CN110412151A - A kind of method of determining oil-gas reservoir phase - Google Patents

A kind of method of determining oil-gas reservoir phase Download PDF

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CN110412151A
CN110412151A CN201910554319.1A CN201910554319A CN110412151A CN 110412151 A CN110412151 A CN 110412151A CN 201910554319 A CN201910554319 A CN 201910554319A CN 110412151 A CN110412151 A CN 110412151A
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oil
gas
gas reservoir
adamantane
ethyl
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CN110412151B (en
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朱光有
池林贤
王萌
张志遥
李婷婷
杨海军
韩剑发
孙崇浩
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China Petroleum and Natural Gas Co Ltd
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • 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
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
    • 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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Abstract

The invention discloses a kind of methods of determining oil-gas reservoir phase.Method includes the following steps: S1, using comprehensive two dimensional gas chromatography-time of-flight mass spectrometer GC × GC-TOFMS in multiple crude oil samples ethyl drop adamantane series compound identified and identified, obtain each compound appearance information；The quantitative analysis of S2, ethyl drop adamantane series compound, obtain the content of ethyl drop adamantane series compound；Relational expression between S3, fitting ethyl drop adamantane series compounds content and oil reservoir gas-oil ratio；S4, the relationship for establishing oil reservoir gas-oil ratio Yu oil-gas reservoir phase；S5, oil-gas reservoir phase is determined.The present invention determines oil-gas reservoir phase by dropping adamantane content using ethyl, and the determination for deep-seated oil gas reservoir phase provides New Set, and new resolving ideas is provided for oil and gas resource evaluation.

Description

A kind of method of determining oil-gas reservoir phase
Technical field
The invention belongs to oil sample analysis technical fields, and in particular to a kind of method of determining oil-gas reservoir phase.
Background technique
The determination of hydrocarbon fluid phase is the basis of Exploration of Oil And Gas evaluation, is primarily solved in oilfield exploitation procedure The problem of.The complexity of fluid phase state is controlled primarily by the type of hydrocarbon matrix and the multistage negotiation of thermal evolution.Meanwhile it is extraneous The variation of temperature, pressure equally affects the phase of hydrocarbon fluid.The phase for determining oil-gas reservoir is determining hydro carbons original phase behavior, The phase of hydrocarbon fluid cannot represent the original phase behavior of hydro carbons under ground table status.PVT phase state analysis can restore hydrocarbon fluid and exist Reservoir state under formation condition is the most effective means for currently judging oil and gas phase.Alternatively, it is also possible to by intending ternary phase The methods of figure diagnostic method, hydrocarbon component block diagram diagnostic method judge hydrocarbon type.But generally existing analysis cost The problems such as height, the period is long.
Comprehensive two dimensional gas chromatography (GC × GC) is that one kind efficiently separates complex mixture, and to the response of low content compound compared with Good completely new analysis means.Qualitative and quantitative analysis has been carried out to the compound in crude oil using complete two-dimentional flight chromatography-mass spectroscopy Expanded application.
Ethyl drop adamantane is the high compound of the current a kind of thermal stability only found in crude oil, and wherein ethyl drops Single adamantane (C12H18) and ethyl drop Double diamantane hydrocarbons (C16H22) it is most stable of two kinds of configurations in its all isomer, because This its enrichment degree can indicate the cracking alteration that crude oil lives through.
Summary of the invention
Based on background above technology, the present invention provides a kind of method of determining oil-gas reservoir phase, and this method is dropped using ethyl Adamantane series compounds content determines oil-gas reservoir phase, and the determination for deep-seated oil gas reservoir phase provides New Set, is oil gas Resource assessment provides new resolving ideas.
In order to achieve the goal above, the present invention uses following scheme:
A kind of method of determining oil-gas reservoir phase, method includes the following steps:
S1, using comprehensive two dimensional gas chromatography-time of-flight mass spectrometer GC × GC-TOFMS to ethyl in multiple crude oil samples Drop adamantane series compound is identified and is identified, each compound appearance information is obtained；
The quantitative analysis of S2, ethyl drop adamantane series compound, obtain the content of ethyl drop adamantane series compound；
Relational expression between S3, fitting ethyl drop adamantane series compounds content and oil reservoir gas-oil ratio；Oil reservoir therein Gas-oil ratio is obtained according to oil reservoir actual production data, is production of hydrocarbons initial stage, the natural gas obtained after stable yields and crude oil total yield The ratio between amount；
S4, the relationship for establishing oil reservoir gas-oil ratio Yu oil-gas reservoir phase；
S5, oil-gas reservoir phase is determined.
