CN106053643B - Identification of CO in natural gas2Method for origin and cause of disease and its application - Google Patents
Identification of CO in natural gas2Method for origin and cause of disease and its application Download PDFInfo
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- CN106053643B CN106053643B CN201610380415.5A CN201610380415A CN106053643B CN 106053643 B CN106053643 B CN 106053643B CN 201610380415 A CN201610380415 A CN 201610380415A CN 106053643 B CN106053643 B CN 106053643B
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- 201000010099 disease Diseases 0.000 title 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 256
- 239000007789 gas Substances 0.000 claims abstract description 213
- 239000003345 natural gas Substances 0.000 claims abstract description 146
- 238000000034 method Methods 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 239000001307 helium Substances 0.000 claims abstract description 28
- 229910052734 helium Inorganic materials 0.000 claims abstract description 28
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 45
- 230000015572 biosynthetic process Effects 0.000 claims description 45
- 229930195733 hydrocarbon Natural products 0.000 claims description 43
- 150000002430 hydrocarbons Chemical class 0.000 claims description 43
- 238000005070 sampling Methods 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000004454 trace mineral analysis Methods 0.000 claims description 5
- 238000004949 mass spectrometry Methods 0.000 claims description 4
- 239000003870 refractory metal Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000155 isotopic effect Effects 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SVPKNMBRVBMTLB-UHFFFAOYSA-N 2,3-dichloronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Cl)=C(Cl)C(=O)C2=C1 SVPKNMBRVBMTLB-UHFFFAOYSA-N 0.000 description 2
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
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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
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- General Health & Medical Sciences (AREA)
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- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a method for judging and identifying CO in natural gas2Origin and cause methods and uses thereof. The method comprises the following steps: collecting natural gas samples, measuring carbon isotope ratio and helium isotope ratio, and establishing an identification index system to identify CO associated with rare gas in natural gas2The origin and origin, the judgment index system is: R/Ra is less than or equal to 1 and delta13CCO2≤‑10‰，CO2Most of the organic causes are shell sources; R/Ra is less than or equal to 1 and delta13CCO2≥‑8‰，CO2Most of the sources are shell sources and inorganic causes; R/Ra is less than or equal to 0.2 and-10 per mill<δ13CCO2<‑8‰，CO2Mostly, the shell source organic cause and the shell source inorganic cause are mixed; 1 is not less than R/Ra>0.2 to-10 ‰<δ13CCO2<‑8‰，CO2Mostly, the mixture of shell source organic cause and mantle source inorganic cause or the mixture of shell source inorganic cause and mantle source inorganic cause; R/Ra>1，CO2Mostly, mantle-derived inorganic causes.
Description
Technical field
The invention belongs to oil-gas exploration technical fields, are related to a kind of non-hydrocarbon gas CO2The organic and inorganic origin cause of formation and source are sentenced
Knowledge method more particularly to one kind, which are sentenced, knows CO in natural gas2The method and its application of the origin cause of formation and source.
Background technique
Natural gas is mainly grouped as by groups such as hydrocarbon gas, a small amount of non-hydrocarbon gas and micro rare gas.Non-hydrocarbon gas
CO2It is the important component of natural gas, and its relationship between hydro carbons is very close.Therefore, carry out non-hydrocarbon gas CO2's
The origin cause of formation and source identification research, the origin cause of formation and source for full appreciation natural gas, instruct natural gas exploration and exploitation to have weight
Want meaning.Currently, about non-hydrocarbon gas CO2The origin cause of formation and source mostly with CO2Component, isotope, which are used as, sentences knowledge index, and in combination
Matter condition carries out comprehensive analysis, but this needs takes a significant amount of time and energy.So far, this field still lacks to nonhydrocarbon
Gas CO2The organic and inorganic origin cause of formation and source carry out quick, the accurate and effective method for sentencing knowledge.
Summary of the invention
The shortcomings that in view of the above-mentioned prior art, is sentenced the purpose of the present invention is to provide one kind and knows CO in natural gas2The origin cause of formation and
The method in source, this method can be to non-hydrocarbon gas CO in natural gas2Organic and/or inorganic and source carry out quickly,
Accurately sentence knowledge.
