CN105866293B - A kind of He and N2Combine the method and its application sentenced and know coal-formed gas, petroliferous gas - Google Patents
A kind of He and N2Combine the method and its application sentenced and know coal-formed gas, petroliferous gas Download PDFInfo
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- CN105866293B CN105866293B CN201610379611.0A CN201610379611A CN105866293B CN 105866293 B CN105866293 B CN 105866293B CN 201610379611 A CN201610379611 A CN 201610379611A CN 105866293 B CN105866293 B CN 105866293B
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Abstract
The present invention provides a kind of He and N2Combine the method and its application sentenced and know coal-formed gas, petroliferous gas.This approach includes the following steps：It acquires gas samples, measure N2Content measures nitrogen isotope ratio, measures helium isotope ratio and establish comprehensive discrimination index system, sentences and knows gas samples；Wherein, this, which is sentenced, comprehensive know index system and is：R/Ra≤0.2, N2Content≤9%, and δ15NN2>=5 ‰, then the gas samples are coal-formed gas；R/Ra≤0.2, N2Content ＞ 9%, and δ15NN2≤ 5 ‰, then the gas samples are mostly petroliferous gas；R/Ra≤0.2, N2Content≤9%, and δ15NN2≤ 5 ‰, then the gas samples are mostly petroliferous gas；R/Ra≤0.2, N2Content≤9%, and 5 ‰ ＜ δ15NN2＜ 5 ‰, then the gas samples are that coal-formed gas or petroliferous gas or the two are mixed into because of gas.
Description
Technical field
The invention belongs to oil-gas exploration technical fields, are related to a kind of He and N2Combine the method sentenced and know coal-formed gas, petroliferous gas
And its application.
Background technology
Natural gas is mainly by CH4、C2H6、C3H8、C4H10Equal hydrocarbon gas, a small amount of CO2、N2Equal non-hydrocarbon gas and trace arrive
The compositions such as micro rare gas He, Ne, Ar, Kr, Xe.The natural gas of China is based on coal-formed gas.Coal-formed gas is that China is natural
The main body of gas reserves and increase of production occupies very important status in China's natural gas industrial expansion.Carry out coal at
Gas, petroliferous gas sentence knowledge, for clear Natural Gas Origin and source, instruct natural gas exploration, push China's natural gas industry fast
Speed development is of great significance.Currently, coal-formed gas and petroliferous gas sentence knowledge mainly from carbon isotope of natural gas and component, lighter hydrocarbons,
The indexs such as biomarker consider.Although the important component of non-hydrocarbon gas and rare gas as natural gas, with hydro carbons gas
Body has very close relationship, but there is no relate to the use of rare gas He and non-hydrocarbon gas N at present2Combine sentence know natural gas be
The method and index of coal-formed gas or petroliferous gas.
Invention content
The shortcomings that in view of the above-mentioned prior art, the purpose of the present invention is to provide a kind of He and N2Combine sentence know coal-formed gas,
The method of petroliferous gas, this method can utilize rare gas He and non-hydrocarbon gas N in natural gas2Combine sentence know the natural gas be
Coal-formed gas or petroliferous gas.
In order to reach goal of the invention above-mentioned, a kind of He and N provided by the invention2Combine to sentence and knows coal-formed gas, petroliferous gas
Method comprising following steps：
Acquire gas samples；
Measure N in the gas samples2Content；
Measure N in the gas samples2Nitrogen isotope ratio
Measure helium in the gas samples isotopic ratio R/Ra or3He/4He；
Comprehensive discrimination index system is established, sentences and knows the gas samples；
Wherein, it is described sentence comprehensive know index system and be：
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThe then natural gas
Sample is mostly coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, andThe then natural gas
Sample is mostly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThe then natural gas
Sample is mostly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andThe then day
Right gas sample sheet is that coal-formed gas or petroliferous gas or the two are mixed into because of gas.
In the above-mentioned methods, the natural gas includes the mixing for naturally containing hydro carbons and non-hydrocarbon gases in stratum
Object.
In the above-mentioned methods, the natural gas includes but not limited to casing-head gas, reservoir gas, coal bed gas, shale gas, mud volcano
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 isotopic ratio of helium
Different representation methods, the two can according to R/Ra=(3He/4He)/(1.4×10-6) relational expression mutually converts.
