CN113252421B - Device and method for measuring trace carbon isotopes and heavy components in natural gas - Google Patents

Device and method for measuring trace carbon isotopes and heavy components in natural gas Download PDF

Info

Publication number
CN113252421B
CN113252421B CN202110669779.6A CN202110669779A CN113252421B CN 113252421 B CN113252421 B CN 113252421B CN 202110669779 A CN202110669779 A CN 202110669779A CN 113252421 B CN113252421 B CN 113252421B
Authority
CN
China
Prior art keywords
gas
intermediate container
natural gas
component
heavy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110669779.6A
Other languages
Chinese (zh)
Other versions
CN113252421A (en
Inventor
刘建仪
李杰柯
文果
余凡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest Petroleum University
Original Assignee
Southwest Petroleum University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest Petroleum University filed Critical Southwest Petroleum University
Priority to CN202110669779.6A priority Critical patent/CN113252421B/en
Publication of CN113252421A publication Critical patent/CN113252421A/en
Application granted granted Critical
Publication of CN113252421B publication Critical patent/CN113252421B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/42—Low-temperature sample treatment, e.g. cryofixation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference
    • G01N7/16—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference by heating the material

Abstract

The invention discloses a device and a method for measuring trace carbon isotopes and heavy components in natural gas, and solves the technical problems that the measurement cannot be carried out due to low carbon isotope content, the detection result of the heavy components is inaccurate, and the detection process is complex when the natural gas components are measured in the prior art. The device comprises an air bottle (1), an intermediate container (4), a buffer device (14), a flow meter (5) for measuring the gas flow and a gas chromatograph which are sequentially connected through pipelines; wherein, the outer side of the intermediate container (4) is provided with a temperature control device (3) for regulating and controlling the temperature of the intermediate container (4); the intermediate container (4) is connected with a pressure control device for maintaining the internal pressure constant; and the intermediate container (4) and the buffer device (14) are both connected with a vacuum pump (8). The invention avoids the evaporation loss of the condensed liquid in the transfer process, simplifies the operation and can more accurately determine trace carbon isotopes and heavy components in the natural gas.

