CN106093225A - Utilize He and CO2combine the method identifying coal-formed gas and/or petroliferous gas - Google Patents
Utilize He and CO2combine the method identifying coal-formed gas and/or petroliferous gas Download PDFInfo
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- CN106093225A CN106093225A CN201610380413.6A CN201610380413A CN106093225A CN 106093225 A CN106093225 A CN 106093225A CN 201610380413 A CN201610380413 A CN 201610380413A CN 106093225 A CN106093225 A CN 106093225A
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- 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
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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Abstract
The invention provides one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.The method comprises the following steps: gather gaseous sample；Isolate CO from the gaseous sample gathering2, and the mensuration of carbon isotope is carried out to it；CO with volume content >=99.999%2For standard, obtain CO in gaseous sample2Carbon isotope value δ13CCO2；Remove the active gases beyond rare gas in gas, isolate He, and it is carried out helium isotope R/Ra or3He/4The mensuration of He；Utilize δ13CCO2And R/Ra, or δ13CCO2With3He/4The origin cause of formation and source to gas for the He is identified.Coal-formed gas and/or petroliferous gas can effectively be identified by the method, for in-depth the gas origin cause of formation and Source Study, instruct gas exploration to provide technical support.
Description
Technical field
The present invention relates to one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas, particularly to one
Utilize He and CO in natural gas2Combine the method identifying coal-formed gas and/or petroliferous gas, belong to oil-gas exploration technical field.
Background technology
Natural gas is mainly by CH4、C2H6、C3H8、C4H10Deng hydrocarbon gas, a small amount of CO2、N2Dilute Deng non-hydrocarbon gas and trace
It is made up of gas He, Ne, Ar, Kr, Xe etc..
Based on the natural gas of China is with coal-formed gas, coal-formed gas is the main body of China's natural gas reserves and increase of production, at me
The development of state's gas industry account for the status holding the balance.Carry out coal-formed gas, petroliferous gas sentences knowledge, for clear and definite Natural Gas Origin
And source, instruct natural gas exploration, promote China's natural gas rapid industrial development significant.
At present, coal-formed gas and sentencing of petroliferous gas are known mainly from carbon isotope of natural gas and component, lighter hydrocarbons, biomarker etc.
Index considers；Non-hydrocarbon gas and rare gas, as the important component part of natural gas, have very close relationship with hydro carbons,
But there is no at present and relate to rare gas He and non-hydrocarbon gas CO2Sentence to combine and sentence knowledge coal-formed gas, the method for petroliferous gas and index.
Content of the invention
For solving above-mentioned technical problem, the invention provides one and utilize He and CO2Combine identification coal-formed gas and/or oil type
The method of gas, the origin cause of formation of natural gas and source can be effectively identified, grind for deepening Natural Gas Origin and source by the method
Study carefully, instruct natural gas exploration to provide technical support.
For reaching above-mentioned purpose, the invention provides one and utilize He and CO2Combine and identify coal-formed gas and/or petroliferous gas
Method, the method comprises the following steps:
Gather gaseous sample；
Isolate CO from the gaseous sample gathering2, and the mensuration of carbon isotope is carried out to it；With volume content >=
The CO of 99.999%2For standard, obtain CO in gaseous sample2Carbon isotope value δ13CCO2(‰, PDB)；
Purified treatment carried out to the gaseous sample gathering, removes the active gases beyond rare gas, and to rare gas
In He separate, the rare gas He of isolated is carried out helium isotope R/Ra or3He/4The mensuration of He；
Utilize the δ obtaining13CCO2And R/Ra, or δ13CCO2With3He/4He carries out coal-formed gas and/or petroliferous gas to gas
Identifying, the standard of identification is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2≤-15 ‰, gas is mainly coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2>=-2.5 ‰, gas is mainly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, gas be mainly coal-formed gas,
Petroliferous gas or the mixing of coal-formed gas and petroliferous gas.
In the above-mentioned methods, it is preferable that when gathering gaseous sample, the stage casing air-flow of gas well is gathered as gaseous sample.
In the above-mentioned methods, it is preferable that the container gathering gas is the stainless steel steel cylinder with bivalve.
In the above-mentioned methods, it is preferable that before gathering gaseous sample, the method also includes being evacuated to described steel cylinder
10-1Below Pa, then utilizes the step that gas carries out pre-flush to described steel cylinder；It is highly preferred that the number of times of described pre-flush is
4-6 time；It is further preferred that when carrying out pre-flush, the time of each pre-flush is more than 10 minutes.
