluating the gas adsorption capacity of a porous medium in consideration of the effect of water and rock, which is carried out in the system according to any one of claims 1 to 5,
the method comprises the following steps:
s1, placing a porous medium in the rock sample holder (1), vacuumizing the system, and measuring the volume of a free space in the rock sample holder (1);
s2, vacuumizing the system, injecting natural gas into the porous medium through the plunger pump (35) for saturation adsorption, and then injecting CO at constant pressure and constant current 2 Collecting gas at the outlet end of the rock sample holder (1) at different moments for component analysis, and recording gas pressure, instantaneous flow and accumulated flow at two ends of the rock sample holder (1) in real time;
s3, adsorbing CO by porous medium in a saturated way 2 Post stop CO injection 2 Calculating the porous Medium CO according to formula (I) 2 The adsorption capacity of the adsorbent is improved,
wherein, P in 、P i And P p CO at the inlet end of the rock sample holder (1) 2 The unit of the injection pressure, the instantaneous pressure at the outlet end of the rock sample holder (1) and the free space pressure in the porous medium during the collection and sampling at different moments is MPa; z in 、Z i 、Z p Respectively corresponding to pressure P in 、P i And P p The gas compression factor of (a); v in And V i CO at the inlet end of the rock sample holder (1) respectively 2 The unit of the injection amount and the collection amount at the outlet end in the process of collecting and sampling at different moments is mL; v p Is the free space volume of the rock sample holder (1) with the unit of mL; x is the number of i Collecting CO in gas at the outlet end of the rock sample holder (1) for sampling at different moments 2 The volume ratio is expressed in%; i is the sampling frequency; n is Adsorption The unit of (A) is mol;
s4, carrying out vacuum pumping to desorb the porous medium, injecting formation water into the porous medium through the plunger pump (35) until the porous medium is saturated, and then injecting carbonic acid into the porous medium through the plunger pump (35) to carry out water-rock reaction;
s5, repeating the step S1 to the step S3, and measuring the porous medium CO after the water rock reaction 2 And (4) the adsorption capacity, namely evaluating the influence of the water rock reaction on the adsorption capacity of the porous medium.
7. A method for evaluating the gas adsorption capacity of a porous medium in consideration of the effect of water and rock, which is carried out in the system according to any one of claims 1 to 5,
the method comprises the following steps:
1) Placing a porous medium in the rock sample holder (1), then evacuating the system and determining the volume of free space in the rock sample holder (1);
2) The system is vacuumized, and natural gas and CO are introduced into the reference kettle (2) 2 Preparation of Natural gas and CO 2 Pressure ratio of K 1 The reference kettle (2) and the rock sample holder (1) are communicated, and the mixed gas is introduced into a porous medium to be adsorbed stably, so that the pretreatment of the porous medium is completed;
3) The system is vacuumized, and natural gas and CO are introduced into the reference kettle (2) 2 Preparation of Natural gas and CO 2 Pressure ratio of K 2 Mixed gas of (2), K 2 And K 1 The same or different;
4) Communicating the reference kettle (2) with the rock sample holder (1) to diffuse the mixed gas into the porous medium, closing the first valve (10) after the intermediate sampling area (11) has diffusion pressure until the porous medium is stably adsorbed, then closing the six-way valve (A), opening the second sampling point valve (12), sampling from the intermediate sampling area (11) to analyze gas components, and measuring the equilibrium pressure of the sampling area (11) at the moment through the first pressure gauge (5);
5) Repeating the step 4), wherein the intermediate sampling region (11) has different diffusion pressures each time the operation is repeated, and calculating the porous medium CO at different diffusion pressures according to the formula (II) 2 The adsorption capacity of the adsorbent is improved,
wherein M is i And N i The equilibrium pressure of the reference kettle (2) and the equilibrium pressure of the sampling area (11) at each sampling are respectively expressed in MPa; a is i And b i Respectively is CO in the gas of the reference kettle (2) during each sampling 2 The volume ratio is expressed in%; s L And S p Respectively the volume of the middle sampling area (11) and the free space volume of the rock sample holder (1), and the unit is mL; t is a unit of i To correspond to the pressure N i The gas compression factor of (a); i is the sampling frequency; m is Adsorption The unit of (A) is mol;
6) Vacuumizing to desorb the porous medium, injecting formation water into the porous medium to saturation through the plunger pump (35), and then injecting carbonic acid into the porous medium through the plunger pump (35) to perform water-rock reaction;
7) Repeating the steps 1) to 6), and measuring the porous medium CO under different diffusion pressures after the water rock reaction 2 And (4) adsorption capacity, namely evaluating the influence of water rock reaction on the adsorption capacity of the porous medium.
8. The method according to claim 6 or 7, further comprising measuring T of a porous medium by the low-field NMR spectrometer (101) 2 And (4) spectrum analysis is carried out on the peak area change of the spectrogram and the gas adsorption-desorption behaviors in the pores of different porous media.
9. The method of claim 6 or 7, wherein the natural gas comprises one or more of methane, ethane, propane, butane, and hydrogen.
10. The method of claim 6 or 7, wherein the porous medium is shale, coal, activated carbon, sandstone or carbonate.
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