CN105866293A - Method for joint judgment of coal formed gas and oil type gas by He and N2 and application thereof - Google Patents
Method for joint judgment of coal formed gas and oil type gas by He and N2 and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 93
- 239000003245 coal Substances 0.000 title abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 454
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 227
- 239000003345 natural gas Substances 0.000 claims abstract description 116
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- 229910052734 helium Inorganic materials 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001307 helium Substances 0.000 claims abstract description 28
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 28
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 27
- 230000000155 isotopic effect Effects 0.000 claims description 21
- 238000005070 sampling Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000004454 trace mineral analysis Methods 0.000 claims description 3
- 239000003870 refractory metal Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract 4
- 239000010742 number 1 fuel oil Substances 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 description 41
- 229930195733 hydrocarbon Natural products 0.000 description 38
- 150000002430 hydrocarbons Chemical class 0.000 description 38
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 230000035800 maturation Effects 0.000 description 5
- 238000004176 ammonification Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008436 biogenesis Effects 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002343 natural gas well Substances 0.000 description 2
- 238000006902 nitrogenation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000476 thermogenic effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 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
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides He and N2A method for jointly identifying coal formed gas and oil type gas and application thereof. The method comprises the following steps: collecting natural gas sample, and measuring N2The content, the ratio of nitrogen isotopes, the ratio of helium isotopes and a comprehensive identification index system are established to identify the natural gas sample; wherein, the comprehensive identification index system is as follows: R/Ra is less than or equal to 0.2, N2The content is less than or equal to 9 percent, and15NN2if the natural gas sample is not less than 5 per thousand, the natural gas sample is coal gas; R/Ra is less than or equal to 0.2, N2The content is more than 9 percent, and15NN2less than or equal to 5 thousandths, the natural gas sample is mostly oil type gas; R/Ra is less than or equal to 0.2, N2The content is less than or equal to 9 percent, and15NN2less than or equal to 5 per thousand, the natural gas sample is mostly oil type gas; R/Ra is less than or equal to 0.2, N2The content is less than or equal to 9 percent and less than-5 per mill15NN2If the natural gas sample is less than 5 per mill, the natural gas sample is coal gas or oil gas or the mixture of the coal gas and the oil gas.
Description
Technical field
The invention belongs to oil-gas exploration technical field, relate to a kind of He and N2Combine to sentence and know coal-formed gas, petroliferous gas
Method and application thereof.
Background technology
Natural gas is mainly by CH4、C2H6、C3H8、C4H10Deng hydrocarbon gas, a small amount of CO2、N2Deng non-hydrocarbon gas
And trace is to the composition such as rare gas He, Ne, Ar, Kr, Xe of trace.The natural gas of China is with coal-formed gas
It is main.Coal-formed gas is the main body of China's natural gas reserves and increase of production, occupies in China's natural gas industrial expansion
Very important status.Carry out coal-formed gas, petroliferous gas sentence knowledge, for clear and definite Natural Gas Origin and source, instruct
Natural gas exploration, promote China's natural gas rapid industrial development significant.Currently, coal-formed gas and petroliferous gas
Sentence knowledge mainly to consider from indexs such as carbon isotope of natural gas and component, lighter hydrocarbons, biomarkers.Although non-hydrocarbon gas and
Rare gas, as the important component part of natural gas, has very close relationship with hydrocarbon gas, but there is no at present
Relate to the use of rare gas He and non-hydrocarbon gas N2Combine sentence knowledge natural gas be coal-formed gas or the method for petroliferous gas and refer to
Mark.
Summary of the invention
In view of the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of He and N2Combine and sentence knowledge coal one-tenth
Gas, the method for petroliferous gas, the method can utilize the rare gas He in natural gas and non-hydrocarbon gas N2Combine and sentence
Knowing this natural gas is coal-formed gas or petroliferous gas.
In order to reach aforesaid goal of the invention, a kind of He and N that the present invention provides2Combine and sentence knowledge coal-formed gas, oil type
The method of gas, it comprises the following steps:
Gather gas samples；
Measure N in described gas samples2Content；
Measure N in described gas samples2Nitrogen isotope ratio
Measure helium in described gas samples isotopic ratio R/Ra or3He/4He；
Set up comprehensive discrimination index system, sentence the described gas samples of knowledge；
Wherein, sentencing comprehensive knowledge index system described in is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThe most described natural
Gas sample mostly originally is coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, andThe most described natural
Gas sample mostly originally is petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThe most described natural
Gas sample mostly originally is petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThen described
Gas samples be coal-formed gas or petroliferous gas or the two be mixed into because of gas.