Description

Device and method for measuring trace carbon isotopes and heavy components in natural gas
Technical Field
The invention belongs to the technical field of natural gas physical property testing, and particularly relates to a device and a method for measuring trace carbon isotopes and heavy components in natural gas.
Background
Natural gas is an important energy source and occupies an important strategic position in the economic development of China. The natural gas is used as an energy source, so that the consumption of coal and petroleum can be reduced, the discharge amount of sulfur dioxide, carbon dioxide, dust and nitrogen oxide is reduced, acid rain can be effectively prevented from forming, the greenhouse effect is slowed down, and the environmental quality is fundamentally improved. Natural gas is a mixed gas existing in underground rock reservoirs, and is mainly hydrocarbons such as methane and ethane. The composition of alkane isotopes in the natural gas can be mastered, so that the determination of the content and the burial depth of the alkane in the natural gas, the cause and the maturity of the natural gas and the like can be facilitated; because the composition of natural gas is relatively complex, the nature of the natural gas can be influenced by the types and the contents of the components, and the economic and safety problems in the development, transportation and processing processes of the natural gas are considered, the accurate metering of the natural gas gradually becomes the key point of attention, and the analysis data of the composition of the natural gas is the basic data in the metering. Therefore, it is necessary to accurately measure trace carbon isotopes and heavy components in the natural gas, understand important physical parameters of the natural gas through composition analysis, and further clarify the properties of the natural gas.
The existing method for measuring carbon isotopes is to directly inject natural gas into an isotope mass spectrometer for analysis, but cannot measure the content of some components in the natural gas when the content of some components in the natural gas is low.
The existing method for measuring the heavy components of the natural gas is to condense and separate the natural gas, gas chromatograph is used for testing gas-liquid phase components in the natural gas, and then the total components of the natural gas are calculated according to the substance balance principle, but the condensate is easy to volatilize, so that the condensate is difficult to ensure that the condensate cannot be lost in the transferring and injecting chromatographic processes, the measuring result is inaccurate, and the whole process of transferring and injecting the condensate is very complicated.
Disclosure of Invention
The invention aims to provide a device for measuring trace carbon isotopes and heavy components in natural gas, and aims to solve the technical problems that in the prior art, when the natural gas components are measured, the carbon isotopes cannot be measured due to low content, the detection result of the heavy components is inaccurate, and the detection process is complex.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a device for measuring trace carbon isotopes and heavy components in natural gas, which comprises a gas cylinder, an intermediate container, a buffer device, a flowmeter for measuring gas flow and a gas component detection device which are sequentially connected through a pipeline; wherein the content of the first and second substances,
a temperature control device for regulating and controlling the temperature of the intermediate container is arranged on the outer side of the intermediate container;
the intermediate container is connected with a pressure control device for maintaining the internal pressure constant;
and the intermediate container and the buffer device are both connected with a vacuum pump.
Further, the pressure control device comprises a pressure control pipeline, a displacement pump and a liquid inlet valve, wherein the displacement pump is connected to one end of the pressure control pipeline, and the other end of the pressure control pipeline is connected with the intermediate container; the liquid inlet valve is connected to the pressure control pipeline.
Further, the temperature control range of the temperature control device is-100 ℃ to 240 ℃.
Further, the temperature control device is a high-low temperature alternating test chamber or a cold-hot bath.
Further, the gas cylinder is communicated with the middle container through a gas inlet pipe, and a pressure reducing valve and a gas inlet valve are sequentially arranged on the gas inlet pipe along the gas inlet direction.
Further, the flowmeter is a turbine flowmeter or a volume flowmeter.
Further, the gas component detection device is a stable isotope ratio mass spectrometer and/or a gas chromatograph.
Furthermore, pipelines between the intermediate container and the gas component detection device are all heat-insulating pipelines.
The invention provides a method for measuring trace carbon isotopes and heavy components in natural gas, which applies the device for measuring trace carbon isotopes and heavy components in natural gas and comprises the following steps:
s1: vacuumizing, wherein a vacuum pump is used for vacuumizing the intermediate container and the buffer device;
s2: sample introduction and condensation are carried out on a sample, a temperature control device is started, and the set temperature is-89.5 to-95 ℃; after the temperature is stable, the natural gas sample in the gas cylinder enters an intermediate container through a pipeline, meanwhile, a pressure control device is utilized to maintain the pressure of the intermediate container constant to be normal pressure, so that light components and heavy components in the natural gas sample are separated from gas and liquid, and the natural gas sample is stopped being injected into the intermediate container when condensate in the intermediate container reaches 8-12 ml;
s3: analyzing the light component gas component, namely, feeding a pump at constant pressure by using a displacement pump, discharging the gas in the intermediate container, feeding the gas into a gas component detection device for detection, and recording the reading of a flowmeter and the result of the gas component detection device (6);
s4: analyzing the components of heavy component gas, setting the temperature of a temperature control device to be 198-210 ℃, after the temperature is stable, feeding the gas into a pump by using a displacement pump at constant pressure, discharging the gas in an intermediate container, detecting the gas in a gas component detection device, and recording the reading of a flowmeter and the result of the gas component detection device;
s5: and (4) calculating the total composition of the sample gas, and calculating the total composition of the natural gas sample according to the substance balance principle by using the results obtained in the step S3 and the step S4.
Further, in step S5, the step of calculating the total composition of the natural gas sample includes:
(ii) calculating the densities of the light component gas and the heavy component gas by the following equation (1)
Figure 546139DEST_PATH_IMAGE001
In formula (1):
Figure 587913DEST_PATH_IMAGE002
-the pressure in the laboratory and the pressure in the laboratory,
Figure 616918DEST_PATH_IMAGE003
；
Figure 71514DEST_PATH_IMAGE004
-the temperature of the laboratory, and,
Figure 10520DEST_PATH_IMAGE005
；
Figure 895300DEST_PATH_IMAGE006
-gas deviation factor, dimensionless;
Figure 224650DEST_PATH_IMAGE007
-molar gas constant, taking
Figure 485867DEST_PATH_IMAGE008
；
Figure 154746DEST_PATH_IMAGE009
Molecular weights of light and heavy gases, respectively
Figure 210426DEST_PATH_IMAGE010
And
Figure 92319DEST_PATH_IMAGE011
；
② calculating the mass of the light component gas and the heavy component gas by the following formula (2)
Figure 891648DEST_PATH_IMAGE012
In formula (2):
Figure 477350DEST_PATH_IMAGE013
the volumes of the light component gas and the heavy component gas recorded by the flow meter in the steps S3 and S4 are respectively recorded as
Figure 969511DEST_PATH_IMAGE014
And
Figure 273454DEST_PATH_IMAGE015
，
Figure 610894DEST_PATH_IMAGE016
；
Figure 316682DEST_PATH_IMAGE017
the densities of the light component gas and the heavy component gas calculated in the step (i) are respectively recorded as
Figure 651848DEST_PATH_IMAGE018
And
Figure 443087DEST_PATH_IMAGE019
，
Figure 581289DEST_PATH_IMAGE020
；
Figure 141583DEST_PATH_IMAGE021
test system dead volume (i.e. the sum of buffer volume and line volume),
Figure 913230DEST_PATH_IMAGE022
；
(iii) calculating the molecular weights of the light component gas and the heavy component gas according to the following formula (3)
Figure 988502DEST_PATH_IMAGE023
In formula (3):
Figure 933324DEST_PATH_IMAGE024
light component gas and heavy component gas detected by gas component detection device (gas chromatograph)
Figure 348125DEST_PATH_IMAGE025
Are respectively recorded as
Figure 290673DEST_PATH_IMAGE026
And
Figure 853242DEST_PATH_IMAGE027
，%；
Figure 339105DEST_PATH_IMAGE028
molecular weights of light and heavy gases, respectively
Figure 873992DEST_PATH_IMAGE010
And
Figure 49758DEST_PATH_IMAGE011
；
calculating the mole number of the light component gas and the heavy component gas according to the following formula (4)
Figure 37306DEST_PATH_IMAGE029
In formula (4):
Figure 323931DEST_PATH_IMAGE030
the number of moles of light component gas and heavy component gas, respectively
Figure 447745DEST_PATH_IMAGE031
And
Figure 794412DEST_PATH_IMAGE032
，
Figure 269256DEST_PATH_IMAGE033
；
Figure 380080DEST_PATH_IMAGE034
the mass of the light component gas and the mass of the heavy component gas calculated in the step II are respectively recorded as
Figure 686296DEST_PATH_IMAGE035
And
Figure 875969DEST_PATH_IMAGE036
，
Figure 900425DEST_PATH_IMAGE037
；
Figure 466536DEST_PATH_IMAGE038
calculating the molecular weights of the light component gas and the heavy component gas in the step III, and respectively recording the molecular weights as
Figure 830521DEST_PATH_IMAGE039
And
Figure 253412DEST_PATH_IMAGE040
；
fifthly, calculating the total composition of the natural gas sample according to the following formula (5)
Figure 768095DEST_PATH_IMAGE041
In formula (5):
Figure 137896DEST_PATH_IMAGE042
in natural gas samples
Figure 90809DEST_PATH_IMAGE025
Mole fraction of components,%;
Figure 950180DEST_PATH_IMAGE043
-the moles of light component gases calculated in step (iv);
Figure 683650DEST_PATH_IMAGE044
the calculated mole number of the heavy component gas in the step (IV);
Figure 857142DEST_PATH_IMAGE045
light component gas detected by gas component detection apparatus (gas chromatograph)
Figure 930141DEST_PATH_IMAGE025
The mole fraction of (c);
Figure 22730DEST_PATH_IMAGE027
heavy component gas detected by a gas component detection device (gas chromatograph)
Figure 240567DEST_PATH_IMAGE025
Mole fraction of (c).
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
according to the device for measuring the trace carbon isotopes and the heavy components in the natural gas, when the trace carbon isotopes and the heavy components in the natural gas are measured, after the natural gas is injected into the middle container, the temperature of the natural gas is controlled by the temperature control device, the natural gas is condensed and separated by adopting a low-temperature condensation method, condensed gas and liquid are respectively obtained, the obtained gas is called as a light component, the light component gas is detected by the gas component detection device, and the volume of the gas and the detection result of the gas component detection device are recorded; heating and evaporating the condensate in the intermediate container into gas by using a temperature control device for controlling the temperature, wherein the obtained gas is called heavy component, detecting the heavy component gas by using the same gas component detection device, and recording the volume of the gas and the detection result of the gas component detection device; and then, calculating the total components of the natural gas according to a substance balance principle, wherein the measuring method provided by the invention does not directly test the components of the condensate, but evaporates the condensate into gas to test the components of the gas, so that the evaporation loss of the condensed liquid in the transfer process is avoided, the operation is simplified, and the trace carbon isotopes and heavy components in the natural gas can be more accurately measured.
Drawings
FIG. 1 is a schematic structural view of embodiment 1 of the present invention;
FIG. 2 is a spectrum diagram of the result of the natural gas sample A detected by the stable isotope ratio mass spectrometer in the comparative example with the ratio as the ordinate;
FIG. 3 is a spectrum diagram of the result of the detection of the stable isotope ratio mass spectrometer with the ion intensity as the ordinate of the natural gas sample A in the comparative example;
FIG. 4 is a spectrum diagram of the result of the natural gas sample B detected by the stable isotope ratio mass spectrometer in the comparative example with the ratio as the ordinate;
FIG. 5 is a spectrum diagram of the result of the detection of the stable isotope ratio mass spectrometer with the ion intensity as the ordinate of the natural gas sample B in the comparative example;
FIG. 6 is a spectrum diagram of the result of the natural gas sample C detected by the stable isotope ratio mass spectrometer in the comparative example with the ratio as the ordinate;
FIG. 7 is a spectrum diagram of the result of the detection of the stable isotope ratio mass spectrometer with the ion intensity as the ordinate of the natural gas sample C in the comparative example;
FIG. 8 is a spectrum of the heavy component of the natural gas sample A detected by the stable isotope ratio mass spectrometer in example 2, with the ratio as the ordinate;
FIG. 9 is a spectrum of the heavy component of the natural gas sample A detected by the stable isotope ratio mass spectrometer in example 2, with the ion intensity as the ordinate;