In order to reach goal of the invention above-mentioned, the present invention provides one kind and sentences CO in knowledge natural gas2The method of the origin cause of formation and source,
Itself the following steps are included:
Acquire gas samples；
Measure CO in the gas samples2Carbon isotope ratio δ13CCO2；
Measure helium isotope ratio R/Ra in the gas samples；
Knowledge index system is sentenced in foundation, sentences and knows CO in the gas samples2The origin cause of formation and source；
It is wherein, described to sentence knowledge index system are as follows:
R/Ra≤1 and δ13CCO2≤ -10 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2Mostly shell
Source organic origin；
R/Ra≤1 and δ13CCO2>=-8 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2Mostly shell
Source inorganic；
R/Ra≤0.2 and -10 ‰ < δ13CCO2< -8 ‰, then the non-hydrocarbon gas in the natural gas with rare gas association
CO2Mostly shell source organic origin with shell source is anorganogene mixes；
1>=R/Ra>0.2 and -10 ‰<δ13CCO2< -8 ‰, then the non-hydrocarbon gas in the natural gas with rare gas association
CO2Mostly shell source organic origin and curtain source it is anorganogene mix or shell source inorganic with curtain source is anorganogene mixes；
R/Ra > 1, then in the natural gas rare gas association non-hydrocarbon gas CO2Mostly curtain source inorganic.
In the above-mentioned methods, the natural gas includes the mixing of the hydro carbons and non-hydrocarbon gases naturally contained in stratum
Object.
In the above-mentioned methods, the natural gas includes but is not limited to casing-head gas, reservoir gas, coal bed gas, shale gas, mud volcano
Gas or biogas etc..
In the above-mentioned methods, it is preferable that the method for the acquisition gas samples are as follows: high-pressure cylinder is evacuated to 10-1Pa with
Under, the middle section air-flow of natural gas is then acquired, until the gas pressure of the high-pressure cylinder is 3-6MPa, obtains natural gas sample
This.
In the above-mentioned methods, the maximum working pressure (MWP) of the high-pressure cylinder is 15MPa.
In the above-mentioned methods, it is preferable that CO in the measurement gas samples2Carbon isotope ratio δ13CCO2Side
Method are as follows: measure the natural gas using gas chromatograph and isotope mass spectrometer or gas-chromatography isotope mass spectrometry combined instrument
CO in sample2Carbon isotope ratio δ13CCO2。
In the above-mentioned methods, it is preferable that helium isotope ratio R/Ra method in the measurement gas samples are as follows:
The high-pressure cylinder is connected with rare gas sample preparation device in natural gas, passes through rare gas sample preparation device in the natural gas
He is isolated from the gas samples, and the He is sent into rare and refractory metals mass spectrograph, is measured described natural
Helium isotope ratio R/Ra in gas sample sheet.
In the above-mentioned methods, it is preferable that the high-pressure cylinder is the high-pressure cylinder with bivalve and double nip.
In the above-mentioned methods, the bivalve includes pressure reducing valve and/or sampling valve.
In the above-mentioned methods, it is preferable that further include cleaning high-pressure cylinder before the acquisition gas samples the step of
Step；
The step is that the high-pressure cylinder is evacuated to 10-1Then Pa is hereinafter, connect the high pressure steel by the first pressure reducing valve
First interface on bottle is passed through natural gas into the high-pressure cylinder and carries out repeated flushing.
In the above-mentioned methods, gas samples can directly be acquired after to high-pressure cylinder cleaning for several times.
In the above-mentioned methods, the high-pressure cylinder includes stainless steel high-pressure cylinder etc., but not limited to this.
In the above-mentioned methods, the capacity of the high-pressure cylinder is 0.7-1.0L.
In the above-mentioned methods, first pressure reducing valve is connected by connecting pipeline with natural gas wellhead, then from the day
High-pressure cylinder described in natural gas flushing is obtained in right gas well, and adopts to obtain above-mentioned gas samples.