Preferably, S5 includes: the pass for establishing the content and oil-gas reservoir phase of ethyl drop adamantane series compound in crude oil Then system directly determines oil-gas reservoir phase according to the content that adamantane series compound drops in ethyl；It is opened with matching corresponding exploration Hair measure, to ensure efficiently quickly exploration and development oil gas field.
It is highly preferred that in S5 further include: the content and oil-gas reservoir phase of ethyl drop adamantane series compound in based on crude The relationship of state, which is established, differentiates plate, intuitively can drop adamantane series total amount of compound by ethyl in crude oil and differentiate oil-gas reservoir class Type determines oil-gas reservoir phase.
Preferably, being added in the crude oil sample has D16Adamantane (deuterated adamantane) standard sample, and it is dilute using solvent It releases to required concentration.Preferably, the solvent is methylene chloride, it is also possible to n-hexane etc., because being free of dichloromethane in crude oil sample Alkane, therefore methylene chloride is smaller on test result influence.
Specific embodiment according to the present invention, it is preferable that being added in the crude oil sample has D16Adamantane standard sample, And the step of being diluted to required concentration using solvent, specifically includes:
50-200mg crude oil sample is taken, the D of 0.25-0.75 μ g/ μ L is added into the crude oil sample16Adamantane 30-50 μ L adds solvent to 1.0-2.0mL, is uniformly mixed stand-by.
Such as treatment process in embodiments of the present invention includes: to take 200mg crude oil sample in 2mL autosampler bottle, The D of (concentration is 0.5 μ g/ μ L, and solvent is methylene chloride) is added1640 μ L of adamantane standard sample is added two after mixing Chloromethanes is to 1.5mL.
Preferably, comprehensive two dimensional gas chromatography described in S1 of the embodiment of the present invention-time of-flight mass spectrometer GC × GC-TOFMS Using is that Leco company, the U.S. produces, and is compared according to the collected mass spectrogram of instrument with standard substance spectrogram, to second Base drop adamantane series compound is identified and is identified, each compound appearance information is obtained.
Preferably, S2 is specifically included:
Crude oil sample is analyzed using comprehensive two dimensional gas chromatography-flame ionization ditector GC × GC-FID, is obtained To GC × GC-FID spectrogram of ethyl drop adamantane；Then adamantane compound is dropped according to the ethyl that GC × GC-TOFMS is provided Appearance information, the peak area of spectrogram in GC × GC-FID is calculated, with D16Adamantane standard sample goes out peak area progress Comparison obtains the content of ethyl drop adamantane series compound.
Preferably, the coefficient R that ethyl drop adamantane series compounds content and oil reservoir gas-oil ratio are fitted in S32It is greater than When 0.9, fitting formula is established.
Such as in embodiments of the present invention, adamantane series compounds content drops in the ethyl of Tarim Basin oil-gas reservoir in S3 Fitting formula with oil reservoir gas-oil ratio is (as shown in Figure 1):
G=5.2797E1.4587(R2=0.9121)；
Wherein, G is gas-oil ratio, and E is that adamantane content, ppm drop in ethyl.
Skilled addressee readily understands that, for other specific oil reservoirs, the formula fitted be will be different, but Method is identical.
Preferably, oil-gas reservoir phase is divided into gas condensate reservoir, volatilization oil reservoir and normal oil reservoir in S4；Such as in tower Tub for craton area ORDOVICIAN CARBONATE oil-gas reservoir, normal oil reservoir gas-oil ratio is generally less than 300m3/m3, volatile oil reservoir Generally in 200~1500m3/m3, gas condensate reservoir is generally higher than 1000m3/m3。
Preferably, this method further includes the steps that verifying validity:
It is compared with conventional oils gas reservoir determining methods such as pseudoternary phase diagram diagnostic method, hydrocarbon component block diagram diagnostic methods, verifies it Validity.
Preferably, required crude oil sample includes normal oil, condensate and heavy crude etc., but need to be from oil well Well head.