In the above-mentioned methods, it is preferable that from the gaseous sample gathering, isolate CO2, and carbon isotope is carried out to it
During mensuration, gas chromatograph (GC) is used to isolate CO from the gaseous sample gathering2；Use isotope mass spectrometer (IRMS) right
The CO of isolated2Carry out the mensuration of carbon isotope.
In the above-mentioned methods, it is preferable that described gas is mainly coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas two
During the mixing of person, the method also includes utilizing the carbon isotope of alkane in described gas to identify described gas further
Step.
In the above-mentioned methods, it is preferable that described gas is natural gas.
In the above-mentioned methods, it is preferable that the method comprises the following steps:
Stainless steel steel cylinder with bivalve is evacuated to 10-1Below Pa；
With pressure-reducing valve, steel cylinder is connected with gas well valve by connecting pipeline, utilizes gas repeatedly to rinse steel cylinder 4-6 time, often
Secondary flushing more than 10 minutes, gathers the stage casing air-flow of gas well as gaseous sample；
Steel cylinder is connected with micro-sampling control valve, gaseous sample is injected in chromatogram-isotope mass spectrometry combined instrument, to gas
CO in body sample2Separate, and the CO to isolated2Carry out the mensuration of carbon isotope；With volume content >=99.999%
CO2For standard, obtain CO in gaseous sample2Carbon isotope value δ13CCO2(‰, PDB)；
Steel cylinder is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film rule and Mini-adjustable valve to control gas
The sample size of sample, the He in rare gas is simultaneously separated by the active gases beyond removal rare gas；
The rare gas He of isolated is sent in isotope mass spectrometer carry out helium isotope R/Ra or3He/4The survey of He
Fixed；
Utilize the δ obtaining13CCO2And R/Ra, or δ13CCO2With3He/4He carries out coal-formed gas and/or petroliferous gas to gas
Identifying, the standard of identification is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2≤-15 ‰, gas is mainly coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2>=-2.5 ‰, gas is mainly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, gas be mainly coal-formed gas,
Petroliferous gas or the mixing of coal-formed gas and petroliferous gas, then utilize the carbon isotope of alkane in gas to enter to advance to gas
One step identification.
In the above-mentioned methods, it is preferable that gather gas well stage casing air-flow as gaseous sample when, when the gas in steel cylinder
When pressure is 3-6MPa, stop sampling.
Beneficial effects of the present invention:
The technical scheme creativeness that the present invention provides utilizes rare gas He and non-hydrocarbon gas CO2Associating knowledge coal-formed gas
And/or petroliferous gas, it has quick, accurate and effective feature, natural for carrying out Natural Gas Origin and Source Study, guidance
Gas exploration is significant.
Brief description
Fig. 1 utilizes He and CO for what embodiment 1 provided2Combine the flow chart of the method identifying coal-formed gas and/or petroliferous gas；
Fig. 2 is the result figure of different gas field coal-formed gas and/or the identification of petroliferous gas.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.
The method, with the natural gas in Kela 2 Gas Field as research object, utilizes He and CO2Combine identification coal-formed gas and/or
Petroliferous gas (identification process is as shown in Figure 1), it comprises the following steps:
(1) select the stainless steel high-pressure cylinder with bivalve to sample, before sample collection, utilize mechanical pump etc. to take out steel cylinder
Vacuum is to 10-1Below Pa；
(2) steel cylinder is connected with the valve of the natural gas well with pressure-reducing valve by connecting pipeline, utilizes natural gas repeatedly to rinse
Steel cylinder 4-6 time, continues more than 10 minutes every time, gathers stage casing air-flow, stops sampling when the gas pressure in steel cylinder is 3-6MPa；
(3) steel cylinder having gathered natural gas sample is connected with micro-sampling control valve, utilizes micro-sampling pin from trace
Sampling valve takes out natural gas sample and injects in chromatogram-isotope mass spectrometry combined instrument (GC/C/IRMS), and natural gas sample is through gas phase look
The CO of spectrum (GC) isolated2Send into the isotope mass spectrometer being connected and carry out the mensuration of carbon isotope, with volume content >=
The CO of 99.999%2For standard, obtain CO in natural gas sample2Carbon isotope value δ13CCO2(‰, PDB)；
(4) steel cylinder having gathered natural gas sample is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film
Rule and the sample size of Mini-adjustable valve control natural gas sample, the active gases beyond purification removal rare gas simultaneously carries out rare