In the above-mentioned methods, it is described sentence comprehensive know index system and beComprehensive discrimination index system, it is describedComprehensive discrimination index system is that two-step method sentences knowledge index system, whereinIndex, which is sentenced, knows institute
State the non-hydrocarbon gas N in gas samples2The origin cause of formation,Index is (i.e.Index) sentence and knows the natural gas
Sample is that coal-formed gas, petroliferous gas, coal-formed gas or petroliferous gas or the two are mixed into because (i.e. coal-formed gas and/or petroliferous gas be not true for gas
It is fixed).
In the above-mentioned methods, as R/Ra≤0.2, the non-hydrocarbon gas N in the gas samples2For organic origin；
The organic origin includes the three big origin causes of formation, wherein
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2It is main for biogenesis
It to come from microorganism denitrification or nitrogenation controls；
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2For organic matter
Thermogenic gas, essentially from the hot ammoniation of ripe, high stage of ripeness organic matter；
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2For organic matter pyrolysis at
Cause, essentially from the splitting action of post-mature stage organic matter.
In the above-mentioned methods, describedIndex is mainly divided into three regions, i.e., the described gas samples include
Three is big：Coal-formed gas type, oil gas type, coal-formed gas and/or petroliferous gas are uncertain.
In the above-mentioned methods, the gas samples are that coal-formed gas and/or petroliferous gas do not know (i.e. coal-formed gas or petroliferous gas
Or the two is mixed into because of gas) be cannot be according to describedIt is specially coal-formed gas, oil gas that index, which is sentenced and knows the gas samples,
Type or the mixing of coal-formed gas and petroliferous gas.
In the above-mentioned methods, it is preferable that it is described acquisition gas samples method be：High-pressure cylinder is evacuated to 10-1Pa with
Under, the stage casing 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 N in the measurement gas samples2The method of content is：Utilize micro-sampling
Needle extracts natural gas sample from sampling valve, and injects in gas chromatograph and measure N in the natural gas sample2Content.
In the above-mentioned methods, it is preferable that N in the measurement gas samples2Nitrogen isotope ratioMethod
For：The natural gas sample is measured using gas chromatograph and isotope mass spectrometer or gas-chromatography isotope mass spectrometry combined instrument
N in this2Nitrogen isotope ratio
In the above-mentioned methods, it is preferable that in the measurement gas samples isotopic ratio R/Ra of helium or3He/4The method of He is：The high-pressure cylinder is connected with rare gas sample preparation device in natural gas, by rare in the natural gas
Gas sample preparation device isolates He from the gas samples, and the He is sent into rare and refractory metals mass spectrograph,
Measure helium isotope ratio R/Ra in the gas samples or3He/4He。
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 the cleaning high pressure steel before the acquisition gas samples the step of
The step of bottle；
The step is that the high-pressure cylinder is evacuated to 10-1Then Pa is hereinafter, pass through the first interface of the high-pressure cylinder
The connection of first pressure reducing valve is connect with the sampling well head, and be passed through natural gas into the high-pressure cylinder is rinsed repeatedly.
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, first pressure reducing valve is connect by connecting pipeline with natural gas well valve, 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, the N in the measurement gas samples2In the step of content, the gas chromatograph
It can be the gas chromatograph of conventional constituents content analysis detection.
In the above-mentioned methods, the N in the measurement gas samples2In the step of content, the natural gas sample
Dosage is controlled by the micro-sampling pin, which is this field conventional amount used.
In the above-mentioned methods, it is preferable that N in the measurement gas samples2Nitrogen isotope ratioThe step of
It is that the gas samples are isolated into N through the gas chromatograph2, it is same to be then fed into progress nitrogen in the isotope mass spectrometer
The measurement of position element, and with N in air2For standard, N in the gas samples is calculated2Nitrogen isotope ratio
In the above-mentioned methods, it is preferable that the N in the measurement gas samples2Nitrogen isotope ratio's
In step, the second interface of the high-pressure cylinder connects the sampling valve, and day is extracted from the sampling valve using micro-sampling pin
Right gas sample product, and natural gas is injected into gas chromatograph, isolate N by gas chromatograph2, measured using isotope mass spectrometer
N in the natural gas sample2Nitrogen isotope ratio
In the above-mentioned methods, the N in the measurement gas samples2Nitrogen isotope ratioThe step of in, institute
The dosage for stating natural gas sample is controlled by the micro-sampling pin, which is this field conventional amount used.