In the above-mentioned methods, described natural gas includes the natural hydro carbons contained in stratum and the mixing of non-hydrocarbon gases
Thing.
In the above-mentioned methods, described natural gas includes but not limited to casing-head gas, reservoir gas, coal bed gas, shale gas, mud
Volcanic gas or biogas etc..
In the above-mentioned methods, the isotopic ratio R/Ra of helium and the isotopic ratio of helium3He/4He is the isotope of helium
The different method for expressing of ratio, both can according to R/Ra=(3He/4He)/(1.4×10-6) relational expression mutually converts.
In the above-mentioned methods, sentencing comprehensive knowledge index system described in isComprehensive discrimination index system, institute
StateComprehensive discrimination index system is that two-step method sentences knowledge index system, wherein,Refer to
Mark sentences the non-hydrocarbon gas N known in described gas samples2The origin cause of formation,Index is (i.e.Index)
Sentence knowledge described gas samples be coal-formed gas, petroliferous gas, coal-formed gas or petroliferous gas or the two be mixed into because of gas (i.e. coal become
Gas and/or petroliferous gas are uncertain).
Non-hydrocarbon gas N in the above-mentioned methods, when R/Ra≤0.2, in described gas samples2For organic origin；
Described organic origin includes the three big origin causes of formation, wherein,
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2For biogenesis,
Control essentially from microorganism denitrification or nitrogenation；
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2For organic
Matter thermogenic gas, essentially from the hot Ammonification that the maturation period ripe, high is organic；
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2It is pyrolyzed for organic matter
The origin cause of formation, essentially from the splitting action that the post-mature stage is organic.
In the above-mentioned methods, describedIndex is mainly divided into three regions, the most described gas samples bag
Include three big: coal-formed gas type, oil gas type, coal-formed gas and/or petroliferous gas are uncertain.
In the above-mentioned methods, described gas samples is coal-formed gas and/or uncertain (i.e. coal-formed gas or the oil type of petroliferous gas
Gas or the two be mixed into because of gas) for can not be according to describedIndex is sentenced this gas samples of knowledge and is specially coal
Gas, oil gas type or coal-formed gas and petroliferous gas mixing.
In the above-mentioned methods, it is preferable that the method for described collection gas samples is: high-pressure cylinder is evacuated to 10-1Pa
Hereinafter, then gather the stage casing air-flow of natural gas, until the gas pressure of described high-pressure cylinder is 3-6MPa, obtain
Gas samples.
In the above-mentioned methods, the maximum working pressure (MWP) of described high-pressure cylinder is 15MPa.
In the above-mentioned methods, it is preferable that N in the described gas samples of this mensuration2The method of content is: utilize trace
Sample introduction needle is extracted in natural gas sample, and injection gas chromatography instrument from sampling valve and is measured N in described natural gas sample2Contain
Amount.
In the above-mentioned methods, it is preferable that N in the described gas samples of this mensuration2Nitrogen isotope ratio's
Method is: utilize gas chromatograph and isotope mass spectrometer, or gas chromatogram isotope mass spectrometry combined instrument measures described
N in gas samples2Nitrogen isotope ratio
In the above-mentioned methods, it is preferable that in the described gas samples of this mensuration helium isotopic ratio R/Ra or3He/4The method of He is: be connected with rare gas sample preparation device in natural gas by described high-pressure cylinder, by described sky
So in gas, rare gas sample preparation device isolates He from described gas samples, and described He is sent into rare gas
In isotope mass spectrometer, measure the helium isotope ratio R/Ra in described gas samples or3He/4He。
In the above-mentioned methods, it is preferable that described high-pressure cylinder is the high-pressure cylinder with bivalve and double nip.
In the above-mentioned methods, described bivalve includes air relief valve and/or sampling valve.
In the above-mentioned methods, it is preferable that also include cleaning described high pressure steel before the step of described collection gas samples
The step of bottle；
This step is for be evacuated to 10 by described high-pressure cylinder-1Below Pa, then passes through the first interface of described high-pressure cylinder
First air relief valve connects and is connected with described sampling well head, is passed through natural gas and repeatedly rinses in described high-pressure cylinder.
In the above-mentioned methods, gas samples can directly be gathered after described high-pressure cylinder is cleaned for several times.