Gas separates, and the He of separation is sent into rare and refractory metals mass spectrograph and carries out rare gas helium isotope R/Ra in natural gas
(or3He/4He) mensuration；
(5) CO in the natural gas sample that step (3) obtains is utilized2Carbon isotope value δ13CCO2(‰, PDB), and step
(4) in the natural gas obtaining rare gas He helium isotope R/Ra value (or3He/4He), coal-formed gas and/or petroliferous gas are set up
Criterion of identification and plate (as shown in Figure 2):
1. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰, natural gas is mainly coal-formed gas；
2. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰, natural gas is mainly petroliferous gas；
3. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, natural gas is mainly coal
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas, then according to the carbon isotope of alkane in gas, gas is entered
Row identifies further；
(6) coal-formed gas set up according to step (5) and/or the criterion of identification of petroliferous gas and the sky to Kela 2 Gas Field for the plate
Right gas is identified, and recognition result is:
The δ that all natural gas sample product in Kela 2 Gas Field are surveyed13Cco2, R/Ra value (or3He/4He) be satisfied by " R/Ra≤
0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰ " this relation, i.e. all natural gas sample product have all fallen within plate
In " coal-formed gas " district；Therefore, all coal-formed gas of natural gas sample of Kela 2 Gas Field.
Embodiment 2
Present embodiments provide one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.
The method, with the natural gas in enlightening Na 2 gas field as research object, utilizes He and CO2Combine identification coal-formed gas and/or
Petroliferous gas, it comprises the following steps:
(1) select the stainless steel high-pressure cylinder with bivalve to sample, before sample collection, utilize mechanical pump etc. to take out steel cylinder
Vacuum is to 10-1Below Pa；
(2) steel cylinder is connected with the valve of the natural gas well with pressure-reducing valve by connecting pipeline, utilizes natural gas repeatedly to rinse
Steel cylinder 4-6 time, continues more than 10 minutes every time, gathers stage casing air-flow, stops sampling when the gas pressure in steel cylinder is 3-6MPa；
(3) steel cylinder having gathered natural gas sample is connected with micro-sampling control valve, utilizes micro-sampling pin from trace
Sampling valve takes out natural gas sample and injects in chromatogram-isotope mass spectrometry combined instrument (GC/C/IRMS), and natural gas sample is through gas phase look
The CO of spectrum (GC) isolated2Send into the isotope mass spectrometer being connected and carry out the mensuration of carbon isotope, with volume content >=
The CO of 99.999%2For standard, obtain CO in natural gas sample2Carbon isotope value δ13CCO2(‰, PDB)；
(4) steel cylinder having gathered natural gas sample is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film
Rule and the sample size of Mini-adjustable valve control natural gas sample, the active gases beyond purification removal rare gas simultaneously carries out rare
Gas separates, and the He of separation is sent into rare and refractory metals mass spectrograph and carries out rare gas helium isotope R/Ra in natural gas
(or3He/4He) mensuration；
(5) CO in the natural gas sample that step (3) obtains is utilized2Carbon isotope value δ13CCO2(‰, PDB), and step
(4) in the natural gas obtaining rare gas He helium isotope R/Ra value (or3He/4He), coal-formed gas and/or petroliferous gas are set up
Criterion of identification and plate (as shown in Figure 2):
1. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰, natural gas is mainly coal-formed gas；
2. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰, natural gas is mainly petroliferous gas；
3. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, natural gas is mainly coal
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas, then according to the carbon isotope of alkane in gas, gas is entered
Row identifies further；
(6) coal-formed gas set up according to step (5) and/or the criterion of identification of petroliferous gas and the sky to enlightening Na 2 gas field for the plate
Right gas is identified, and recognition result is:
The δ of a part of natural gas sample in enlightening Na 2 gas field13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰ " this relation, i.e. this portion of natural gas sample fall the " coal in plate
Become gas " district, therefore this portion of natural gas sample is coal-formed gas；
The δ of another part natural gas sample13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤
2.8×10-7) and-15 ‰ ＜ δ13Cco2This relation of ＜-2.5 ‰ ", i.e. this portion of natural gas sample fall the " coal in plate
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas " district, this portion of natural gas sample needs according to alkane in gas
Gas is identified by the carbon isotope of hydrocarbon further.
Embodiment 3
Present embodiments provide one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.