In the above-mentioned methods, N in the natural gas sample2Content is also N in the gas samples2Content；The natural gas
N in sample2Nitrogen isotope ratioAlso it is the N in the gas samples2Nitrogen isotope ratio
In the above-mentioned methods, it is preferable that in the measurement gas samples isotopic ratio R/Ra of helium or3He/4In the step of He, the second interface of the high-pressure cylinder connects the second pressure reducing valve, and second pressure reducing valve connection is described natural
Injection port in gas on rare gas sample preparation device, film rule and microsampling valve, and advised by the film and microsampling
Valve control enters the natural gas sample size of rare gas sample preparation device in the natural gas.
In the above-mentioned methods, the natural gas sample size is depending on specific implementation needs.
In the above-mentioned methods, in the measurement gas samples isotopic ratio R/Ra of helium or3He/4He's
In step, using the active gases other than the purification of rare gas sample preparation device, removing rare gas in the natural gas, and carry out
The separation of rare gas, isolates He.
In the above-mentioned methods, it is preferable that in the measurement gas samples isotopic ratio R/Ra of helium or3He/4In the step of He, rare gas sample preparation device includes the sample preparation for being used to prepare rare gas in natural gas in the natural gas
Rare gas trace analysis device in device or natural gas, but not limited to this.
In the above-mentioned methods, it is preferable that in the cleaning high-pressure cylinder the step of, the method rinsed repeatedly is：
It is rinsed 4-6 times repeatedly using natural gas, each washing time is 10 minutes or more.
In the above-mentioned methods, it is preferable that comprehensive discrimination index system is established, is sentenced in the step of knowing the gas samples,
The gas samples are coal-formed gas or petroliferous gas or when the two are mixed into because of gas, need to measure alkane in the gas samples
Carbon isotope ratio, and according to the carbon isotope ratio distinguish the gas samples be coal-formed gas, petroliferous gas or coal at
Gas and petroliferous gas mixing.
In the above-mentioned methods, the carbon isotope ratio for measuring alkane in the gas samples can be with this field routine
Method.
In the above-mentioned methods, described that the gas samples are distinguished as coal-formed gas, oil type according to the carbon isotope ratio
Gas or the method for coal-formed gas and petroliferous gas mixing are this field routine techniques.
In the above-mentioned methods, it is preferable that this method further include the comprehensive discrimination index system is made plate, and according to
The plate intuitively sentences the step of knowing the gas samples.
The present invention also provides above-mentioned He and N2Combine method the answering in natural gas exploration sentenced and know coal-formed gas, petroliferous gas
With.
Above-mentioned He and N provided by the invention2Combine the method sentenced and know coal-formed gas, petroliferous gas, can utilize dilute in natural gas
There are gas He and non-hydrocarbon gas N2To the natural gas be coal-formed gas or petroliferous gas carry out it is quick, accurate and effective sentence knowledges, this method has
Have the characteristics that it is easy to operate, efficient, reliable, this be in-depth Natural Gas Origin and Source Study, instruct natural gas exploration to provide
Technical support.By above-mentioned He and N2Combine sentence know coal-formed gas, petroliferous gas method be applied to natural gas exploration in, for carry out day
Right the gas origin cause of formation and Source Study instruct natural gas exploration to be of great significance.