In the above-mentioned methods, in the acquisition gas samples the step of and/or the step of the cleaning high-pressure cylinder,
The high-pressure cylinder is vacuumized using vacuum pumps such as mechanical pumps, is evacuated to 10-1Pa or less.
In the above-mentioned methods, it is preferable that CO in the measurement gas samples2Carbon isotope ratio δ13CCO2Step
It suddenly is that the natural gas sample is isolated into CO through the gas chromatograph2, it is then fed into the isotope mass spectrometer and carries out
The measurement of carbon isotope, and with high-purity CO of content >=99.999%2For Standard Gases, CO in the natural gas sample is calculated2Carbon
Isotopic ratio δ13CCO2。
In the above-mentioned methods, in the measurement carbon isotope ratio the step of, the dosage of the natural gas sample passes through
The micro-sampling pin control, the dosage are this field conventional amount used.
In the above-mentioned methods, it is preferable that the CO in the measurement gas samples2Carbon isotope ratio δ13CCO2's
In step, the second interface of the high-pressure cylinder connects sampling valve, takes natural gas sample from the sampling valve using micro-sampling pin,
And natural gas sample is injected into gas chromatograph, the CO separated by gas-chromatography2Into isotope mass spectrometer, isotope is utilized
Mass spectrograph measures CO in the natural gas sample2Carbon isotope ratio δ13CCO2。
In the above-mentioned methods, it is preferable that the step of helium isotope ratio R/Ra in the measurement gas samples
In, the second interface of the high-pressure cylinder connects the second pressure reducing valve, which connects rare gas in the natural gas
Injection port, film rule and micro-sampling valve on sample preparation device, and enter institute by film rule and the control of micro-sampling valve
State the natural gas sample volume of rare gas sample preparation device in natural gas.
In the above-mentioned methods, the natural gas sample volume is depending on specific implementation needs.
In the above-mentioned methods, in the measurement helium isotope ratio the step of, using rare gas in the natural gas
Active gases other than sample preparation device purification, removing rare gas, and the separation of rare gas is carried out, isolate He.
In the above-mentioned methods, it is preferable that the step of helium isotope ratio R/Ra in the measurement gas samples
In, rare gas sample preparation device includes the sample preparation device or natural gas for being used to prepare rare gas in natural gas in the natural gas
Middle rare gas trace analysis device, but not limited to this.
In the above-mentioned methods, described to be used to prepare in natural gas rare gas in the sample preparation device or natural gas of rare gas
Trace analysis device can be this field conventional equipment.
In the above-mentioned methods, the step of measurement carbon isotope ratio and the step of measurement helium isotope ratio, are suitable
Sequence can be depending on practical operation.
In the above-mentioned methods, it is preferable that in the cleaning high-pressure cylinder the step of, the method for the repeated flushing are as follows:
Using natural gas repeated flushing 4-6 times, each washing time is 10 minutes or more.
In the above-mentioned methods, it is preferable that this, which is sentenced, knows CO in natural gas2The origin cause of formation and the method in source further include sentencing knowledge for described
Plate is made in index system, and is intuitively sentenced according to the plate and know CO in the gas samples2The origin cause of formation and source.
In the above-mentioned methods, sentence in the step of knowing index system in the foundation, the shell source inorganic is mainly rock
The stone Thermochemical Decomposition origin cause of formation.
CO in knowledge natural gas is sentenced the present invention also provides above-mentioned2The origin cause of formation and the method in source answering in natural gas exploration
With.
It is provided by the invention it is above-mentioned sentence know natural gas in CO2The method of the origin cause of formation and source, can be to the hydrocarbon gas non-in natural gas
Body CO2Organic and/or inorganic and source carry out it is quick, accurate and effective sentence knowledge, this is in-depth Natural Gas Origin and comes
Source research instructs natural gas exploration to provide technical support.And this method has strong operability, analyzes quick, high reliablity
The features such as；CO in knowledge natural gas is sentenced by above-mentioned2The origin cause of formation and the method in source are applied in natural gas exploration, for carrying out natural gas
The origin cause of formation and Source Study instruct natural gas exploration to be of great significance.