In the above-mentioned methods, described high-pressure cylinder includes rustless steel high-pressure cylinder etc., but is not limited to this.
In the above-mentioned methods, described first air relief valve is connected with natural gas well valve, then from this sky by connecting pipeline
Gas well so obtains natural gas and rinses described high-pressure cylinder, and adopt to obtain above-mentioned gas samples.
In the above-mentioned methods, in the step of described collection gas samples and/or the step of described cleaning high-pressure cylinder,
Use the vacuum pumps such as mechanical pump by described high-pressure cylinder evacuation, be evacuated to 10-1Below Pa.
In the above-mentioned methods, N in the described gas samples of described mensuration2In the step of content, described gas chromatogram
Instrument can be the gas chromatograph of conventional constituents content analysis detection.
In the above-mentioned methods, N in the described gas samples of this mensuration2In the step of content, described natural gas sample
Consumption by described micro-sampling pin control, this consumption is this area conventional amount used.
In the above-mentioned methods, it is preferable that N in the described gas samples of this mensuration2Nitrogen isotope ratio's
Step is that through described gas chromatograph, described gas samples is isolated N2, it is then fed into described isotope mass spectrometer
In carry out the mensuration of nitrogen isotope, and with N in air2For standard, it is calculated N in described gas samples2Nitrogen
Isotopic ratio
In the above-mentioned methods, it is preferable that N in the described gas samples of this mensuration2Nitrogen isotope ratio
Step in, described high-pressure cylinder second interface connect described sampling valve, utilize micro-sampling pin at this sampling valve
Extract natural gas sample, and natural gas is injected gas chromatograph, isolate N through gas chromatograph2, utilize coordination
Quality spectrometer measures N in described natural gas sample2Nitrogen isotope ratio
In the above-mentioned methods, N in the described gas samples of this mensuration2Nitrogen isotope ratioStep in,
The consumption of described natural gas sample is controlled by described micro-sampling pin, and this consumption is this area conventional amount used.
In the above-mentioned methods, N in described natural gas sample2Content is also N in this gas samples2Content；Described sky
So N in gas sample product2Nitrogen isotope ratioAlso it is the N in this gas samples2Nitrogen isotope ratio
In the above-mentioned methods, it is preferable that in the described gas samples of this mensuration helium isotopic ratio R/Ra or3He/4In the step of He, the second interface of described high-pressure cylinder connects the second air relief valve, and this second air relief valve connects institute
Injection port, thin film rule and the microsampling valve stated in natural gas on rare gas sample preparation device, and advised by described thin film
Control to enter the natural gas sample size of rare gas sample preparation device in described natural gas with microsampling valve.
In the above-mentioned methods, depending on described natural gas sample size is according to being embodied as needing.
In the above-mentioned methods, in the described gas samples of this mensuration helium isotopic ratio R/Ra or3He/4He
Step in, use rare gas sample preparation device in described natural gas to purify, remove the active gases beyond rare gas,
And carry out the separation of rare gas, isolate He.
In the above-mentioned methods, it is preferable that in the described gas samples of this mensuration helium isotopic ratio R/Ra or3He/4In the step of He, in described natural gas, rare gas sample preparation device includes for preparing rare gas in natural gas
Sample preparation device or natural gas in rare gas trace analysis device, but be not limited to this.
In the above-mentioned methods, it is preferable that in the step of described cleaning high-pressure cylinder, the described method repeatedly rinsed is:
Utilizing natural gas repeatedly to rinse 4-6 time, each washing time is more than 10 minutes.
In the above-mentioned methods, it is preferable that set up comprehensive discrimination index system, sentence in the step knowing described gas samples,
Described gas samples is coal-formed gas or petroliferous gas or the two is when being mixed into because of gas, need to measure alkane in described gas samples
The carbon isotope ratio of hydrocarbon, and be coal-formed gas, petroliferous gas according to the described carbon isotope ratio described gas samples of differentiation
Or coal-formed gas and petroliferous gas mixing.
In the above-mentioned methods, in the described gas samples of described mensuration, the carbon isotope ratio of alkane can be conventional with this area
Method.
In the above-mentioned methods, described is coal-formed gas, oil type according to the described carbon isotope ratio described gas samples of differentiation
The method of gas or coal-formed gas and petroliferous gas mixing is this area routine techniques.