FIG. 10 is a spectrum diagram of the heavy component of the natural gas sample B detected by the stable isotope ratio mass spectrometer in example 2, wherein the ratio is taken as the ordinate;
FIG. 11 is a spectrum of heavy component of natural gas sample B detected by the stable isotope ratio mass spectrometer in example 2 with ion intensity as ordinate;
FIG. 12 is a spectrum diagram of the heavy component of the natural gas sample C detected by the stable isotope ratio mass spectrometer in example 2, with the ratio as the ordinate;
fig. 13 is a spectrum of the heavy component of the natural gas sample C detected by the stable isotope ratio mass spectrometer in example 2, with the ion intensity as the ordinate.
In the figure: 1. a gas cylinder; 2. a displacement pump; 3. a temperature control device; 4. an intermediate container; 5. a flow meter; 6. a gas component detection device; 7. an air outlet valve; 8. a vacuum pump; 9. a pressure reducing valve; 10. an intake valve; 11. a liquid inlet valve; 12. a three-way pipe; 13. a vacuum valve; 14. a buffer device.
Detailed Description
Example 1:
as shown in fig. 1:
the invention provides a device for measuring trace carbon isotopes and heavy components in natural gas, which comprises a gas cylinder 1, an intermediate container 4, a buffer device 14, a flow meter 5 for measuring gas flow and a gas component detection device 6 which are sequentially connected through pipelines; wherein the content of the first and second substances,
the outer side of the intermediate container 4 is provided with a temperature control device 3 for regulating and controlling the temperature of the intermediate container 4;
the intermediate container 4 is connected with a pressure control device for maintaining the internal pressure constant;
the intermediate container 4 and the buffer device 14 are both connected with a vacuum pump 8.
According to the device for measuring the trace carbon isotopes and the heavy components in the natural gas, when the trace carbon isotopes and the heavy components in the natural gas are measured, after the natural gas is injected into the intermediate container 4, the temperature of the natural gas is controlled by the temperature control device 3, the natural gas is condensed and separated by adopting a low-temperature condensation method, condensed gas and condensed liquid are obtained respectively, the obtained gas is called as the light components, the light component gas is detected by the gas component detection device 6, and the gas volume and the detection results of the gas component detection device 6 are recorded; heating and evaporating the condensate in the intermediate container 4 into gas by using the temperature control device 3 to control the temperature, wherein the obtained gas is called heavy component, detecting the heavy component gas by using the same gas component detection device 6, and recording the gas volume and the detection result of the gas component detection device 6; and then, calculating the total components of the natural gas according to a substance balance principle, wherein the measuring method provided by the invention does not directly test the components of the condensate, but evaporates the condensate into gas to test the components of the gas, so that the evaporation loss of the condensed liquid in the transfer process is avoided, the operation is simplified, and the trace carbon isotopes and heavy components in the natural gas can be more accurately measured.
As an optional implementation manner, the pressure control device comprises a pressure control pipeline, a displacement pump 2 and a liquid inlet valve 11, wherein the displacement pump 2 is connected to one end of the pressure control pipeline, and the other end of the pressure control pipeline is connected with the intermediate container 4; the liquid inlet valve 11 is connected to a pressure control pipeline.
As an optional embodiment, the temperature control range of the temperature control device 3 is-100 ℃ to 240 ℃.
As an alternative embodiment, the temperature control device 3 is a high-low temperature alternating test chamber or a cold-hot bath.
As an alternative embodiment, the gas cylinder 1 and the intermediate container 4 are communicated through an air inlet pipe, and a pressure reducing valve 9 and an air inlet valve 10 are sequentially arranged on the air inlet pipe along the air inlet direction.
As an alternative embodiment, the flow meter 5 is a turbine flow meter or a volumetric flow meter.
As an alternative embodiment, the gas component detection device 6 is a stable isotope ratio mass spectrometer and/or a gas chromatograph.
In the present embodiment, the gas component detection apparatus 6 is a stable isotope ratio mass spectrometer and a gas chromatograph; detecting a stable isotope ratio mass spectrometer and a gas chromatograph respectively during detection; when the stable isotope ratio mass spectrometer needs to be detected, the stable isotope ratio mass spectrometer is injected for detection; when the detection of the gas chromatograph is needed, the gas chromatograph is injected for detection.
As an alternative embodiment, the pipelines between the intermediate container 4 and the gas component detection device 6 are both heat-insulating pipelines; the purpose of providing a heat-insulated pipe is to minimize the change in gas due to a change in temperature before the gas discharged from the intermediate container 4 enters the gas component detection apparatus 6.
In the embodiment, a three-way pipe 12 is connected to the heat insulation pipeline between the intermediate container 4 and the buffer device 14, and the other end of the three-way pipe 12 is connected to the vacuum pump 8 through an air extraction pipeline; a vacuum valve 13 is arranged on the air exhaust pipeline; and an air outlet valve 7 is connected on the heat insulation pipeline between the buffer device 14 and the flowmeter 5.
Example 2:
the device for measuring the trace carbon isotopes and the heavy components in the natural gas in the embodiment 1 is used for measuring the trace carbon isotopes and the heavy components in the natural gas sample A, and comprises the following steps:
s1: vacuumizing, opening a vacuum valve 13, and vacuumizing the intermediate container 4 and the buffer device 14 by using a vacuum pump 8; after vacuumizing, closing the vacuum valve 13 and taking down the vacuum pump 8;
s2: sample introduction and condensation are carried out, a temperature control device 3 is started, and the set temperature is-90 ℃; after the temperature is stable, opening a pressure reducing valve 9, an air inlet valve 10 and a liquid inlet valve 11, enabling a natural gas sample A in the gas cylinder 1 to enter the intermediate container 4 through the air inlet pipe, and simultaneously maintaining the pressure of the intermediate container 4 to be constant by using the displacement pump 2 to separate the light component and the heavy component in the natural gas sample A into gas and liquid;