Description of the drawings
Fig. 1 is the He and N of embodiment 1-32Combine the method flow diagram sentenced and know coal-formed gas, petroliferous gas；
Fig. 2 is embodiment 1 under the conditions of R/Ra≤0.2Sentence knowledge plate；
Fig. 3 is embodiment 1-3 and verifies the He and N of example 1-22Combine the result map sentenced and know coal-formed gas, petroliferous gas.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide a kind of He and N2Combine sentence know coal-formed gas, petroliferous gas method, according to the following steps into
Row：
Using the natural gas (i.e. oil gas field in tower) of natural gas from Tarim Basin field exploitation as research sample, according to Fig. 1
Shown in flow be detected and analyzed：
It is the stainless steel high-pressure cylinder that 1L carries bivalve and double nip to select volume, and machine is utilized before gas samples acquisition
Above-mentioned stainless steel high-pressure cylinder is evacuated to 10 by tool 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, it rinses above-mentioned steel cylinder repeatedly using natural gas 4-6 times, continues 10 minutes or more every time, then acquire the stage casing 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 institute
It states and takes appropriate first natural gas sample at sampling valve, in the gas chromatograph of injection conventional constituents content analysis detection described in measurement
N in first natural gas sample2Content, in percentage (%)；
The second interface of the high-pressure cylinder of the acquisition gas samples is connected with sampling valve, utilizes the micro-sampling pin
Appropriate second natural gas sample is taken from the sampling valve again, is injected in the gas-chromatography isotope mass spectrometry combined instrument, described
Two natural gas samples isolate the N in natural gas by gas-chromatography2, the N that then isolates this2It is sent into connected isotope
The measurement that nitrogen isotope is carried out in mass spectrograph, with N in air2For standard, N in the second natural gas sample is calculated2The same position of nitrogen
Plain ratioIn terms of permillage (‰)；
By 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 microsampling valve, then by the film advise with it is micro
Sampling valve controls the sample size 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, the He of separation 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 meters；
Utilize the isotopic ratio R/Ra of rare gas helium, non-hydrocarbon gas N in above-mentioned gas samples2Content and N2Nitrogen
Isotopic ratioEstablish He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system and figure
Version, the domain is as shown in Fig. 2, the comprehensive discrimination index system is：
(1) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andWhen, then it is described
Gas samples are mostly generally coal-formed gas, as shown in the IVth areas Fig. 2；
(2) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, andWhen, then it is described
Gas samples are mostly generally petroliferous gas, as shown in the Ith areas Fig. 2；
(3) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andWhen, then institute
It is mostly petroliferous gas to state gas samples generally, as shown in the IIth areas Fig. 2；
(4) when R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, andWhen,
Then the gas samples are that coal-formed gas or petroliferous gas or the two are mixed into because of gas, as shown in the IIIth areas Fig. 2, need to measure at this time
The carbon isotope ratio of alkane in the gas samples, and the natural gas sample is further discriminated between according to the carbon isotope ratio
This is that coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas mix.
Through testing and analyzing above, the natural gas for the natural gas from Tarim Basin field exploitation that the present embodiment uses, wherein rare
The isotope of gas helium3He/4He is substantially 10-8Magnitude, R/Ra ＜ 0.1, therefore, the rare gas He in the natural gas are allusion quotation
The crustal origin of type；
According to He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIn index systemRefer to
Target sentences knowledge, the R/Ra ＜ 0.1 that the gas samples measure, therefore, the non-hydrocarbon gas N in the natural gas2It is organic for shell source
The origin cause of formation；
The organic origin includes the three big origin causes of formation, wherein
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2It is main for biogenesis
To come from microorganism denitrification or nitrogenation；
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2For organic matter
Thermogenic gas, essentially from the hot ammoniation of ripe, high stage of ripeness organic matter；
When R/Ra≤0.2,When, the non-hydrocarbon gas N in the gas samples2For organic matter pyrolysis at
Cause, essentially from the splitting action of post-mature stage organic matter；
Non-hydrocarbon gas N in the natural gas for the natural gas from Tarim Basin field exploitation that the present embodiment uses2Nitrogen isotope
RatioMainly fallRange in, fall into individuallyRange in, because
This, the non-hydrocarbon gas N in the natural gas for the natural gas from Tarim Basin field exploitation that the present embodiment uses2Predominantly organic matter at
Cause, essentially from ripe, high stage of ripeness organic matter pyrolysis；
It further utilizes according to above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system
InIndex sentences knowledges to what the hydrocarbon gas of the natural gas carried out coal-formed gas and petroliferous gas, gas samples survey
The N obtained2Content andRange fall in N2Content ＞ 9% andAnd N2Content≤9% and
Region in, as shown in the Ith area and the IIth area in Fig. 3；Combine above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasThe natural gas of index system and plate, the natural gas from Tarim Basin field exploitation that the present embodiment uses is basic
For petroliferous gas.