In the above-mentioned methods, it is preferable that the method also includes described comprehensive discrimination index system is made plate, and root
The step knowing described gas samples is intuitively sentenced according to described plate.
Present invention also offers above-mentioned He and N2Combine sentence know coal-formed gas, petroliferous gas method in natural gas exploration
Application.
Above-mentioned He and N that the present invention provides2Combine and sentence knowledge coal-formed gas, the method for petroliferous gas, it is possible to use natural gas
Middle rare gas He and non-hydrocarbon gas N2To this natural gas it is coal-formed gas or petroliferous gas carries out quick, accurate and effective
Sentencing knowledge, the method has feature easy and simple to handle, efficient, reliable, this for in-depth Natural Gas Origin and Source Study,
Natural gas exploration is instructed to provide technical support.By above-mentioned He and N2Combine and sentence knowledge coal-formed gas, the method for petroliferous gas
It is applied in natural gas exploration, for carrying out Natural Gas Origin and Source Study, instructing natural gas exploration to have important meaning
Justice.
Accompanying drawing explanation
Fig. 1 is He and N of embodiment 1-32Combine and sentence knowledge coal-formed gas, the method flow diagram of petroliferous gas；
Fig. 2 is that embodiment 1 is under the conditions of R/Ra≤0.2Sentence knowledge plate；
Fig. 3 is embodiment 1-3 and He and N of checking example 1-22Combine and sentence knowledge coal-formed gas, the result map 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 can the restriction of practical range to the present invention.
Embodiment 1
Present embodiments provide a kind of He and N2Combining and sentence knowledge coal-formed gas, the method for petroliferous gas, it is according to following step
Suddenly carry out:
Use natural gas (i.e. oil gas field in tower) the conduct research sample of natural gas from Tarim Basin field exploitation, according to figure
Flow process shown in 1 is detected and analyzed:
Selecting volume is the 1L rustless steel high-pressure cylinder with bivalve and double nip, utilizes before gas samples gathers
Above-mentioned rustless steel high-pressure cylinder is evacuated to 10 by mechanical pump-1Below Pa；
By the first interface of above-mentioned rustless steel high-pressure cylinder by connecting pipeline and the first air relief valve and natural gas well head phase
Even, utilize natural gas repeatedly to rinse above-mentioned steel cylinder 4-6 time, continue more than 10 minutes every time, then gather this natural
The stage casing air-flow of gas, until the gas pressure of described steel cylinder is 3-6MPa, then stops sampling, it is thus achieved that to be measured natural
Gas sample is originally；
Second interface of the high-pressure cylinder of this collection gas samples is connected with sampling valve, utilizes micro-sampling pin from institute
State and take appropriate first natural gas sample at sampling valve, inject in the gas chromatograph of conventional constituents content analysis detection and measure
N in described first natural gas sample2Content, in percentage (%)；
Second interface of the high-pressure cylinder of this collection gas samples is connected with sampling valve, utilizes described micro-sampling pin
At described sampling valve, take appropriate second natural gas sample again, inject in this gas chromatogram isotope mass spectrometry combined instrument, institute
State second natural gas sample N in gas chromatogram isolates natural gas2, then by this isolated N2Send into phase
Isotope mass spectrometer even carries out the mensuration of nitrogen isotope, with N in air2For standard, calculate described second natural
N in gas sample product2Nitrogen isotope ratioIn terms of permillage (‰)；
The second interface that collection has the high-pressure cylinder of gas samples is dilute with natural gas successively by the second air relief valve
Have the injection port on gas trace analytical equipment, thin film rule be connected with microsampling valve, then by described thin film rule with
Microsampling valve controls the sample size of gas samples, utilize rare gas trace analysis device in this natural gas to purify,
Remove the active gases in addition to rare gas in described gas samples, and carry out the separation of rare gas, will separate
He send in rare and refractory metals mass spectrograph, measure the isotopic ratio of rare gas helium in this gas samples,
With3He/4He or R/Ra counts；
Utilize the isotopic ratio R/Ra of rare gas helium in above-mentioned gas samples, non-hydrocarbon gas N2Content and N2
Nitrogen isotope ratioSet up He and N2Combine to sentence and know coal-formed gas, petroliferous gas
Index system and plate, this domain is as in figure 2 it is shown, described comprehensive discrimination index system is:
(1) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andTime,
The most described gas samples mostly typically is coal-formed gas, as shown in Fig. 2 the IVth district；
(2) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, andTime,
The most described gas samples mostly typically is petroliferous gas, as shown in Fig. 2 the Ith district；
(3) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andTime,
The most described gas samples mostly typically is petroliferous gas, as shown in Fig. 2 the IIth district；
(4) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and
Time, the most described gas samples be coal-formed gas or petroliferous gas or the two be mixed into because of gas, as shown in Fig. 2 the IIIth district, this
Time need to measure the carbon isotope ratio of alkane in described gas samples, and according to this further district of carbon isotope ratio
Dividing described gas samples is coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas mixing.