s3: analyzing the light component gas component, opening the gas outlet valve 7, using the displacement pump 2 to pressurize the pump, discharging the gas in the middle container 4, detecting the gas in the gas component detecting device 6 (stable isotope ratio mass spectrometer and gas chromatograph), recording the reading of the flow meter 5
Figure 14488DEST_PATH_IMAGE046
And the detection result of the gas component detection means 6; the detection of the stable isotope ratio mass spectrometer and the gas chromatograph is carried out separately;
s4: analyzing the gas component of heavy component, setting the temperature of a temperature control device 3 at 200 ℃, after the temperature is stable, using a displacement pump 2 to perform constant pressure pump feeding, discharging the gas in an intermediate container 4, introducing the gas into a gas component detection device 6 (a stable isotope ratio mass spectrometer and a gas chromatograph) for detection, and recording the reading of a flow meter 5
Figure 879675DEST_PATH_IMAGE047
And the detection result of the gas component detection means 6; the detection of the stable isotope ratio mass spectrometer and the gas chromatograph is carried out separately;
s5: and (3) calculating the total composition of the sample gas, namely calculating the total composition of the natural gas sample A according to the substance balance principle by using the results obtained in the steps S3 and S4, wherein the specific calculation steps are as follows:
(ii) calculating the densities of the light component gas and the heavy component gas by the following equation (1)
Figure 80850DEST_PATH_IMAGE048
In formula (1):
Figure 726595DEST_PATH_IMAGE049
-the pressure in the laboratory and the pressure in the laboratory,
Figure 100944DEST_PATH_IMAGE050
；
Figure 86218DEST_PATH_IMAGE051
-the temperature of the laboratory, and,
Figure 458293DEST_PATH_IMAGE052
；
Figure 594264DEST_PATH_IMAGE053
-gas deviation factor, dimensionless;
Figure 772304DEST_PATH_IMAGE054
-molar gas constant, taking
Figure 612084DEST_PATH_IMAGE055
；
Figure 217378DEST_PATH_IMAGE056
Molecular weights of light and heavy gases, respectively
Figure 509819DEST_PATH_IMAGE057
And
Figure 429234DEST_PATH_IMAGE058
；
② calculating the mass of the light component gas and the heavy component gas by the following formula (2)
Figure 185837DEST_PATH_IMAGE059
In formula (2):
Figure 959102DEST_PATH_IMAGE060
the volumes of the light component gas and the heavy component gas recorded by the flow meter 5 in the steps S3 and S4 are respectively recorded as
Figure 4419DEST_PATH_IMAGE046
And
Figure 461945DEST_PATH_IMAGE047
，
Figure 73055DEST_PATH_IMAGE061
；
Figure 223413DEST_PATH_IMAGE062
the densities of the light component gas and the heavy component gas calculated in the step (i) are respectively recorded as
Figure 552764DEST_PATH_IMAGE063
And
Figure 813981DEST_PATH_IMAGE064
，
Figure 279597DEST_PATH_IMAGE065
；
Figure 600857DEST_PATH_IMAGE066
-the dead volume of the test system is,
Figure 420433DEST_PATH_IMAGE061
；
(iii) calculating the molecular weights of the light component gas and the heavy component gas according to the following formula (3)
Figure 219762DEST_PATH_IMAGE067
In formula (3):
Figure 805464DEST_PATH_IMAGE068
light component gas, heavy component gas
Figure 297625DEST_PATH_IMAGE069
Are respectively recorded as
Figure 335988DEST_PATH_IMAGE070
And
Figure 939008DEST_PATH_IMAGE071
，%；
Figure 644796DEST_PATH_IMAGE072
molecular weights of light and heavy gases, respectively
Figure 42279DEST_PATH_IMAGE073
And
Figure 830588DEST_PATH_IMAGE058
；
calculating the mole number of the light component gas and the heavy component gas according to the following formula (4)
Figure 971719DEST_PATH_IMAGE074
In formula (4):
Figure 532013DEST_PATH_IMAGE075
the number of moles of light component gas and heavy component gas, respectively
Figure 38081DEST_PATH_IMAGE076
And
Figure 378933DEST_PATH_IMAGE077
，
Figure 323755DEST_PATH_IMAGE078
；
Figure 738556DEST_PATH_IMAGE079
the mass of the light component gas and the mass of the heavy component gas calculated in the step II are respectively recorded as
Figure 743421DEST_PATH_IMAGE080
And
Figure 246602DEST_PATH_IMAGE081
，
Figure 729536DEST_PATH_IMAGE082
；
Figure 264422DEST_PATH_IMAGE083
calculating the molecular weights of the light component gas and the heavy component gas in the step III, and respectively recording the molecular weights as
Figure 112293DEST_PATH_IMAGE084
And
Figure 162157DEST_PATH_IMAGE085
；
fifthly, calculating the total composition of the natural gas sample A according to the following formula (5)
Figure 448782DEST_PATH_IMAGE086
In formula (5):
Figure 838175DEST_PATH_IMAGE087
in-Natural gas sample A
Figure 184843DEST_PATH_IMAGE069
Mole fraction of components,%;
Figure 492694DEST_PATH_IMAGE076
-the moles of light component gases calculated in step (iv);
Figure 317431DEST_PATH_IMAGE088
the calculated mole number of the heavy component gas in the step (IV);
Figure 499013DEST_PATH_IMAGE089
light component gas detected by gas component detection device 6 (gas chromatograph)
Figure 78899DEST_PATH_IMAGE069
The mole fraction of (c);
Figure 978722DEST_PATH_IMAGE071
heavy component gas detected by gas component detection device 6 (gas chromatograph)
Figure 669466DEST_PATH_IMAGE069
Mole fraction of (c).
The results of measuring trace carbon isotopes and heavy components of natural gas sample a are shown in table 1 below, fig. 8, and fig. 9.
The trace carbon isotopes and the heavy components were measured for the natural gas sample B and the natural gas sample C, respectively, in the same manner as in example 2, and the results are shown in table 1, fig. 10, fig. 11, fig. 12, and fig. 13 below.
Comparative example:
1. the results of analyzing the natural gas sample a, the natural gas sample B, and the natural gas sample C by injecting the natural gas sample a, the natural gas sample B, and the natural gas sample C directly into the same stable isotope ratio mass spectrometer used in example 2 are shown in table 1 and fig. 2 to 7.
Table 1 comparison of trace carbon isotope measurement results of example 2 and comparative example
Figure 705556DEST_PATH_IMAGE091
As can be seen from table 1, the results of the natural gas carbon isotope test of the measurement methods of the examples and comparative examples are comparatively exemplified. The direct gas sample injection and gas sample condensation separation liquid evaporation gas injection stable isotope ratio mass spectrometer test results are shown in table 1, and the comparison tests show the isotopes of 3 gas samples: for the natural gas sample A and the natural gas sample B, only carbon isotopes in methane can be measured by adopting a direct sample introduction method in a comparative example, and the carbon isotopes in methane and ethane can be measured by adopting the method in the invention; for the natural gas sample C, only carbon isotopes in methane and ethane can be measured by the direct injection method in the comparative example, and carbon isotopes in methane, ethane and propane can be measured by the method in the invention. Therefore, the direct sampling method can not detect the isotopes of the trace components, and the method can be used for measuring the isotopes of the trace components.