Preferably, the one-dimensional chromatographic column of GC × GC-TOFMS is HP-PONA (50m × 0.2mm × 0.5 μm), and program is arranged Heating:, keeping 1min, rise to 120 DEG C with 20 DEG C/min by 50 DEG C of initial temperature, rises to 310 DEG C with 3 DEG C/min, keeps 25min；Two dimension Chromatographic column is Rx17HT (1.5m × 0.1mm × 0.1 μm), and temperature programming temperature is higher than 10 DEG C of one-dimensional chromatographic column；Injector temperature It is 300 DEG C, Splitless injecting samples, carrier gas is helium, flow velocity 1mL/min；Modulation period 6s, wherein 1.8s hot blow time；Mass spectrum Aspect, transmission line and ion source temperature are respectively 300 DEG C and 240 DEG C, detector voltage 1600V, and mass scan range 40~ 600amu, 100 spectrograms of acquisition rate/s, solvent delay time are 0min.
Preferably, GC × GC-FID analysis method, using chromatography experiment condition identical with GC × GC-TOFMS, carrier gas, Hydrogen, air flow velocity be respectively 23mL/min, 60mL/min, 400mL/min；310 DEG C of detector temperature, frequency acquisition 200 Spectrogram/s, solvent delay time are 9min.
The software kit of the used instrument of the embodiment of the present invention is Chroma TOF software, is GC × GC system by equipped with hydrogen The Agilent 7890A gas chromatograph of flame ionization detector (FID) and the cold and hot modulator composition of double spouts, flight time Mass spectrometric work station is Chroma TOF software, and adamantane compound structure can be identified automatically according to software, and be led to It crosses standard specimen and carries out quantitative analysis, the accurate quantitative analysis data of adamantane compounds content are provided.
The method of determining oil-gas reservoir phase provided by the invention only relies on a drop crude oil sample, without cumbersome pre-treatment Journey is analyzed by complete two-dimentional instrument, directly carries out qualitative analysis and quantitative calculating to ethyl drop adamantane in crude oil sample, in turn Oil-gas reservoir phase is judged, so as to quickly determine the related relevant equipment and scheme of exploration and development, is realized efficiently fast Fast exploration and development oil gas field.
Detailed description of the invention
Fig. 1 is the fit correlation figure between gas-oil ratio and ethyl drop adamantane content.
Fig. 2 a is that adamantane comprehensive two dimensional gas chromatography dot chart drops in 8 well ethyl of the Tarim Basin middle ancient times.
Fig. 2 b is that adamantane comprehensive two dimensional gas chromatography dot chart drops in 5 well ethyl of the Tarim Basin middle ancient times.
Fig. 2 c is that ancient 101 well ethyls drop adamantane comprehensive two dimensional gas chromatography dot chart is taken turns in Tarim Basin.
Fig. 2 d is that ancient 11 well ethyls drop adamantane comprehensive two dimensional gas chromatography dot chart is taken turns in Tarim Basin.
Fig. 2 e is that ancient 701 well ethyls drop adamantane comprehensive two dimensional gas chromatography dot chart is taken turns in Tarim Basin.
Fig. 2 f is that Gu 7-5 well ethyl drop adamantane comprehensive two dimensional gas chromatography dot chart is taken turns in Tarim Basin.
Fig. 3 a is that adamantane comprehensive two dimensional gas chromatography dot chart drops in the 8 well ethyl of the middle ancient times that GC × GC-TOFMS is provided.
Mass spectrogram corresponding to 1 in Fig. 3 a that Fig. 3 b provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 2 in Fig. 3 a that Fig. 3 c provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 3 in Fig. 3 a that Fig. 3 d provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 4 in Fig. 3 a that Fig. 3 e provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 5 in Fig. 3 a that Fig. 3 f provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 6 in Fig. 3 a that Fig. 3 g provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 7 in Fig. 3 a that Fig. 3 h provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 8 in Fig. 3 a that Fig. 3 i provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 9 in Fig. 3 a that Fig. 3 j provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 10 in Fig. 3 a that Fig. 3 k provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 11 in Fig. 3 a that Fig. 3 l provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 12 in Fig. 3 a that Fig. 3 m provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 13 in Fig. 3 a that Fig. 3 n provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 14 in Fig. 3 a that Fig. 3 o provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 15 in Fig. 3 a that Fig. 3 p provides for GC × GC-TOFMS.
Mass spectrogram corresponding to 16 in Fig. 3 a that Fig. 3 q provides for GC × GC-TOFMS.
Fig. 3 r is the D that GC × GC-TOFMS is provided16The mass spectrogram of adamantane.