Through detecting analysis above, the natural gas of the natural gas from Tarim Basin field exploitation that the present embodiment uses, the rarest
The isotope of gas helium3He/4He is substantially 10-8Magnitude, R/Ra ＜ 0.1, therefore, the rare gas in this natural gas
Body He is typical crustal origin；
According to He and N2Combine to sentence and know coal-formed gas, petroliferous gasIn index system
Index sentence knowledge, the R/Ra ＜ 0.1 that described gas samples records, therefore, the non-hydrocarbon gas N in this natural gas2
For shell source organic origin；
Described organic origin includes the three big origin causes of formation, wherein,
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2For biogenesis,
Essentially from microorganism denitrification or nitrogenation；
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2For organic
Matter thermogenic gas, essentially from the hot Ammonification that the maturation period ripe, high is organic；
When R/Ra≤0.2,Time, the non-hydrocarbon gas N in described gas samples2It is pyrolyzed for organic matter
The origin cause of formation, essentially from the splitting action that the post-mature stage is organic；
Non-hydrocarbon gas N in the natural gas of the natural gas from Tarim Basin field exploitation that the present embodiment uses2Nitrogen isotope
RatioMainly fallScope in, fall into individuallyScope
In, therefore, the non-hydrocarbon gas N in the natural gas of the natural gas from Tarim Basin field exploitation that the present embodiment uses2Mainly
For the organic origin cause of formation, essentially from maturation period organic matter pyrolysis ripe, high；
Further with according to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex body
In systemWhat index carried out coal-formed gas and petroliferous gas to the hydrocarbon gas of this natural gas sentences knowledge, this natural gas
The N that sample records2Content andScope fall at N2Content ＞ 9% andAnd N2Content≤9%
AndRegion in, as shown in the Ith district in Fig. 3 and the IIth district；Combine above-mentioned He and N2Associating
Sentence and know coal-formed gas, petroliferous gasIndex system and plate, the Tarim Basin that the present embodiment uses
The natural gas of gas field exploitation is essentially petroliferous gas.
In the present embodiment, the natural gas of actual Tarim Basin gas field exploitation is essentially petroliferous gas, this and this enforcement
He and N that example provides2The identifying result combining the method sentencing knowledge coal-formed gas, petroliferous gas is consistent.
As can be seen here, He and N that the present embodiment provides2Combine and sentence knowledge coal-formed gas, the method for petroliferous gas, can be in order to
With rare gas He in natural gas and non-hydrocarbon gas N2To this natural gas it is coal-formed gas or petroliferous gas carries out quick, accurate
Really, effectively sentencing knowledge, the method has feature easy and simple to handle, efficient, reliable, for in-depth Natural Gas Origin and source
Study, instruct natural gas exploration to provide technical support.
Embodiment 2
Present embodiments provide a kind of He and N2Combining and sentence knowledge coal-formed gas, the method for petroliferous gas, it is according to following step
Suddenly carry out:
The present embodiment uses the natural as research sample of enlightening Na 2 gas-field exploitation, examines according to the flow process shown in Fig. 1
Survey and analyze:
The present embodiment uses the method for embodiment 1 to sample the gas samples of described enlightening Na 2 gas-field exploitation,
And this gas samples is carried out N2The detection of content, N2Nitrogen isotope ratioAnd the isotopic ratio of helium
The detection of R/Ra；Then He and N set up according to embodiment 12Combine to sentence and know coal-formed gas, petroliferous gas Helium isotope ratio R/Ra, the non-hydrocarbon gas N that the present embodiment gas samples is recorded by index system and plate2
Content and N2Nitrogen isotope ratioIt is analyzed；
After measured, the isotopic ratio R/Ra ＜ 0.1 (i.e. R/Ra≤0.2) of rare gas helium in this gas samples,
And3He/4He ＜ 2.8 × 10-7, therefore, the rare gas He in this gas samples is typical crustal origin；Root
According to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIn index system
Index sentence knowledge, the non-hydrocarbon gas N in described gas samples2Nitrogen isotope ratioFall Scope in, therefore, the non-hydrocarbon gas N in this gas samples2For the organic origin cause of formation, essentially from post-mature
Stage organic matter splitting action；
Further with according to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex body
In systemWhat the hydrocarbon gas in this gas samples of index carried out coal-formed gas and petroliferous gas sentences knowledge, this sky
The N that so gas sample originally records2Content andScope fall at N2Content≤9% andRegion in,
As shown in the IVth district in Fig. 3；Combine above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gas
Index system and plate, the natural gas of enlightening Na 2 gas-field exploitation that the present embodiment uses is essentially coal-formed gas.