Claims (10)

1. A device for measuring trace carbon isotopes and heavy components in natural gas is characterized by comprising a gas cylinder (1), an intermediate container (4), a buffer device (14), a flow meter (5) for measuring gas flow and a gas component detection device (6) which are sequentially connected through a pipeline; wherein the content of the first and second substances,
a temperature control device (3) for regulating and controlling the temperature of the intermediate container (4) is arranged on the outer side of the intermediate container (4);
the intermediate container (4) is connected with a pressure control device for maintaining the internal pressure constant;
the intermediate container (4) and the buffer device (14) are both connected with a vacuum pump (8);
the device for measuring the trace carbon isotopes and the heavy components in the natural gas is used for measuring the trace carbon isotopes and the heavy components in the natural gas, and comprises the following steps:
s1: vacuumizing, wherein a vacuum pump (8) is used for vacuumizing the intermediate container (4) and the buffer device (14);
s2: sample introduction and condensation are carried out, a temperature control device (3) is started, and the set temperature is-89.5 to-95 ℃; after the temperature is stable, the natural gas sample in the gas cylinder (1) enters the intermediate container (4) through a pipeline, meanwhile, the pressure of the intermediate container (4) is kept constant at normal pressure by using a pressure control device, so that the light component and the heavy component in the natural gas sample are subjected to gas-liquid separation, and the natural gas sample is stopped being injected into the intermediate container (4) when condensate in the intermediate container (4) reaches 8-12 ml;
s3: analyzing the light component gas component, namely, using a displacement pump (2) to feed the gas into the pump at constant pressure, discharging the gas in the intermediate container (4), feeding the gas into a gas component detection device (6) for detection, and recording the reading of the flowmeter (5) and the result of the gas component detection device (6);
s4: analyzing the components of heavy component gas, setting the temperature of a temperature control device (3) to be 198-210 ℃, after the temperature is stable, feeding the gas into a pump by using a displacement pump (2) at a constant pressure, discharging the gas in an intermediate container (4), detecting the gas in a gas component detection device (6), and recording the reading of a flowmeter (5) and the result of the gas component detection device (6);
s5: and (4) calculating the total composition of the sample gas by using the results obtained in the step S3 and the step S4.
2. The device for measuring the trace carbon isotopes and the heavy components in the natural gas as claimed in claim 1, wherein the pressure control device comprises a pressure control pipeline, a displacement pump (2) and a liquid inlet valve (11), the displacement pump (2) is connected to one end of the pressure control pipeline, and the other end of the pressure control pipeline is connected with the intermediate container (4); the liquid inlet valve (11) is connected to the pressure control pipeline.
3. The device for measuring the trace carbon isotopes and heavy components in the natural gas as claimed in claim 1, wherein the temperature control range of the temperature control device (3) is-100 ℃ to 240 ℃.
4. The device for measuring the trace carbon isotopes and heavy components in natural gas as claimed in claim 1, wherein the temperature control device (3) is a high-low temperature alternating test chamber or a cold-hot bath.
5. The device for measuring the trace carbon isotopes and heavy components in the natural gas as claimed in claim 1, wherein the gas cylinder (1) is communicated with the intermediate container (4) through a gas inlet pipe, and a pressure reducing valve (9) and a gas inlet valve (10) are sequentially arranged on the gas inlet pipe along the gas inlet direction.
6. The apparatus for measuring trace carbon isotopes and heavy components in natural gas according to claim 1, characterized in that the flowmeter (5) is a turbine flowmeter (5) or a volumetric flowmeter (5).
7. The apparatus for measuring trace carbon isotopes and heavy components in natural gas according to claim 1, wherein the gas component detection apparatus (6) is a stable isotope ratio mass spectrometer and/or a gas chromatograph.
8. The device for measuring trace carbon isotopes and heavy components in natural gas according to any one of claims 1 to 7, wherein the pipelines between the intermediate container (4) and the gas component detection device (6) are insulated pipelines.
9. A method for measuring trace carbon isotopes and heavy components in natural gas, which applies the device for measuring trace carbon isotopes and heavy components in natural gas as claimed in any one of claims 1-8, and is characterized by comprising the following steps:
s1: vacuumizing, wherein a vacuum pump (8) is used for vacuumizing the intermediate container (4) and the buffer device (14);
s2: sample introduction and condensation are carried out, a temperature control device (3) is started, and the set temperature is-89.5 to-95 ℃; after the temperature is stable, the natural gas sample in the gas cylinder (1) enters the intermediate container (4) through a pipeline, meanwhile, the pressure of the intermediate container (4) is kept constant at normal pressure by using a pressure control device, so that the light component and the heavy component in the natural gas sample are subjected to gas-liquid separation, and the natural gas sample is stopped being injected into the intermediate container (4) when condensate in the intermediate container (4) reaches 8-12 ml;
s3: analyzing the light component gas component, namely, using a displacement pump (2) to feed the gas into the pump at constant pressure, discharging the gas in the intermediate container (4), feeding the gas into a gas component detection device (6) for detection, and recording the reading of the flowmeter (5) and the result of the gas component detection device (6);
s4: analyzing the components of heavy component gas, setting the temperature of a temperature control device (3) to be 198-210 ℃, after the temperature is stable, feeding the gas into a pump by using a displacement pump (2) at a constant pressure, discharging the gas in an intermediate container (4), detecting the gas in a gas component detection device (6), and recording the reading of a flowmeter (5) and the result of the gas component detection device (6);
s5: and (4) calculating the total composition of the sample gas by using the results obtained in the step S3 and the step S4.
10. The method for measuring trace carbon isotopes and heavy components in natural gas as claimed in claim 9, wherein in the step S5, the total composition of the natural gas sample is calculated by the following steps:
(ii) calculating the densities of the light component gas and the heavy component gas by the following equation (1)
Figure 355862DEST_PATH_IMAGE001
Figure 86052DEST_PATH_IMAGE002
Figure 865789DEST_PATH_IMAGE003
；
② calculating the mass of the light component gas and the heavy component gas by the following formula (2)
Figure 323315DEST_PATH_IMAGE004
Figure 950736DEST_PATH_IMAGE005
(iii) calculating the molecular weights of the light component gas and the heavy component gas according to the following formula (3)
Figure 773199DEST_PATH_IMAGE006
Figure 102549DEST_PATH_IMAGE007
Calculating the mole number of the light component gas and the heavy component gas according to the following formula (4)
Figure 114499DEST_PATH_IMAGE008
Figure 845694DEST_PATH_IMAGE010
Fifthly, calculating the total composition of the natural gas sample according to the following formula (5)
Figure 839058DEST_PATH_IMAGE011
Figure 406437DEST_PATH_IMAGE012
CN202110669779.6A 2021-06-17 2021-06-17 Device and method for measuring trace carbon isotopes and heavy components in natural gas Active CN113252421B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110669779.6A CN113252421B (en) 2021-06-17 2021-06-17 Device and method for measuring trace carbon isotopes and heavy components in natural gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110669779.6A CN113252421B (en) 2021-06-17 2021-06-17 Device and method for measuring trace carbon isotopes and heavy components in natural gas