Detailed description of the invention
Fig. 1 is that embodiment 1-3 sentences CO in knowledge natural gas2The flow chart of the origin cause of formation and the method in source；
Fig. 2 is in embodiment 1 according to CO2The organic and inorganic origin cause of formation and sentencing for source know the plate that index system is established；
Fig. 3 is embodiment 1-3 and verifies CO in the natural gas or geology abjection gas of each gas field of example 1-32The origin cause of formation and come
Sentence knowledge result map in source.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out following detailed description, but should not be understood as the restriction to enforceable range of the present invention.
Embodiment 1
It present embodiments provides one kind and sentences CO in knowledge natural gas2The method of the origin cause of formation and source, follows the steps below:
Using 2 gas field of carat exploitation natural gas as research sample, according to process shown in FIG. 1 carry out detection and
Analysis:
Selecting volume is 1L band there are two the stainless steel high-pressure cylinder of valve and double nip, the benefit before gas samples acquire
Above-mentioned stainless steel high-pressure cylinder is evacuated to 10 with mechanical pump-1Pa or less；
The first interface of above-mentioned stainless steel high-pressure cylinder is passed through into connecting pipeline and the first pressure reducing valve and natural gas wellhead phase
Even, using natural gas repeated flushing above-mentioned steel cylinder 4-6 times, continue 10 minutes or more every time, then acquire the middle section of the natural gas
Then air-flow stops sampling, obtains gas samples to be measured until the gas pressure of the steel cylinder is 3-6MPa；
The second interface of the high-pressure cylinder of the acquisition gas samples is connected with sampling valve, using micro-sampling pin from described
It is taken at sampling valve in appropriate natural gas sample injection gas-chromatography isotope mass spectrometry combined instrument, the natural gas sample passes through gas phase
Chromatographic isolation goes out the CO in natural gas2, the CO that then isolates this2It is sent into connected isotope mass spectrometer and carries out the same position of carbon
Element measurement, with high-purity CO of content >=99.999%2For Standard Gases, CO in the natural gas sample is calculated2Carbon isotope ratio
δ13CCO2, in terms of International Carbon isotopic standard (PDB)；
Will acquisition have gas samples high-pressure cylinder second interface by the second pressure reducing valve successively with it is dilute in natural gas
Have the injection port on gas trace analytical equipment, film rule be connected with micro-sampling valve, then by the film rule with it is micro
Sampling valve controls the sample volume of gas samples, is purified using rare gas trace analysis device in the natural gas, described in removal
Active gases in gas samples in addition to rare gas, and the separation of rare gas is carried out, isolated He is sent into rare
In gas isotope mass spectrograph, the isotopic ratio of rare gas helium in the gas samples is measured, with3He/4He or R/Ra meter；
Utilize the isotopic ratio R/Ra and non-hydrocarbon gas CO of rare gas helium in above-mentioned gas samples2Carbon isotope
Ratio delta13CCO2Two key parameters, establish CO2Knowledge index system is sentenced in the organic and inorganic origin cause of formation and source, according to the index body
System establishes plate, as shown in Fig. 2, and sentencing the non-hydrocarbon gas CO known in the natural gas with rare gas association according to the plate2
The organic and inorganic origin cause of formation and source；
It is described to sentence knowledge index system are as follows:
(1) as R/Ra≤1 and δ13CCO2When≤- 10 ‰, then the non-hydrocarbon gas in the natural gas with rare gas association
CO2It is mostly generally shell source organic origin, as shown in the region A of Fig. 2；
(2) as R/Ra≤1 and δ13CCO2When >=-8 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2
It is generally mostly shell source inorganic, i.e. the generally predominantly CO of rock Thermochemical Decomposition formation2, as shown in the region of Fig. 2 D；
(3) as R/Ra≤0.2 and -10 ‰ < δ13CCO2When < -8 ‰, then the nonhydrocarbon in the natural gas with rare gas association
Gas CO2It is generally mostly shell source organic origin and shell source is anorganogene mixes, as shown in the region B of Fig. 2；
(4) as 1>=R/Ra>0.2 and -10 ‰<δ13CCO2It is when < -8 ‰, then non-with rare gas association in the natural gas
Appropriate hydrocarbon gas CO2Mostly shell source organic origin and curtain source it is anorganogene mix or shell source inorganic and curtain source it is anorganogene mixed
It closes, as shown in the region C of Fig. 2；
(5) as R/Ra > 1, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2Generally be mostly curtain source without
The machine origin cause of formation, as shown in the region E of Fig. 2；
Through testing and analyzing, the isotopic ratio R/ of the helium of the natural gas for 2 gas field of the carat exploitation that the present embodiment uses
Ra≤1, and its CO2Carbon isotope ratio δ13CCO2≤ -10 ‰, as shown in the region A in Fig. 3, therefore, 2 gas field of carat
In the natural gas of exploitation with the non-hydrocarbon gas CO of rare gas association2Predominantly shell source organic origin.