The method, with the natural gas in Xinchang Gas Field as research object, utilizes He and CO2Combine identification coal-formed gas and/or oil
Type gas, it comprises the following steps:
(1) select the stainless steel high-pressure cylinder with bivalve to sample, before sample collection, utilize mechanical pump etc. to take out steel cylinder
Vacuum is to 10-1Below Pa；
(2) steel cylinder is connected with the valve of the natural gas well with pressure-reducing valve by connecting pipeline, utilizes natural gas repeatedly to rinse
Steel cylinder 4-6 time, continues more than 10 minutes every time, gathers stage casing air-flow, stops sampling when the gas pressure in steel cylinder is 3-6MPa；
(3) steel cylinder having gathered natural gas sample is connected with micro-sampling control valve, utilizes micro-sampling pin from trace
Sampling valve takes out natural gas sample and injects in chromatogram-isotope mass spectrometry combined instrument (GC/C/IRMS), and natural gas sample is through gas phase look
The CO of spectrum (GC) isolated2Send into the isotope mass spectrometer being connected and carry out the mensuration of carbon isotope, with volume content >=
The CO of 99.999%2For standard, obtain CO in natural gas sample2Carbon isotope value δ13CCO2(‰, PDB)；
(4) steel cylinder having gathered natural gas sample is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film
Rule and the sample size of Mini-adjustable valve control natural gas sample, the active gases beyond purification removal rare gas simultaneously carries out rare
Gas separates, and the He of separation is sent into rare and refractory metals mass spectrograph and carries out rare gas helium isotope R/Ra in natural gas
(or3He/4He) mensuration；
(5) CO in the natural gas sample that step (3) obtains is utilized2Carbon isotope value δ13CCO2(‰, PDB), and step
(4) in the natural gas obtaining rare gas He helium isotope R/Ra value (or3He/4He), coal-formed gas and/or petroliferous gas are set up
Criterion of identification and plate (as shown in Figure 2):
1. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰, natural gas is mainly coal-formed gas；
2. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰, natural gas is mainly petroliferous gas；
3. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, natural gas is mainly coal
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas, then according to the carbon isotope of alkane in gas, gas is entered
Row identifies further；
(6) natural to Xinchang Gas Field of the coal-formed gas set up according to step (5) and/or the criterion of identification of petroliferous gas and plate
Gas is identified, and recognition result is:
The δ of a part of natural gas sample in Xinchang Gas Field13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰ " this relation, i.e. this portion of natural gas sample fall the " coal in plate
Become gas " district, therefore this portion of natural gas sample is coal-formed gas；
The δ of another part natural gas sample13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤
2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰ ", i.e. this portion of natural gas sample fall " coal-formed gas, oil in plate
Type gas or the mixing of coal-formed gas and petroliferous gas " district, this portion of natural gas sample needs the carbon according to alkane in gas same
Gas is identified by position element further.
Embodiment 4
Present embodiments provide one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.
The method, with the natural gas in Ordovician of Tahe oil as research object, utilizes He and CO2Associating identification coal-formed gas
And/or petroliferous gas, it comprises the following steps:
(1) select the stainless steel high-pressure cylinder with bivalve to sample, before sample collection, utilize mechanical pump etc. to take out steel cylinder
Vacuum is to 10-1Below Pa；
(2) steel cylinder is connected with the valve of the natural gas well with pressure-reducing valve by connecting pipeline, utilizes natural gas repeatedly to rinse
Steel cylinder 4-6 time, continues more than 10 minutes every time, gathers stage casing air-flow, stops sampling when the gas pressure in steel cylinder is 3-6MPa；
(3) steel cylinder having gathered natural gas sample is connected with micro-sampling control valve, utilizes micro-sampling pin from trace
Sampling valve takes out natural gas sample and injects in chromatogram-isotope mass spectrometry combined instrument (GC/C/IRMS), and natural gas sample is through gas phase look
The CO of spectrum (GC) isolated2Send into the isotope mass spectrometer being connected and carry out the mensuration of carbon isotope, with volume content >=
The CO of 99.999%2For standard, obtain CO in natural gas sample2Carbon isotope value δ13CCO2(‰, PDB)；
(4) steel cylinder having gathered natural gas sample is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film
Rule and the sample size of Mini-adjustable valve control natural gas sample, the active gases beyond purification removal rare gas simultaneously carries out rare
Gas separates, and the He of separation is sent into rare and refractory metals mass spectrograph and carries out rare gas helium isotope R/Ra in natural gas
(or3He/4He) mensuration；
(5) CO in the natural gas sample that step (3) obtains is utilized2Carbon isotope value δ13CCO2(‰, PDB), and step
(4) in the natural gas obtaining rare gas He helium isotope R/Ra value (or3He/4He), coal-formed gas and/or petroliferous gas are set up
Criterion of identification and plate (as shown in Figure 2):
1. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰, natural gas is mainly coal-formed gas；
2. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰, natural gas is mainly petroliferous gas；
3. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, natural gas is mainly coal
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas, then according to the carbon isotope of alkane in gas, gas is entered
Row identifies further；
(6) coal-formed gas set up according to step (5) and/or the criterion of identification of petroliferous gas and plate are to Ordovician of Tahe oil
Natural gas be identified, recognition result is:
The δ of a part of natural gas sample in Ordovician of Tahe oil13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤
0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰ " this relation, i.e. this portion of natural gas sample fall at plate
In " petroliferous gas " district, therefore this portion of natural gas sample is petroliferous gas；
The δ of another part natural gas sample13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤
2.8×10-7) and-15 ‰ ＜ δ13Cco2This relation of ＜-2.5 ‰ ", i.e. this portion of natural gas sample fall the " coal in plate
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas " district, need the carbon isotope according to alkane in gas to gas
Body identifies further.