In the present embodiment, the natural gas of practical Tarim Basin gas field exploitation is essentially petroliferous gas, this and this implementation
The He and N that example provides2The identifying result for combining the method for sentencing knowledge coal-formed gas, petroliferous gas is consistent.
It can be seen that He provided in this embodiment and N2Combine the method sentenced and know coal-formed gas, petroliferous gas, can utilize natural
Rare gas He and non-hydrocarbon gas N in gas2To the natural gas be coal-formed gas or petroliferous gas carry out it is quick, accurate and effective sentence knowledges, this
Method have the characteristics that it is easy to operate, efficient, reliable, for in-depth Natural Gas Origin and Source Study, instruct natural gas exploration to carry
Technical support is supplied.
Embodiment 2
Present embodiments provide a kind of He and N2Combine sentence know coal-formed gas, petroliferous gas method, according to the following steps into
Row：
The present embodiment is detected using the natural as research sample of 2 gas-field exploitation of enlightening Na according to flow shown in FIG. 1
And analysis：
The present embodiment samples the gas samples of 2 gas-field exploitation of enlightening Na using the method for embodiment 1, and
N is carried out to the gas samples2The detection of content, N2Nitrogen isotope ratioAnd the inspection of the isotopic ratio R/Ra of helium
It surveys；Then the He and N established according to embodiment 12Combine to sentence and knows coal-formed gas, petroliferous gas Index system and
Helium isotope ratio R/Ra, the non-hydrocarbon gas N that plate measures the present embodiment gas samples2Content and N2Nitrogen isotope
RatioIt is analyzed；
After measured, in the gas samples rare gas helium isotopic ratio R/Ra ＜ 0.1 (i.e. R/Ra≤0.2), and3He/4He ＜ 2.8 × 10-7, therefore, the rare gas He in the gas samples is typical crustal origin；According to above-mentioned He
And N2Combine to sentence and knows coal-formed gas, petroliferous gasIn index systemIndex sentences knowledge, described
Non-hydrocarbon gas N in gas samples2Nitrogen isotope ratioIt falls Range in, therefore, the day
Non-hydrocarbon gas N in right gas sample sheet2For the organic matter origin cause of formation, essentially from post-mature stage organic matter splitting action；
It further utilizes according to above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system
InWhat hydrocarbon gas in the index gas samples carried out coal-formed gas and petroliferous gas sentences knowledge, the natural gas sample
Originally the N measured2Content andRange fall in N2Content≤9% andRegion in, such as the IVth in Fig. 3
Shown in area；Combine above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system and plate, this reality
The natural gas for applying 2 gas-field exploitation of enlightening Na of example use is essentially coal-formed gas.
In the present embodiment, the natural gas of practical 2 gas-field exploitation of enlightening Na is essentially coal-formed gas, this with it is provided in this embodiment
He and N2The identifying result for combining the method for sentencing knowledge coal-formed gas, petroliferous gas is consistent.
Embodiment 3
Present embodiments provide a kind of He and N2Combine sentence know coal-formed gas, petroliferous gas method, according to the following steps into
Row：
The present embodiment is detected using the natural as research sample of Kela 2 Gas Field exploitation according to flow shown in FIG. 1
And analysis：
The present embodiment is sampled using the method for embodiment 1 come the gas samples exploited to the Kela 2 Gas Field, and
N is carried out to the gas samples2The detection of content, N2Nitrogen isotope ratioAnd the inspection of the isotopic ratio R/Ra of helium
It surveys；Then the He and N established according to embodiment 12Combine the R/Ra- δ for sentencing and knowing coal-formed gas, petroliferous gas15N N2-N2Index system and
Helium isotope ratio R/Ra, the non-hydrocarbon gas N that plate measures the present embodiment gas samples2Content and N2Nitrogen isotope
RatioIt is analyzed；
After measured, in the gas samples rare gas helium isotopic ratio R/Ra ＜ 0.1 (i.e. R/Ra≤0.2), and3He/4He ＜ 2.8 × 10-7, therefore, the rare gas He in the gas samples is typical crustal origin；According to above-mentioned He
And N2Combine to sentence and knows coal-formed gas, petroliferous gasIn index systemIndex sentences knowledge, described
Non-hydrocarbon gas N in gas samples2Nitrogen isotope ratioIt falls in -10 ‰ ＜Range in, because
This, the non-hydrocarbon gas N in the gas samples2For organic origin, make essentially from ripe, the high hot ammonification of stage of ripeness organic matter
With；
It further utilizes according to above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system
InIndex sentences knowledge to what the hydrocarbon gas in the gas samples carried out coal-formed gas and petroliferous gas, the natural gas
The N that sample measures2Content andRange fall in N2Content≤9% andRegion in, i.e. coal
It is mixed at gas or petroliferous gas or the two because in gas region, as shown in the IIIth area in Fig. 3, therefore, combining above-mentioned He and N2Connection
It closes to sentence and knows coal-formed gas, petroliferous gasIndex system and plate, the Kela 2 Gas Field exploitation that the present embodiment uses
Natural gas also need further to measure the carbon isotope ratio of alkane in the gas samples, and according to the carbon isotope ratio pair
The gas samples are that coal-formed gas, petroliferous gas or coal-formed gas and petroliferous gas mixing are distinguish.