The present embodiment also uses the natural gas of 2 gas-field exploitation of enlightening Na as research sample, to 2 gas-field exploitation of enlightening Na
Gas samples carry out CO2Carbon isotope ratio δ13CCO2And the detection of the isotopic ratio R/Ra of helium；After measured, the enlightening Na 2
Helium isotope ratio R/Ra≤1 in the gas samples of gas-field exploitation, and measure CO2Carbon isotope ratio be concentrated mainly on δ13CCO2In≤- 10 ‰ range, as shown in the region A in Fig. 3, therefore, in the natural gas of 2 gas-field exploitation of enlightening Na with rare gas
The non-hydrocarbon gas CO of body association2It also is shell source organic origin.
In the present embodiment, in the natural gas of 2 gas-field exploitation of natural gas and Di Na of practical 2 gas field of carat exploitation with it is dilute
There is the non-hydrocarbon gas CO of gas association2For shell source organic origin, this sentences CO in knowledge natural gas with provided in this embodiment2The origin cause of formation and
The identifying result of the method in source and consistent.
Embodiment 2
It present embodiments provides one kind and sentences CO in knowledge natural gas2The method of the origin cause of formation and source, follows the steps below:
Using the natural gas of I gas-field exploitation in tower as research sample, is detected and divided according to process shown in FIG. 1
Analysis:
Selecting volume is the stainless steel high-pressure cylinder that 0.7L has double valve and double nip, the benefit before gas samples acquire
Above-mentioned stainless steel high-pressure cylinder is evacuated to 10 with mechanical pump-1Pa or less；
The first interface of above-mentioned stainless steel high-pressure cylinder is passed through into connecting pipeline and the first pressure reducing valve and natural gas wellhead phase
Even, using natural gas repeated flushing above-mentioned steel cylinder 4-6 times, continue 10 minutes or more every time, the steel cylinder is then evacuated to 10- 1Pa is hereinafter, acquire the middle section air-flow of the natural gas, until the gas pressure of the steel cylinder is 3-6MPa, then stopping sampling, is obtained
Obtain gas samples to be measured；
The second interface of the high-pressure cylinder of the acquisition gas samples is connected with sampling valve, using micro-sampling pin from described
It is taken at sampling valve in appropriate natural gas sample injection gas-chromatography isotope mass spectrometry combined instrument, the natural gas sample passes through gas phase
Chromatographic isolation goes out the CO in natural gas2, the CO that then isolates this2It is sent into connected isotope mass spectrometer and carries out the same position of carbon
Element measurement, with high-purity CO of content >=99.999%2For Standard Gases, CO in the natural gas sample is calculated2Carbon isotope ratio
δ13CCO2, in terms of International Carbon isotopic standard (PDB)；
Will acquisition have gas samples high-pressure cylinder second interface by the second pressure reducing valve successively with it is dilute in natural gas
Have the injection port on gas trace analytical equipment, film rule be connected with micro-sampling valve, then by the film rule with it is micro
Sampling valve controls the sample volume of gas samples, is purified using rare gas trace analysis device in the natural gas, described in removal
Active gases in gas samples in addition to rare gas, and the separation of rare gas is carried out, isolated He is sent into rare
In gas isotope mass spectrograph, the isotopic ratio of rare gas helium in the gas samples is measured, with3He/4He or R/Ra meter；
Then the CO established according to embodiment 12The organic and inorganic origin cause of formation and source identifications are to the natural gas sample of the present embodiment
Originally the helium isotope ratio R/Ra and CO measured2Carbon isotope ratio δ13CCO2It is analyzed, the present embodiment measures R/Ra≤1,
And measure CO2Carbon isotope ratio δ13CCO2>=-8 ‰, as shown in the region D in Fig. 3, therefore, I gas-field exploitation in tower
In natural gas with the non-hydrocarbon gas CO of rare gas association2Predominantly shell source inorganic, as rock Thermochemical Decomposition are formed
CO2。
Non-hydrocarbon gas CO in the present embodiment, in actual column in the natural gas of I gas-field exploitation with rare gas association2It is main
It to be shell source inorganic, this sentences CO in knowledge natural gas with provided in this embodiment2The identifying result of the origin cause of formation and the method in source
With it is consistent.