In the present embodiment, the natural gas of actual enlightening Na 2 gas-field exploitation is essentially coal-formed gas, and this provides with the present embodiment
He and N2The identifying result combining the method sentencing knowledge coal-formed gas, petroliferous gas is consistent.
Embodiment 3
Present embodiments provide a kind of He and N2Combining and sentence knowledge coal-formed gas, the method for petroliferous gas, it is according to following step
Suddenly carry out:
The present embodiment uses the natural as research sample of Kela 2 Gas Field exploitation, examines according to the flow process shown in Fig. 1
Survey and analyze:
The gas samples that the present embodiment uses the method for embodiment 1 to exploit described Kela 2 Gas Field is sampled,
And this gas samples is carried out N2The detection of content, N2Nitrogen isotope ratioAnd the isotopic ratio of helium
The detection of R/Ra；Then He and N set up according to embodiment 12Combine and sentence knowledge coal-formed gas, the R/Ra-δ of petroliferous gas15NN2-N2Helium isotope ratio R/Ra, the non-hydrocarbon gas N that the present embodiment gas samples is recorded by index system and plate2
Content and N2Nitrogen isotope ratioIt is analyzed；
After measured, the isotopic ratio R/Ra ＜ 0.1 (i.e. R/Ra≤0.2) of rare gas helium in this gas samples,
And3He/4He ＜ 2.8 × 10-7, therefore, the rare gas He in this gas samples is typical crustal origin；Root
According to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIn index system
Index sentence knowledge, the non-hydrocarbon gas N in described gas samples2Nitrogen isotope ratioFall at-10 ‰ ＜Scope in, therefore, the non-hydrocarbon gas N in this gas samples2For organic origin, essentially from
Maturation period ripe, high organic hot Ammonification；
Further with according to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex body
In systemWhat index carried out coal-formed gas and petroliferous gas to the hydrocarbon gas in this gas samples sentences knowledge, should
The N that gas samples records2Content andScope fall at N2Content≤9% and's
In region, i.e. coal-formed gas or petroliferous gas or the two be mixed into because of in gas region, as shown in the IIIth district in Fig. 3, therefore,
Combine above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex system and plate, this reality
The natural gas executing the Kela 2 Gas Field exploitation that example uses also needs to measure further the carbon coordination of alkane in this gas samples
Element ratio, and be coal-formed gas, petroliferous gas or coal-formed gas and oil type according to this carbon isotope ratio to this gas samples
Gas mixing is distinguish between.
Additionally, great Bei gas field, Ke Keya gas field, Donghetang oil gas field, wheel south oil gas field are also gathered by the present embodiment
Gas samples is respectively adopted the method for embodiment 1 and tests and analyze, and all records the non-hydrocarbon gas in gas samples
Body N2For shell source organic origin；Additionally, record the N of each gas samples2Content andScope all fall within
N2Content≤9% andRegion in, i.e. coal-formed gas or petroliferous gas or the two be mixed into because of gas district
In territory, as shown in the IIIth district in Fig. 3, therefore, above-mentioned He and N is combined2Combine and sentence knowledge coal-formed gas, petroliferous gas
'sIndex system and plate, to great Bei gas field, Ke Keya gas field, Donghetang oil gas field, wheel south
The natural gas of exploitation of oil-gas field also needs to measure the most further the carbon isotope ratio of each middle alkane, and according to this carbon coordination
Element ratio to each gas samples be coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas mixing be distinguish between respectively.