In addition, the day that the present embodiment also acquires the gas fields great Bei, the gas fields Ke Keya, Donghetang oil gas field, the southern oil gas field of wheel
The method that embodiment 1 is originally respectively adopted in right gas sample is tested and is analyzed, and the non-hydrocarbon gas N in gas samples is measured2For
Shell source organic origin；In addition, measuring the N of each gas samples2Content andRange all fall within N2Content≤9% andRegion in, i.e., coal-formed gas or petroliferous gas or the two are mixed into because in gas region, such as the IIIth in Fig. 3
Shown in area, therefore, combine above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system and plate,
Also need the further measurement of difference each the natural gas of the gas fields great Bei, the gas fields Ke Keya, Donghetang oil gas field, the southern exploitation of oil-gas field of wheel
The carbon isotope ratio of middle alkane, and be coal-formed gas, petroliferous gas or coal to each gas samples according to the carbon isotope ratio
It is distinguish respectively at gas and petroliferous gas mixing.
Verify example 1
This verification example uses and the natural gas of field river exploitation of oil-gas field is as identifying object, comes according to the method for embodiment 1
Described and field river exploitation of oil-gas field gas samples are tested, the He and N then established according to embodiment 12Combine and sentences
Know coal-formed gas, petroliferous gasThe same position of helium that index system and plate measure this verification example gas samples
Plain ratio R/Ra, non-hydrocarbon gas N2Content and N2Nitrogen isotope ratioCarry out verification analysis；
The isotopic ratio R/Ra ＜ 0.2 of rare gas helium in the gas samples, and3He/4He ＜ 2.8 × 10-7, because
This, the rare gas He in the gas samples is typical crustal origin；According to above-mentioned He and N2Combine to sentence and knows coal-formed gas, oil
Type gasIn index systemIndex sentences knowledge, the non-hydrocarbon gas in the gas samples
N2Nitrogen isotope ratioIt fallsRange in, it is therefore, non-in the gas samples
Appropriate hydrocarbon gas N2For organic origin, essentially from ripe, the high hot ammoniation of stage of ripeness organic matter；
It further utilizes according to above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system
InIndex sentences knowledge to what the hydrocarbon gas in the gas samples carried out coal-formed gas and petroliferous gas, the natural gas
The N that sample measures2Content andRange fall in N2Content ＞ 9% andRegion in, in Fig. 3
Shown in Ith area；Combine above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gas Index system and plate, this
Natural gas that verification example uses and field river exploitation of oil-gas field is essentially petroliferous gas, and the identifying result is consistent with actual result.