Embodiment 3
It present embodiments provides one kind and sentences CO in knowledge natural gas2The method of the origin cause of formation and source, follows the steps below:
Using the natural gas of the not wooden gas field exploitation of Acker as research sample, examined according to process shown in FIG. 1
It surveys and analyzes:
The present embodiment carries out the gas samples of the not wooden gas field exploitation of the Acker using the method for embodiment 1
Sampling, and CO is carried out to the gas samples2Carbon isotope ratio δ13CCO2And the detection of the isotopic ratio R/Ra of helium；So
The CO established afterwards according to embodiment 12The helium that the organic and inorganic origin cause of formation and source identifications measure the present embodiment gas samples
Isotopic ratio R/Ra and CO2Carbon isotope ratio δ13CCO2It is analyzed；The present embodiment measures 1 >=R/Ra > 0.2, and measures
CO2- 10 ‰ < δ of carbon isotope ratio13CCO2< -8 ‰, as shown in the region C in Fig. 3, therefore, the not wooden gas field of Acker is opened
In the natural gas adopted with the non-hydrocarbon gas CO of rare gas association2Based on shell source organic origin, there are partial crustal it is organic-curtain
Source is inorganic be mixed into because or shell source inorganic and curtain source it is anorganogene be mixed into because.
Non-hydrocarbon gas in the present embodiment, in the natural gas of the not wooden gas field exploitation of practical Acker with rare gas association
CO2Based on shell source organic origin, there are partial crustal it is organic-curtain source it is inorganic be mixed into because or shell source inorganic and curtain source without
The machine origin cause of formation is mixed into because this sentences CO in knowledge natural gas with provided in this embodiment2The identifying result of the origin cause of formation and the method in source
With it is consistent.
Verify example 1
The natural gas that this verifying example also uses Ordovician of Tahe oil gas field to exploit is as identifying object.System in Tahe Oilfield
Helium isotope ratio R/Ra≤1 in the gas samples of Ordovician Natural Gas field exploitation, and CO2Carbon isotope ratio mainly collect
In in δ13CCO2In >=-8 ‰ range, as shown in the region D in Fig. 3, therefore, Ordovician of Tahe oil gas field exploitation
Natural gas in non-hydrocarbon gas CO with rare gas association2Predominantly shell source inorganic, as rock Thermochemical Decomposition shape
At CO2。
It is non-with rare gas association in the natural gas of practical system in Tahe Oilfield Ordovician Natural Gas field exploitation in this verifying example
Appropriate hydrocarbon gas CO2Predominantly shell source inorganic, this sentences CO in knowledge natural gas with what embodiment 1 provided2The origin cause of formation and the method in source
Identifying result and consistent.
Verify example 2
This verifying example is using the natural gas of Hadexun oilfield gas field exploitation as identifying object.Hadexun oilfield is natural
Helium isotope ratio R/Ra≤0.2 in the gas samples of gas field, and CO2Carbon isotope ratio be concentrated mainly on -10 ‰ < δ13CCO2In < -8 ‰ range, as shown in the region B in Fig. 3, therefore, in Hadexun oilfield gas field natural gas with rare gas
The non-hydrocarbon gas CO of body association2Predominantly shell source organic origin with shell source is anorganogene mixes.