Fig. 4 is that adamantane differentiation oil-gas reservoir phase plate and hydrocarbon component block diagram drop in the ethyl that the present invention establishes.
Fig. 5 is that the pseudoternary phase diagram in the middle ancient times 26, middle ancient times 15-2 and the middle ancient times 22 differentiates plate.
Fig. 6 is the PVT phase diagram in the middle ancient times 26.
Fig. 7 is the PVT phase diagram of middle ancient times 15-2.
Fig. 8 is the PVT phase diagram in the middle ancient times 22.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.
The present invention is illustrated by taking the oil-gas reservoir of Tarim Basin as an example:
1) it takes 200mg crude oil sample in 2mL autosampler bottle, the D of 0.5 μ g/ μ L is added1640 μ of adamantane standard sample Methylene chloride is added to 1.5mL after mixing in L.
2) comprehensive two dimensional gas chromatography-time of-flight mass spectrometer (GC × GC-TOFMS) using the production of U.S. Leco company is right Crude oil sample is analyzed, and is compared according to the collected mass spectrogram of instrument with standard substance spectrogram, drops adamantane to ethyl Series compound is identified and is identified, each compound appearance information is obtained, if Fig. 2 a- Fig. 2 f is the corresponding ethyl drop gold of each well Rigid alkane comprehensive two dimensional gas chromatography dot chart, wherein abscissa is 1D retention time (s), and ordinate is 2D retention time (s)；In figure The drop adamantane of ethyl corresponding to each signal peak is marked, dotted line separates the ethyl drop adamantane of different substituents number It opens, the typical structure formula of the region compound of the formula in dashed region, C1Representing the compound substituent has one Carbon, C2-、C3Analogize.
Fig. 3 a- Fig. 3 q is that adamantane chromatography-mass spectroscopy figure drops in 8 well ethyl of the middle ancient times therein.Wherein Fig. 3 a is GC × GC- Adamantane comprehensive two dimensional gas chromatography dot chart drops in the 8 well ethyl of the middle ancient times that TOFMS is provided, and number represents each ethyl drop Buddha's warrior attendant in figure Alkane series compound, Fig. 3 b- Fig. 3 q are the corresponding mass spectrogram of compound each in Fig. 3 a.Fig. 3 r is D16The matter of adamantane reference substance Spectrogram.
3) it is analyzed using comprehensive two dimensional gas chromatography-flame ionization ditector GC × GC-FID, obtains ethyl drop GC × GC-FID spectrogram of adamantane.
4) according to the appearance information of GC × GC-TOFMS ethyl drop adamantane compound provided, in GC × GC-FID The peak area of spectrogram calculated, with D16Adamantane standard sample goes out peak area and compares, and obtains ethyl drop Buddha's warrior attendant methane series The content of column compound.
Such as D16Adamantane peak area is 54458, and total amount amount is 20 μ g, and content is 20 μ g/ oil sample weight 183.6mg/2 (methylene chloride dilute one times)=54.5ppm, the peak EA-1 (number is 2 in Fig. 3 a) area is 12241 in 8 well of the middle ancient times, then it contains Amount is 12241 × 54.5ppm/54458=12.25ppm.
5) ethyl obtained is calculated by step 4) and drops adamantane content (ppm), tests the crude oil sample of multiple groups difference well location Product obtain 1 data of table:
Adamantane content data table drops in 1 Tarim Basin gas-oil ratio of table and ethyl
It is fitted the relational expression between ethyl drop adamantane content and oil reservoir gas-oil ratio according to 1 data of table, in coefficient R2 When greater than 0.9, fitting formula (as shown in Figure 1) is established:
G=5.2797E1.4587(R2=0.9121)；
Wherein, G- gas-oil ratio, corresponding to the y in figure；Adamantane content (ppm) drops in E- ethyl, corresponding to the x in figure.
6) relationship of gas-oil ratio Yu oil-gas reservoir phase is established.Oil-gas reservoir phase is divided into gas condensate reservoir, volatilization oil reservoir, just Normal oil reservoir.For the ORDOVICIAN CARBONATE oil-gas reservoir of Platform-basin Region In Tarim Basin, normal oil reservoir gas-oil ratio is generally less than 300m3/m3, volatile oil reservoir is generally in 200~1500m3/m3, gas condensate reservoir is generally higher than 1000m3/m3。
7) it is compared with conventional oils gas reservoir determining methods such as pseudoternary phase diagram diagnostic method, hydrocarbon component block diagram diagnostic methods, verifying Its validity.