Publications (2)

Publication Number Publication Date
CN113252421A CN113252421A (en) 2021-08-13
CN113252421B true CN113252421B (en) 2021-09-21

Family

ID=77188329

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110669779.6A Active CN113252421B (en) 2021-06-17 2021-06-17 Device and method for measuring trace carbon isotopes and heavy components in natural gas

Country Status (1)

Country Link
CN (1) CN113252421B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114062550B (en) * 2021-11-16 2024-02-02 西南石油大学 Natural gas full-component analysis device and method
CN116296671B (en) * 2023-03-10 2023-10-17 中国科学院西北生态环境资源研究院 Buffer piece matched with rare gas isotope analysis device in natural gas and method

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0272861A2 (en) * 1986-12-22 1988-06-29 E.I. Du Pont De Nemours And Company Analyzer for dissolved gas in liquids
CA2116706A1 (en) * 1993-03-04 1995-09-02 David B. Layzell Gas analyzer
US5929442A (en) * 1996-05-01 1999-07-27 Japan Radio Co., Ltd. Apparatus for and method of analyzing carbon isotopes
CA2246564A1 (en) * 1998-09-02 2000-03-03 Tekran Inc. Apparatus for and method of collecting gaseous mercury and differentiating between different mercury components
WO2012125675A1 (en) * 2011-03-14 2012-09-20 Weatherford Switzerland Trading And Development Gmbh Sampling container for collection of fluids
CN105987947A (en) * 2016-07-07 2016-10-05 南京师范大学 Method for determining nitrogen or carbon isotope ratio of N2 or CO2 gas on basis of elemental analyzer-stable isotope mass spectrometer combined device
CN205656091U (en) * 2016-04-08 2016-10-19 中国石油大学(北京) Volumetric method shale isothermal adsorption experimental apparatus
CN106970000A (en) * 2017-04-21 2017-07-21 西南石油大学 Coal/shale extra-high absorption and Seepage Experiment evaluate shale gas adsorption method
CN107421864A (en) * 2016-05-23 2017-12-01 中国石油化工股份有限公司 The assay method of the total specific surface area of micro- mesoporous solid material and micropore specific area
CN110196264A (en) * 2019-06-05 2019-09-03 西南石油大学 A kind of high temperature and pressure condensation air elutriation wax amount test device and method
CN110940613A (en) * 2019-11-05 2020-03-31 苏州冠德能源科技有限公司 Simulation experiment device for carbon isotope analysis in shale gas release process
CN112240186A (en) * 2019-07-18 2021-01-19 中国石油天然气股份有限公司 Natural gas hydrate heat injection-replacement combined simulation mining device and method
CN112255369A (en) * 2020-10-21 2021-01-22 核工业北京地质研究院 Online continuous flow analysis and extraction device and method for methane carbon isotope composition in gas
CN112345667A (en) * 2020-11-06 2021-02-09 中国石油化工股份有限公司 Gaseous hydrocarbon preparation and online carbon isotope analysis device and method
CN112505209A (en) * 2020-11-05 2021-03-16 中国石油集团渤海钻探工程有限公司 Gas chromatography-isotope analysis combined device for logging field measurement of carbon isotope

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7011154B2 (en) * 2000-04-24 2006-03-14 Shell Oil Company In situ recovery from a kerogen and liquid hydrocarbon containing formation
US6932155B2 (en) * 2001-10-24 2005-08-23 Shell Oil Company In situ thermal processing of a hydrocarbon containing formation via backproducing through a heater well
US6807874B2 (en) * 2002-01-21 2004-10-26 Shimadzu Corporation Collecting apparatus of floating dusts in atmosphere
CA2524689C (en) * 2003-04-24 2012-05-22 Shell Canada Limited Thermal processes for subsurface formations
US7028478B2 (en) * 2003-12-16 2006-04-18 Advanced Combustion Energy Systems, Inc. Method and apparatus for the production of energy
CA2649394C (en) * 2006-04-21 2015-11-24 Shell Internationale Research Maatschappij B.V. Adjusting alloy compositions for selected properties in temperature limited heaters
CN103063575B (en) * 2011-10-19 2015-05-20 中国石油化工股份有限公司 Fluid inclusion laser ablation sample pool
KR101461064B1 (en) * 2014-06-09 2014-11-13 한국지질자원연구원 Measurement method of dissolved methane in seawater
CN105259080A (en) * 2015-11-12 2016-01-20 西南石油大学 Shale gas reservoir gas diffusion coefficient experiment test method
CN110402384A (en) * 2017-01-20 2019-11-01 积水医疗株式会社 Carbon isotope analysis device and carbon isotope analysis method