Checking example 1
This checking example uses the natural gas with river, field exploitation of oil-gas field as identifying object, comes according to the method for embodiment 1
Described and river, field exploitation of oil-gas field gas samples is tested, then according to embodiment 1 set up He and
N2Combine to sentence and know coal-formed gas, petroliferous gasIndex system and plate gas sample natural to this checking example
Originally helium isotope ratio R/Ra, the non-hydrocarbon gas N recorded2Content and N2Nitrogen isotope ratioCarry out
Checking is analyzed；
The isotopic ratio R/Ra ＜ 0.2 of rare gas helium in this gas samples, and3He/4He ＜ 2.8 × 10-7, because of
This, the rare gas He in this gas samples is typical crustal origin；According to above-mentioned He and N2Combine and sentence knowledge
Coal-formed gas, petroliferous gasIn index systemIndex sentence knowledge, described natural gas
Non-hydrocarbon gas N in sample2Nitrogen isotope ratioFallScope in, because of
This, the non-hydrocarbon gas N in this gas samples2For organic origin, organic essentially from the maturation period ripe, high
Hot Ammonification；
Further with according to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex body
In systemWhat index carried out coal-formed gas and petroliferous gas to the hydrocarbon gas in this gas samples sentences knowledge, should
The N that gas samples records2Content andScope fall at N2Content ＞ 9% andRegion
In, as shown in the Ith district in Fig. 3；Combine above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gas Index system and plate, that this checking example uses and river, field exploitation of oil-gas field natural gas is essentially petroliferous gas,
This identifying result is consistent with actual result.
Checking example 2
This checking example uses the natural gas of Yaha gas field exploitation as identifying object, comes institute according to the method for embodiment 1
The gas samples stating Yaha gas field exploitation is tested, He and N then set up according to embodiment 12Combine and sentence
Know coal-formed gas, petroliferous gasThe helium that this checking example gas samples is recorded by index system and plate
Isotopic ratio R/Ra, non-hydrocarbon gas N2Content and N2Nitrogen isotope ratioCarry out checking to analyze；
The isotopic ratio R/Ra ＜ 0.2 of rare gas helium in this gas samples, and3He/4He ＜ 2.8 × 10-7, because of
This, the rare gas He in this gas samples is typical crustal origin；According to above-mentioned He and N2Combine and sentence knowledge
Coal-formed gas, petroliferous gasIn index systemIndex sentence knowledge, described natural gas
Non-hydrocarbon gas N in sample2Nitrogen isotope ratioFallScope in, therefore, should
Non-hydrocarbon gas N in gas samples2For organic origin, essentially from the splitting action that the post-mature stage is organic；
Further with according to above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex body
In systemWhat the hydrocarbon gas in this gas samples of index carried out coal-formed gas and petroliferous gas sentences knowledge, this sky
The N that so gas sample originally records2Content andScope fall≤9% andRegion in, such as Fig. 3
In the IVth district shown in；Combine above-mentioned He and N2Combine to sentence and know coal-formed gas, petroliferous gasIndex
System and plate, the natural gas of the Yaha gas field exploitation that this checking example uses is essentially coal-formed gas, this identifying result and reality
Border result is consistent.
In sum, above-mentioned He and N that the present invention provides2Combine knowledge coal-formed gas, the method for petroliferous gas sentenced, permissible
Utilize rare gas He and non-hydrocarbon gas N in natural gas2To this natural gas it is coal-formed gas or petroliferous gas is carried out substantially soon
Fast, accurate and effective sentencing knowledge, the method has feature easy and simple to handle, efficient, reliable, and this becomes for in-depth natural gas
Cause and Source Study, natural gas exploration is instructed to provide technical support.By above-mentioned He and N2Combine sentence knowledge coal-formed gas,
The method of petroliferous gas is applied in natural gas exploration, for carrying out Natural Gas Origin and Source Study, instructing natural gas to survey
Visit significant.
Claims (10)
1. He and N2Combining and sentence knowledge coal-formed gas, the method for petroliferous gas, it comprises the following steps:
Gather gas samples；
Measure N in described gas samples2Content；
Measure N in described gas samples2Nitrogen isotope ratio δ15NN2；
Measure helium in described gas samples isotopic ratio R/Ra or3He/4He；
Set up comprehensive discrimination index system, sentence the described gas samples of knowledge；
Wherein, sentencing comprehensive knowledge index system described in is:
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and δ15NN2>=5 ‰, the most described natural
Gas sample mostly originally is coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, and δ15NN2≤ 5 ‰, the most described natural
Gas sample mostly originally is petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and δ15NN2≤-5 ‰, the most described natural
Gas sample mostly originally is petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and-5 ‰ ＜ δ15NN2＜ 5 ‰, then described
Gas samples be coal-formed gas or petroliferous gas or the two be mixed into because of gas.