Pseudoternary phase diagram diagnostic method (Fig. 5), using three lighter hydrocarbons parameters as partitioning standards, with C7Above lighter hydrocarbons content is to draw Divide foundation, is normal oil reservoir (marking 3 region in Fig. 5) less than 11%, is greater than 11% and less than 32% is volatile oil area (Fig. 5 The region of middle mark 2), it is greater than 32% for condensation reservoir region (marking 1 region in Fig. 5)；As seen from Figure 5, the middle ancient times 26 are normal Oil reservoir, middle ancient times 15-2 are volatilization oil reservoir, and the middle ancient times 22 are condensation oil reservoir.
PVT phase diagram (Fig. 6, Fig. 7 and Fig. 8) display, the middle ancient times 26 are normal oil reservoir, and middle ancient times 15-2 is volatilization oil reservoir, the middle ancient times 22 be condensation oil reservoir.
Block diagram in Fig. 4 is that hydrocarbon component block diagram sentences knowledge, differentiates oil-gas reservoir phase by four aspect ratios of lighter hydrocarbons State；Central axes therein are the relationship between the gas-oil ratio of the invention derived and ethyl drop adamantane, phon scale on central axes For and drop adamantane content, lower phon scale be gas-oil ratio；By means of the present invention, it is only necessary to determine ethyl drop gold The content of rigid alkane, corresponding point can be directly found on the central axes, that is, can determine the phase of oil reservoir.
As shown in Figure 4, in hydrocarbon component block diagram, four hydrocarbon component parameters in the middle ancient times 26 are respectively positioned on normal oil reservoir Area indicates that the oil reservoir is normal oil reservoir, and middle ancient times 15-2 is volatilization oil reservoir, and the middle ancient times 22 are condensation oil reservoir.Such as 26 well oil sample of the middle ancient times, intend Ternary phase diagrams (Fig. 5) indicates that it is bored and meets oil reservoir as normal oil reservoir；In its PVT phase diagram (Fig. 6), critical-temperature pressure condition is aobvious Show that oil reservoir is normal oil reservoir；In hydrocarbon component block diagram (Fig. 4), the middle ancient times 26 well oil sample, four hydrocarbon component parameters are respectively positioned on normally Reservoir region indicates that the oil reservoir is normal oil reservoir.The above method of discrimination is excessively complicated, and requirement of experiment is higher, and the present invention passes through fitting Relationship between adamantane and oil reservoir gas-oil ratio drops in ethyl, directly can determine its oil reservoir phase by ethyl drop adamantane content.In Ancient 26 well ethyls drop adamantane content is 14.22ppm, and calculating display oil reservoir gas-oil ratio is about 249, indicates that the oil reservoir is normal oil Hiding.Differentiate that result is consistent with the prior art, shows the reliability of the method for the present invention；And compared with the above prior art, this hair It is bright easier to be direct.
8) new differentiation plate is established, as shown in figure 4, adamantane series chemical combination intuitively can be dropped by ethyl in crude oil Object total amount differentiates Oil-gas Accumulation Types, determines oil-gas reservoir phase, matches corresponding exploration and development measure, to ensure efficiently quickly exploration Development of fields.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.

Claims (13)

1. a kind of method of determining oil-gas reservoir phase, which is characterized in that method includes the following steps:
S1, gold is dropped to ethyl in multiple crude oil samples using comprehensive two dimensional gas chromatography-time of-flight mass spectrometer GC × GC-TOFMS Rigid alkane series compound is identified and is identified, each compound appearance information is obtained；
The quantitative analysis of S2, ethyl drop adamantane series compound, obtain the content of ethyl drop adamantane series compound；
Relational expression between S3, fitting ethyl drop adamantane series compounds content and oil reservoir gas-oil ratio；
S4, the relationship for establishing oil reservoir gas-oil ratio Yu oil-gas reservoir phase；
S5, oil-gas reservoir phase is determined.
2. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that S5 includes: to establish ethyl in crude oil The content of adamantane series compound and the relationship of oil-gas reservoir phase are dropped, containing for adamantane series compound is then dropped according to ethyl Amount directly determines oil-gas reservoir phase.