Embodiment 5
Present embodiments provide one and utilize He and CO2Combine the method identifying coal-formed gas and/or petroliferous gas.
The method, with the natural gas in I gas field in tower as research object, utilizes He and CO2Combine identification coal-formed gas and/
Or petroliferous gas, it comprises the following steps:
(1) select the stainless steel high-pressure cylinder with bivalve to sample, before sample collection, utilize mechanical pump etc. to take out steel cylinder
Vacuum is to 10-1Below Pa；
(2) steel cylinder is connected with the valve of the natural gas well with pressure-reducing valve by connecting pipeline, utilizes natural gas repeatedly to rinse
Steel cylinder 4-6 time, continues more than 10 minutes every time, gathers stage casing air-flow, stops sampling when the gas pressure in steel cylinder is 3-6MPa；
(3) steel cylinder having gathered natural gas sample is connected with micro-sampling control valve, utilizes micro-sampling pin from trace
Sampling valve takes out natural gas sample and injects in chromatogram-isotope mass spectrometry combined instrument (GC/C/IRMS), and natural gas sample is through gas phase look
The CO of spectrum (GC) isolated2Send into the isotope mass spectrometer being connected and carry out the mensuration of carbon isotope, with volume content >=
The CO of 99.999%2For standard, obtain CO in natural gas sample2Carbon isotope value δ13CCO2(‰, PDB)；
(4) steel cylinder having gathered natural gas sample is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film
Rule and the sample size of Mini-adjustable valve control natural gas sample, the active gases beyond purification removal rare gas simultaneously carries out rare
Gas separates, and the He of separation is sent into rare and refractory metals mass spectrograph and carries out rare gas helium isotope R/Ra in natural gas
(or3He/4He) mensuration；
(5) CO in the natural gas sample that step (3) obtains is utilized2Carbon isotope value δ13CCO2(‰, PDB), and step
(4) in the natural gas obtaining rare gas He helium isotope R/Ra value (or3He/4He), coal-formed gas and/or petroliferous gas are set up
Criterion of identification and plate (as shown in Figure 2):
1. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2≤-15 ‰, natural gas is mainly coal-formed gas；
2. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰, natural gas is mainly petroliferous gas；
3. R/Ra≤0.2 (or3He/4He≤2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, natural gas is mainly coal
Become the mixing of gas, petroliferous gas or coal-formed gas and petroliferous gas, then according to the carbon isotope of alkane in gas, gas is entered
Row identifies further；
(6) coal-formed gas set up according to step (5) and/or the criterion of identification of petroliferous gas and plate are to I gas field in tower
Natural gas is identified, and recognition result is:
The δ of a part of natural gas sample in I gas field in tower13Cco2, R/Ra value (or3He/4He) " R/Ra≤0.2 is met
(or3He/4He≤2.8×10-7) and δ13Cco2>=-2.5 ‰ " this relation, i.e. this portion of natural gas sample fall in plate
" petroliferous gas " district, therefore this portion of natural gas sample is petroliferous gas；
The δ of another part natural gas sample13Cco2, R/Ra value (or3He/4He) meet " R/Ra≤0.2 (or3He/4He≤
2.8×10-7) and-15 ‰ ＜ δ13Cco2＜-2.5 ‰ ", i.e. this portion of natural gas sample fall " coal-formed gas, oil in plate
Type gas or the mixing of coal-formed gas and petroliferous gas " district, needs the carbon isotope according to alkane in gas to enter to advance to gas
One step identification.