In this verifying example, in practical Hadexun oilfield gas field natural gas with the non-hydrocarbon gas CO of rare gas association2
Predominantly shell source organic origin with shell source is anorganogene mixes, what this was provided with embodiment 1, which sentence, knows CO in natural gas2The origin cause of formation and
The identifying result of the method in source and consistent.
Verify example 3
This verifying example is using non-hydrocarbon gas CO in HUANGHUA DEPRESSION Gangxi faulted zone inclusion enclave2Carbon isotope ratio δ13C CO2
And helium isotope ratio R/Ra verifies plate.In HUANGHUA DEPRESSION Gangxi faulted zone inclusion enclave with non-hydrocarbon gas CO2Association
Rare gas helium isotopic ratio R/Ra > 1, sample spot falls into as in the region E in Fig. 3, and therefore, HUANGHUA DEPRESSION port west is disconnected
It splits with the non-hydrocarbon gas CO in inclusion enclave with rare gas association2For curtain source inorganic.
This verifying example has also been respectively adopted in the regional natural gas such as Wudalianchi Volcanic gas, northern Suzhou Huang Qiao, Song Liaowan quintar
Non-hydrocarbon gas CO2Carbon isotope ratio δ13CCO2And helium isotope ratio R/Ra verifies plate.Wudalianchi Volcanic
Gas, northern Suzhou Huang Qiao, Song Liaowan quintar etc. area natural gas in non-hydrocarbon gas CO2The rare gas helium isotope ratio of association is equal
For R/Ra > 1, sample spot is each fallen within as in the region E in Fig. 3, therefore, above-mentioned Wudalianchi Volcanic gas, northern Suzhou Huang Qiao, Song Liaowan
The non-hydrocarbon gas CO in the area and rare gas association such as quintar2It is curtain source inorganic.
In this verifying example, non-hydrocarbon gas CO in practical HUANGHUA DEPRESSION Gangxi faulted zone inclusion enclave2, Wudalianchi Volcanic gas,
The non-hydrocarbon gas CO in the area and rare gas association such as northern Suzhou Huang Qiao, Song Liaowan quintar2For curtain source inorganic, this and embodiment
CO in natural gas is known in sentencing for 1 offer2The identifying result of the origin cause of formation and the method in source and consistent
In conclusion provided by the invention sentence CO in knowledge natural gas2The method of the origin cause of formation and source, can be to non-in natural gas
Appropriate hydrocarbon gas CO2Organic and/or inorganic and source carry out it is quick, accurate and effective sentence knowledge, this is in-depth Natural Gas Origin
With Source Study, instruct natural gas exploration to provide technical support.And this method has strong operability, analysis quick, reliable
The features such as property is high；CO in knowledge natural gas is sentenced by above-mentioned2The origin cause of formation and the method in source are applied in natural gas exploration, for carrying out day
Right the gas origin cause of formation and Source Study instruct natural gas exploration to be of great significance.
Claims (12)
1. one kind, which is sentenced, knows CO in natural gas2The method of the origin cause of formation and source comprising following steps:
Acquire gas samples；Measure CO in the gas samples2Carbon isotope ratioMeasure the natural gas
Helium isotope ratio R/Ra in sample；Knowledge index system is sentenced in foundation, sentences and knows CO in the gas samples2The origin cause of formation and source；
It is wherein, described to sentence knowledge index system are as follows:
R/Ra≤1 andThen in the natural gas with the non-hydrocarbon gas CO of rare gas association2Mostly shell source has
The machine origin cause of formation；
R/Ra≤1 and δ13CCO2>=-8 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2Mostly shell source without
The machine origin cause of formation；
R/Ra≤0.2 and -10 ‰ < δ13CCO2< -8 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2Mostly
Shell source organic origin with shell source is anorganogene mixes；
1>=R/Ra>0.2 and -10 ‰<δ13CCO2< -8 ‰, then in the natural gas with the non-hydrocarbon gas CO of rare gas association2It is more
For shell source organic origin and curtain source it is anorganogene mix or shell source inorganic with curtain source is anorganogene mixes；
R/Ra > 1, then in the natural gas rare gas association non-hydrocarbon gas CO2Mostly curtain source inorganic.