Verify example 2
The natural gas that this verification example is exploited using Yaha gas field is as identifying object, according to the method for embodiment 1 come to institute
The gas samples for stating Yaha gas field exploitation are tested, the He and N then established according to embodiment 12Combine sentence know coal-formed gas,
Petroliferous gasThe helium isotope ratio R that index system and plate measure this verification example gas samples/
Ra, non-hydrocarbon gas N2Content and N2Nitrogen isotope ratioCarry out verification analysis；
The isotopic ratio R/Ra ＜ 0.2 of rare gas helium in the gas samples, and3He/4He ＜ 2.8 × 10-7, because
This, the rare gas He in the gas samples is typical crustal origin；According to above-mentioned He and N2Combine to sentence and knows coal-formed gas, oil
Type gasIn index systemIndex sentences knowledge, the non-hydrocarbon gas in the gas samples
N2Nitrogen isotope ratioIt fallsRange in, therefore, the non-hydrocarbon gas N in the gas samples2
For organic origin, essentially from the splitting action of post-mature stage organic matter；
It further utilizes according to above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system
InWhat hydrocarbon gas in the index gas samples carried out coal-formed gas and petroliferous gas sentences knowledge, the natural gas sample
Originally the N measured2Content andRange fall≤9% andRegion in, such as the IVth institute of area in Fig. 3
Show；Combine above-mentioned He and N2Combine to sentence and knows coal-formed gas, petroliferous gasIndex system and plate, this verification example
The natural gas of the Yaha gas field exploitation of use is essentially coal-formed gas, and the identifying result is consistent with actual result.
In conclusion above-mentioned He and N provided by the invention2Combine the method sentenced and know coal-formed gas, petroliferous gas, day can be utilized
Rare gas He and non-hydrocarbon gas N in right gas2It is quick, accurate and effective to be that coal-formed gas or petroliferous gas carry out substantially to the natural gas
Sentence knowledge, this method has the characteristics that easy to operate, efficient, reliable, this is in-depth Natural Gas Origin and Source Study, guidance is natural
Gas exploration provides technical support.By above-mentioned He and N2Combine and sentences the method for knowing coal-formed gas, petroliferous gas applied to natural gas exploration
In, for carrying out Natural Gas Origin and Source Study, natural gas exploration being instructed to be of great significance.
Claims (18)
1. a kind of He and N2Combine the method sentenced and know coal-formed gas, petroliferous gas comprising following steps：
Acquire gas samples；
Measure N in the gas samples2Content；
Measure N in the gas samples2Nitrogen isotope ratio δ15NN2；
Measure helium in the gas samples isotopic ratio R/Ra or3He/4He；
Comprehensive discrimination index system is established, sentences and knows the gas samples；
Wherein, the comprehensive discrimination index system is：
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and δ15NN2>=5 ‰, then the gas samples are more
For coal-formed gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content ＞ 9%, and δ15NN2≤ 5 ‰, then the gas samples are more
For petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and δ15NN2≤ -5 ‰, then gas samples
Mostly petroliferous gas；
R/Ra≤0.2 or3He/4He≤2.8×10-7, N2Content≤9%, and -5 ‰ ＜ δ15NN2＜ 5 ‰, the then natural gas
Sample is that coal-formed gas or petroliferous gas or the two are mixed into because of gas.
2. according to the method described in claim 1, it is characterized in that：It is described acquisition gas samples method be：By high pressure steel
Bottle is evacuated to 10-1Pa hereinafter, then acquire natural gas stage casing air-flow, until the high-pressure cylinder gas pressure be 3-6MPa,
Obtain gas samples.
3. according to the method described in claim 2, it is characterized in that：Measure N in the gas samples2The method of content is：Profit
Natural gas sample is extracted from sampling valve with micro-sampling pin, and injects in gas chromatograph and measures N in the natural gas sample2Contain
Amount.
4. according to the method described in claim 2, it is characterized in that：Measure N in the gas samples2Nitrogen isotope ratio
δ15NN2Method be：Institute is measured using gas chromatograph and isotope mass spectrometer or gas-chromatography isotope mass spectrometry combined instrument
State N in gas samples2Nitrogen isotope ratio δ15NN2。
5. according to the method described in claim 2, it is characterized in that：Measure the isotopic ratio R/ of helium in the gas samples
Ra or3He/4The method of He is：The high-pressure cylinder is connected with rare gas sample preparation device in natural gas, passes through the day
Rare gas sample preparation device isolates He from the gas samples in right gas, and the He is sent into rare and refractory metals
In mass spectrograph, measure helium isotope ratio R/Ra in the gas samples or3He/4He。
6. according to the method described in claim 2, it is characterized in that：The high-pressure cylinder is the high pressure with bivalve and double nip
Steel cylinder.