Claims (10)
1. one kind utilizes He and CO2Combining the method identifying coal-formed gas and/or petroliferous gas, it comprises the following steps:
Gather gaseous sample；
Isolate CO from the gaseous sample gathering2, and the mensuration of carbon isotope is carried out to it；With volume content >=99.999%
CO2For standard, obtain CO in gaseous sample2Carbon isotope value δ13CCO2；
Carry out purified treatment, the active gases beyond removing rare gas to the gaseous sample gathering, separate from rare gas
Go out He, and it is carried out helium isotope R/Ra or3He/4The mensuration of He；
Utilize the δ obtaining13CCO2And R/Ra, or δ13CCO2With3He/4He carries out the knowledge of coal-formed gas and/or petroliferous gas to gas
Not, the standard of identification is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2≤-15 ‰, gas is mainly coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2>=-2.5 ‰, gas is mainly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, gas is mainly coal-formed gas, oil type
Gas or the mixing of coal-formed gas and petroliferous gas.
2. method according to claim 1, wherein, when gathering gaseous sample, gathers the stage casing air-flow of gas well as gas
Body sample.
3. method according to claim 1, wherein, the container gathering gas is the stainless steel steel cylinder with bivalve.
4. method according to claim 3, wherein, before gathering gaseous sample, the method also includes taking out described steel cylinder
Vacuum is to 10-1Below Pa, then utilizes the step that gas carries out pre-flush to described steel cylinder.
5. method according to claim 4, wherein, the number of times of described pre-flush is 4-6 time；
Preferably, the time of each pre-flush is more than 10 minutes.
6. method according to claim 1, wherein, described gas is natural gas.
7. method according to claim 1, wherein, isolates CO from the gaseous sample gathering2, and carry out carbon to it same
Position element mensuration when, use gas chromatograph from gather gaseous sample isolate CO2, use isotope mass spectrometer to separation
The CO obtaining2Carry out the mensuration of carbon isotope.
8. method according to claim 1, wherein, described gas is mainly coal-formed gas, petroliferous gas or coal-formed gas and oil
During the mixing of both type gas, the method also includes that described gas is carried out further by the carbon isotope utilizing alkane in described gas
The step identifying.
9. method according to claim 1, wherein, the method comprises the following steps:
Stainless steel steel cylinder with bivalve is evacuated to 10-1Below Pa；
With pressure-reducing valve, steel cylinder is connected with the valve of gas well by connecting pipeline, utilizes gas repeatedly to rinse steel cylinder 4-6 time, every time
Rinse more than 10 minutes, gather the stage casing air-flow of gas well as gaseous sample；
Steel cylinder is connected with micro-sampling control valve, gaseous sample is injected in chromatogram-isotope mass spectrometry combined instrument, to gas sample
CO in product2Separate, and the CO to isolated2Carry out the mensuration of carbon isotope；With volume content >=99.999%
CO2For standard, obtain CO in gaseous sample2Carbon isotope value δ13CCO2；
Steel cylinder is connected with rare gas sample preparation device by pressure-reducing valve, utilizes film rule and Mini-adjustable valve to control gaseous sample
Sample size, remove the active gases beyond rare gas and simultaneously the He in rare gas separated；
The rare gas He of isolated is sent in isotope mass spectrometer carry out helium isotope R/Ra or3He/4The mensuration of He；
Utilize the δ obtaining13CCO2And R/Ra, or δ13CCO2With3He/4He carries out the knowledge of coal-formed gas and/or petroliferous gas to gas
Not, the standard of identification is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2≤-15 ‰, gas is mainly coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and δ13Cco2>=-2.5 ‰, gas is mainly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, and-15 ‰ ＜ δ13Cco2＜-2.5 ‰, gas is mainly coal-formed gas, oil type
Gas or the mixing of coal-formed gas and petroliferous gas, then utilize the carbon isotope of alkane in gas to carry out gas further
Identify.
10. method according to claim 9, wherein, gather gas well stage casing air-flow as gaseous sample when, work as steel cylinder
When interior gas pressure is 3-6MPa, stop sampling.
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