3. determining the method for oil-gas reservoir phase according to claim 2, which is characterized in that in S5 further include: in based on crude The relationship of content and oil-gas reservoir phase that adamantane series compound drops in ethyl, which is established, differentiates plate.
4. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that being added in the crude oil sample has D16Adamantane standard sample, and required concentration is diluted to using solvent.
5. determining the method for oil-gas reservoir phase according to claim 4, which is characterized in that the solvent is methylene chloride.
6. determining the method for oil-gas reservoir phase according to claim 4, which is characterized in that being added in the crude oil sample has D16Adamantane standard sample, and the step of being diluted to required concentration using solvent specifically includes:
50-200mg crude oil sample is taken, the D of 0.25-0.75 μ g/ μ L is added into the crude oil sample16Adamantane 30-50 μ L, then Solvent is added to 1.0-2.0mL, is uniformly mixed stand-by.
7. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that S2 is specifically included:
Crude oil sample is analyzed using comprehensive two dimensional gas chromatography-flame ionization ditector GC × GC-FID, obtains second GC × GC-FID spectrogram of base drop adamantane；Then the ethyl drop adamantane compound provided according to GC × GC-TOFMS goes out Peak information calculates the peak area of spectrogram in GC × GC-FID, with D16Adamantane standard sample, which goes out peak area, to carry out pair Than obtaining the content of ethyl drop adamantane series compound.
8. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that adamantane series drop in ethyl in S3 Close the coefficient R of object content and the fitting of oil reservoir gas-oil ratio2When greater than 0.9, fitting formula is established.
9. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that be divided into oil-gas reservoir phase in S4 Gas condensate reservoir, volatilization oil reservoir and normal oil reservoir.
10. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that this method further includes that verifying is effective The step of property:
It is compared with pseudoternary phase diagram diagnostic method and/or hydrocarbon component block diagram diagnostic method, verifies its validity.
11. determining the method for oil-gas reservoir phase according to claim 1, which is characterized in that required crude oil sample includes just Often oil, condensate or heavy crude, are both needed to from well mouth of oil well.
12. determining the method for oil-gas reservoir phase according to claim 6, which is characterized in that the one-dimensional color of GC × GC-TOFMS Spectrum column is HP-PONA, and 50m × 0.2mm × 0.5 μm is arranged temperature programming: 50 DEG C of initial temperature, keeping 1min, risen to 20 DEG C/min 120 DEG C, 310 DEG C are risen to 3 DEG C/min, keeps 25min；Two way chromatograms column is Rx17HT, 1.5m × 0.1mm × 0.1 μm, program Warming temperature is higher than 10 DEG C of one-dimensional chromatographic column；Injector temperature is 300 DEG C, and Splitless injecting samples, carrier gas is helium, flow velocity 1mL/ min；Modulation period 6s, wherein 1.8s hot blow time；In terms of mass spectrum, transmission line and ion source temperature are respectively 300 DEG C and 240 DEG C, detector voltage 1600V, 40~600amu of mass scan range, 100 spectrograms of acquisition rate/s, the solvent delay time is 0min。
13. determining the method for oil-gas reservoir phase according to claim 12, which is characterized in that GC × GC-FID analysis method is adopted With chromatography experiment condition identical with GC × GC-TOFMS, carrier gas, hydrogen, air flow velocity be respectively 23mL/min, 60mL/ min,400mL/min；310 DEG C of detector temperature, 200 spectrograms of frequency acquisition/s, the solvent delay time is 9min.
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Cited By (5)

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CN111595930A (en) * 2020-04-29 2020-08-28 中国石油天然气股份有限公司 Method for determining TSR degree of crude oil according to aromatic hydrocarbon compounds
CN111595925A (en) * 2020-04-29 2020-08-28 中国石油天然气股份有限公司 Method for judging TSR (condensate oil recovery) degree according to petromics
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CN113933483A (en) * 2020-06-29 2022-01-14 中国石油化工股份有限公司 Method for judging and identifying alteration transformation action type and strength of deep oil and gas reservoir
CN113933483B (en) * 2020-06-29 2024-05-24 中国石油化工股份有限公司 Method for judging type and intensity of alteration modification action of deep oil and gas reservoir
CN114994189A (en) * 2021-03-02 2022-09-02 中国石油化工股份有限公司 Method for tracing migration direction of highly mature crude oil
CN114994189B (en) * 2021-03-02 2024-04-16 中国石油化工股份有限公司 Method for tracing migration direction of high-ripeness crude oil

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