7. according to claim 1-6 any one of them methods, it is characterised in that：Before the acquisition gas samples the step of
It further include the steps that cleaning high-pressure cylinder；
The step is that the high-pressure cylinder is evacuated to 10-1Then Pa by the first interface of the high-pressure cylinder hereinafter, pass through first
Pressure reducing valve is connect with sampling well head, and be passed through natural gas into the high-pressure cylinder is rinsed repeatedly.
8. according to claim 1-6 any one of them methods, it is characterised in that：N in the measurement gas samples2Nitrogen
Isotopic ratio δ15NN2The step of be that the gas samples are isolated into N through gas chromatograph2, it is then fed into isotope mass spectrometry
The measurement of nitrogen isotope is carried out in instrument, and with N in air2For standard, N in the gas samples is calculated2Nitrogen isotope
Ratio delta15NN2。
9. according to the method described in claim 4, it is characterized in that：The N in the measurement gas samples2Nitrogen isotope
Ratio delta15NN2The step of in, the second interface of the high-pressure cylinder connects sampling valve, using micro-sampling pin from the sampling valve
Natural gas sample is extracted, and natural gas is injected into gas chromatograph, N is isolated by gas chromatograph2, utilize isotope mass spectrometry
Instrument measures N in the natural gas sample2Nitrogen isotope ratio δ15NN2。
10. according to the method described in claim 5, it is characterized in that：The isotope of helium in the measurement gas samples
Ratio R/Ra or3He/4In the step of He, the second interface of the high-pressure cylinder connects the second pressure reducing valve, second pressure reducing valve
Injection port, film rule and the microsampling valve in the natural gas on rare gas sample preparation device are connected, and passes through the film
Rule and the control of microsampling valve enter the natural gas sample size of rare gas sample preparation device in the natural gas.
11. the method according to claim 5 or 10, it is characterised in that：Helium is same in the measurement gas samples
Position element ratio R/Ra or3He/4In the step of He, rare gas sample preparation device includes being used to prepare natural gas in the natural gas
Rare gas trace analysis device in the sample preparation device or natural gas of middle rare gas.
12. according to the method described in claim 7, it is characterized in that：In the step of cleaning the high-pressure cylinder, it is described repeatedly
The method of flushing is：It is rinsed 4-6 times repeatedly using natural gas, each washing time is 10 minutes or more.
13. according to the method described in claim 1, it is characterized in that：Comprehensive discrimination index system is established, sentences and knows the natural gas
In the step of sample, the gas samples are coal-formed gas or petroliferous gas or when the two are mixed into because of gas, need to measure described natural
The carbon isotope ratio of alkane in gas sample sheet, and according to the carbon isotope ratio distinguish the gas samples be coal-formed gas,
Petroliferous gas or the mixing of coal-formed gas and petroliferous gas.
14. according to the method described in claim 1, it is characterized in that：This method further includes by the comprehensive discrimination index system
Plate is made, and intuitively sentences the step of knowing the gas samples according to the plate.
15. claim 1-6,9-10,12-14 any one of them He and N2Combine and sentences the method for knowing coal-formed gas, petroliferous gas in day
Application in right gas exploration.
16. the He described in claim 7 and N2Combine the application for sentencing the method for knowing coal-formed gas, petroliferous gas in natural gas exploration.
17. He according to any one of claims 8 and N2Combine the application for sentencing the method for knowing coal-formed gas, petroliferous gas in natural gas exploration.
18. claim 11 any one of them He and N2Combine and sentences the method for knowing coal-formed gas, petroliferous gas in natural gas exploration
Using.
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| CN106371151B (en) * | 2016-09-06 | 2019-09-10 | 中国石油天然气股份有限公司 | It is a kind of to sentence the method and device for knowing genetic types of natural gas |
| CN109141963B (en) * | 2018-09-27 | 2023-12-19 | 上海海洋大学 | Isotope determination sample trace sampling and embedding device |
| CN114200026A (en) * | 2020-09-18 | 2022-03-18 | 中国石油天然气股份有限公司 | Method for identifying natural gas cause by using cis-1, 3-dimethylcyclohexane/n-octane and 2-methylheptane/n-octane |
| CN116124917B (en) * | 2022-11-21 | 2023-10-31 | 中国科学院西北生态环境资源研究院 | Method for distinguishing atmosphere, coal gas, oil gas and biological gas by adopting argon and oxygen groups |
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