2. according to the method described in claim 1, it is characterized by: the method for the acquisition gas samples are as follows: by high pressure steel
Bottle is evacuated to 10-1Pa hereinafter, then acquire natural gas middle section air-flow, until the high-pressure cylinder gas pressure be 3-6MPa,
Obtain gas samples.
3. according to the method described in claim 1, it is characterized by: measuring CO in the gas samples2Carbon isotope ratioMethod are as follows: measured using gas chromatograph and isotope mass spectrometer or gas-chromatography isotope mass spectrometry combined instrument
CO in the natural gas sample2Carbon isotope ratio
4. according to the method described in claim 1, it is characterized by: measure helium isotope ratio R in the gas samples/
The method of Ra are as follows: high-pressure cylinder is connected with rare gas sample preparation device in natural gas, passes through rare gas in the natural gas
Sample preparation device isolates He from the gas samples, and the He is sent into rare and refractory metals mass spectrograph, measurement
Helium isotope ratio R/Ra in the gas samples.
5. according to the method described in claim 4, it is characterized by: the high-pressure cylinder is the high pressure with bivalve and double nip
Steel cylinder.
6. method according to claim 1 or 2, it is characterised in that: also wrapped before the acquisition gas samples the step of
The step of including cleaning high-pressure cylinder；
The step is that high-pressure cylinder is evacuated to 10-1Pa connects hereinafter, then connecting first on high-pressure cylinder by the first pressure reducing valve
Mouth is passed through natural gas into high-pressure cylinder and carries out repeated flushing.
7. method according to claim 1 or 3, it is characterised in that: measure CO in the gas samples2Carbon isotope
RatioThe step of be that the natural gas sample is isolated into CO through gas chromatograph2, it is then fed into isotope mass spectrometer
The middle measurement for carrying out carbon isotope, and with high-purity CO of content >=99.999%2For Standard Gases, calculate in the natural gas sample
CO2Carbon isotope ratio
8. according to the method described in claim 3, it is characterized by:
The CO in measuring the gas samples2Carbon isotope ratioThe step of in, the second interface of high-pressure cylinder
Sampling valve is connected, takes natural gas sample from the sampling valve using micro-sampling pin, and natural gas sample is injected into gas chromatograph,
The CO separated by gas-chromatography2Into isotope mass spectrometer, CO in the natural gas sample is measured using isotope mass spectrometer2
Carbon isotope ratio
In the step of measuring helium isotope ratio R/Ra in the gas samples, the second interface connection of high-pressure cylinder the
Two pressure reducing valves, second pressure reducing valve connect injection port in the natural gas on rare gas sample preparation device, film rule and micro
Sampling valve, and by the film rule and micro-sampling valve control enter natural gas in rare gas sample preparation device natural gas into
Sample amount.
9. according to the method described in claim 3, it is characterized by: measuring helium isotope ratio R/Ra in gas samples
The step of in, rare gas sample preparation device includes being used to prepare in natural gas the sample preparation device of rare gas or natural in natural gas
Rare gas trace analysis device in gas.
10. according to the method described in claim 6, it is characterized by: in the cleaning high-pressure cylinder the step of, it is described repeatedly
The method of flushing are as follows: utilize natural gas repeated flushing 4-6 times, each washing time is 10 minutes or more.
11. according to the method described in claim 1, it is characterized by: this, which is sentenced, knows CO in natural gas2The origin cause of formation and the method in source are also
Including by it is described sentence know index system plate be made, and intuitively sentenced according to the plate and know CO in the gas samples2The origin cause of formation
The source and.
12. claim 1-11 is described in any item to sentence CO in knowledge natural gas2The origin cause of formation and the method in source are in natural gas exploration
Using.
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| CN118311168A (en) * | 2024-04-15 | 2024-07-09 | 中国石油大学(华东) | Identifying non-hydrocarbon gas CO combined with helium source2Method for evaluating relative contribution of genes |
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