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0272861A2 (en) * 1986-12-22 1988-06-29 E.I. Du Pont De Nemours And Company Analyzer for dissolved gas in liquids
CA2116706A1 (en) * 1993-03-04 1995-09-02 David B. Layzell Gas analyzer
US5929442A (en) * 1996-05-01 1999-07-27 Japan Radio Co., Ltd. Apparatus for and method of analyzing carbon isotopes
CA2246564A1 (en) * 1998-09-02 2000-03-03 Tekran Inc. Apparatus for and method of collecting gaseous mercury and differentiating between different mercury components
WO2012125675A1 (en) * 2011-03-14 2012-09-20 Weatherford Switzerland Trading And Development Gmbh Sampling container for collection of fluids
CN205656091U (en) * 2016-04-08 2016-10-19 中国石油大学(北京) Volumetric method shale isothermal adsorption experimental apparatus
CN107421864A (en) * 2016-05-23 2017-12-01 中国石油化工股份有限公司 The assay method of the total specific surface area of micro- mesoporous solid material and micropore specific area
CN105987947A (en) * 2016-07-07 2016-10-05 南京师范大学 Method for determining nitrogen or carbon isotope ratio of N2 or CO2 gas on basis of elemental analyzer-stable isotope mass spectrometer combined device
CN106970000A (en) * 2017-04-21 2017-07-21 西南石油大学 Coal/shale extra-high absorption and Seepage Experiment evaluate shale gas adsorption method
CN110196264A (en) * 2019-06-05 2019-09-03 西南石油大学 A kind of high temperature and pressure condensation air elutriation wax amount test device and method
CN112240186A (en) * 2019-07-18 2021-01-19 中国石油天然气股份有限公司 Natural gas hydrate heat injection-replacement combined simulation mining device and method
CN110940613A (en) * 2019-11-05 2020-03-31 苏州冠德能源科技有限公司 Simulation experiment device for carbon isotope analysis in shale gas release process
CN112255369A (en) * 2020-10-21 2021-01-22 核工业北京地质研究院 Online continuous flow analysis and extraction device and method for methane carbon isotope composition in gas
CN112505209A (en) * 2020-11-05 2021-03-16 中国石油集团渤海钻探工程有限公司 Gas chromatography-isotope analysis combined device for logging field measurement of carbon isotope
CN112345667A (en) * 2020-11-06 2021-02-09 中国石油化工股份有限公司 Gaseous hydrocarbon preparation and online carbon isotope analysis device and method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CO_2分子置换法开采页岩气实验;张广东等;《成都理工大学学报. 自然科学版》;20150331;第42卷(第3期);第366-371页 *
Device for measuring wobble in cylindrical components and rings;Larichev K K;《Measurement Techniques》;19640531;第7卷(第5期);第373页 *
应用显微激光拉曼光谱测定CO_2气体碳同位素值δ~(13)C的定量方法研究;李佳佳等;《光谱学与光谱分析》;20170415(第04期);第1139-1144页 *

Also Published As

Publication number Publication date
CN113252421A (en) 2021-08-13

Similar Documents

Publication Publication Date Title
CN113252421B (en) Device and method for measuring trace carbon isotopes and heavy components in natural gas
CN110308216A (en) The integrated analysis system and its application method of micro permanent foreign gas and water in a kind of gas
WO2022000891A1 (en) Hydrate evaluation experiment system and method
CN105092350A (en) Pretreatment apparatus and method for determination of dissolved helium and neon in water
CN103675080A (en) Headspace sampler and ion mobility spectrometry combined system
CN110780015A (en) Detection device and detection method for non-methane total hydrocarbons
US9207227B2 (en) Composition of multiphase flow
CN202008464U (en) Detector for volatile matter in water
CN107976552A (en) The universal sampling device and general sample injection method of gaseous hydrocarbon and liquefied petroleum gas
CN206627464U (en) The detection means of gas dew point
CN105954416B (en) The apparatus and method of isoprene are dissolved in a kind of measure water body
CN207007641U (en) High strength ammonia Gas content detection means based on absorption process
CN114062517B (en) Mixed gas adsorption testing device and method for shale gas and coalbed gas
CN202942115U (en) Gas recovery rate determination device for detecting open type animal respiratory calorimetric system
CN117405551A (en) Device for detecting oil, gas and water content in rock and application thereof
CN102081038B (en) Detection device for volatile substance in water and detection method thereof
CN104390831A (en) Method and device for preparing standard methacrylic acid gas sample
CN100552451C (en) The assay method of micro oxygen containing compound and equipment in a kind of low boiling point hydrocarbon
CN104155207A (en) Gas content desorption testing device
CN209784284U (en) Sampling device for detecting components of coke oven flue gas
CN114034776A (en) Device and method for measuring distribution coefficient of dissolved gas in insulating oil
CN113804807A (en) Carbon isotope separation and enrichment device for hydrocarbon gas components in natural gas and sample preparation method
CN107315079A (en) System integration method for cryogenic natural gas Concentration Testing
CN219104842U (en) Liquefied gas moisture testing arrangement
CN220795139U (en) Gas sampling device for collecting thermal decomposition gas of synchronous thermal analyzer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information

Inventor after: Liu Jianyi

Inventor after: Li Jieke

Inventor after: Wen Guo

Inventor after: Yu Fan

Inventor before: Liu Jianyi

Inventor before: Li Jieke

Inventor before: Wen Guo

Inventor before: Yu Fan

CB03 Change of inventor or designer information