Method the most according to claim 1, it is characterised in that: the method for described collection gas samples is:
High-pressure cylinder is evacuated to 10-1Below Pa, then gathers the stage casing air-flow of natural gas, until the gas of described high-pressure cylinder
Pressure is 3-6MPa, obtains gas samples；
Preferably, N in described gas samples is measured2The method of content is: utilize micro-sampling pin to carry from sampling valve
Take and natural gas sample, and injection gas chromatography instrument measure N in described natural gas sample2Content；
Preferably, N in described gas samples is measured2Nitrogen isotope ratio δ15NN2Method be: utilize gas phase
N in chromatograph and isotope mass spectrometer, or the gas chromatogram isotope mass spectrometry combined instrument described gas samples of mensuration2
Nitrogen isotope ratio δ15NN2；
Preferably, measure helium in described gas samples isotopic ratio R/Ra or3He/4The method of He is:
Described high-pressure cylinder is connected with rare gas sample preparation device in natural gas, by rare gas sample preparation in described natural gas
Device isolates He from described gas samples, and is sent into by described He in rare and refractory metals mass spectrograph, surveys
Helium isotope ratio R/Ra in fixed described gas samples or3He/4He；
Preferably, described high-pressure cylinder is the high-pressure cylinder with bivalve and double nip.
Method the most according to claim 1 and 2, it is characterised in that: in the step of described collection gas samples
The step cleaning described high-pressure cylinder is also included before Zhou；
This step is for be evacuated to 10 by described high-pressure cylinder-1Below Pa, then passes through the first interface of described high-pressure cylinder
First air relief valve is connected with described sampling well head, is passed through natural gas and repeatedly rinses in described high-pressure cylinder.
Method the most according to claim 1 and 2, it is characterised in that: N in the described gas samples of this mensuration2
Nitrogen isotope ratio δ15NN2Step be that described gas samples is isolated N through described gas chromatograph2, so
The described isotope mass spectrometer of rear feeding carries out the mensuration of nitrogen isotope, and with N in air2For standard, it is calculated
N in described gas samples2Nitrogen isotope ratio δ15NN2。
Method the most according to claim 2, it is characterised in that:
N in the described gas samples of this mensuration2Nitrogen isotope ratio δ15NN2Step in, described high-pressure cylinder
The second interface connect described sampling valve, utilize micro-sampling pin to extract natural gas sample at this sampling valve, and by sky
So gas injection gas chromatography instrument, isolates N through gas chromatograph2, utilize isotope mass spectrometer to measure described natural gas
N in sample2Nitrogen isotope ratio δ15NN2；
Preferably, in the described gas samples of this mensuration helium isotopic ratio R/Ra or3He/4The step of He
In, the second interface of described high-pressure cylinder connects the second air relief valve, and this second air relief valve connects in described natural gas rare
Injection port, thin film rule and microsampling valve on gas sample preparation device, and by described thin film rule and microsampling valve control
System enters the natural gas sample size of rare gas sample preparation device in described natural gas.
6. according to the method described in claim 2 or 5, it is characterised in that: in the described gas samples of this mensuration
The isotopic ratio R/Ra of helium or3He/4In the step of He, in described natural gas, rare gas sample preparation device includes
Rare gas trace analysis device in the sample preparation device preparing rare gas in natural gas or natural gas.
Method the most according to claim 3, it is characterised in that: in the step of described cleaning high-pressure cylinder,
The described method repeatedly rinsed is: utilizing natural gas repeatedly to rinse 4-6 time, each washing time is more than 10 minutes.
Method the most according to claim 1, it is characterised in that: set up comprehensive discrimination index system, sentence knowledge institute
Stating in the step of gas samples, described gas samples is coal-formed gas or petroliferous gas or the two is when being mixed into because of gas, needs
Measure the carbon isotope ratio of alkane in described gas samples, and distinguish described natural according to described carbon isotope ratio
Gas sample is originally coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas mixing.
Method the most according to claim 1, it is characterised in that: the method also includes referring to described comprehensive discrimination
Mark system makes plate, and intuitively sentences the step knowing described gas samples according to described plate.
10. He and N described in any one of claim 1-92Combine sentence know coal-formed gas, petroliferous gas method natural
Application in gas exploration.
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