CN110243919A - A method of Oil-gas origin and source are analyzed using vanadium isotope - Google Patents
A method of Oil-gas origin and source are analyzed using vanadium isotope Download PDFInfo
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- CN110243919A CN110243919A CN201910397232.8A CN201910397232A CN110243919A CN 110243919 A CN110243919 A CN 110243919A CN 201910397232 A CN201910397232 A CN 201910397232A CN 110243919 A CN110243919 A CN 110243919A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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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
Abstract
The present invention provides a kind of methods analyzed using vanadium isotope Oil-gas origin and source, wherein described method includes following steps: (1) extracting: the oil source rock of acquisition and/or crude oil sample being extracted, the sample containing vanadium is obtained；(2) ion exchange: the sample containing vanadium that step (1) is obtained carries out column chromatography using cation exchange resin, and the sample obtained by cation exchange resin column chromatography is reused into anion exchange resin and carries out column chromatography, obtain column chromatography samples；(3) the vanadium isotope composition in the column chromatography samples obtained to step (2) and content detect；(4) composition and content results of the vanadium isotope obtained using step (3) detection, Oil-gas origin in oil and gas reservoir is analyzed with source.
Description
Technical field
The present invention relates to oil-gas mining fields, and specifically, the present invention relates to a kind of using vanadium isotope to Oil-gas origin
The method analyzed with source.
Background technique
With the fine of investigation and prospecting and deeply, the Oil-gas origin of some complex areas and source, by conventional method, such as
The indexs such as biomarker, carbon isotope, it is difficult to determine Oil-gas origin and source, therefore, it is necessary to new index system is researched and developed,
Determine Oil-gas origin.
Vanadium (V) is the transition metal element of a multivalent state in nature, is distributed widely in the earth's crust, river, lake, sea
Midocean.V is also enriched with very much in crude oil, pitch, hydrocarbon source rock, and content can be used to refer to redox state up to thousands of μ g/g
Deng.V there are two types of stable isotope,50V (0.24%) and51V (99.76%), the wherein V of marine facies asphalt matter50Isotope is rich
Spend the V than inorganic origin50Isotope abundance is higher by 3.5%；Equally, DIFFERENT DEPOSITIONAL ENVIRONMENTS and evolution level hydrocarbon source rock and original
The V isotope of oil is different there are larger point, using source rock kerogen and the V isotopic ratio relationship of association asphalt matter, determines
Oil sources relationship.Therefore, with V isotope, these differences can carry out Oil-gas origin sentencing knowledge, instruct oil-gas exploration.
Summary of the invention
It is an object of the present invention to provide a kind of sides analyzed using vanadium isotope Oil-gas origin and source
Method.
In order to achieve the above object, the present invention provides a kind of sides analyzed using vanadium isotope Oil-gas origin and source
Method, wherein described method includes following steps:
(1) it extracts: the oil source rock of acquisition and/or crude oil sample being extracted, the sample containing vanadium is obtained；
(2) ion exchange: the sample containing vanadium that step (1) is obtained carries out column chromatography using cation exchange resin,
And the sample obtained by cation exchange resin column chromatography is reused into anion exchange resin and carries out column chromatography, obtain column layer
Analyse sample；
(3) the vanadium isotope composition in the column chromatography samples obtained to step (2) and content detect；
(4) composition and content results of the vanadium isotope obtained using step (3) detection, to Oil-gas origin in oil and gas reservoir
It is analyzed with source.
Some specific embodiments according to the present invention, wherein step (1) is using concentrated nitric acid as digestion solution, by that will acquire
Oil source rock and/or crude oil sample cleared up using digestion solution to extract the sample containing vanadium isotope.
Some specific embodiments according to the present invention, wherein the dosage of digestion solution is that every 50-100mg is adopted in step (1)
The oil source rock and/or crude oil sample of collection, need digestion solution 4ml.
Some specific embodiments according to the present invention, wherein it is 250-300 DEG C that step (1) resolution, which is in temperature, pressure
Power is to clear up 10-14h under 90-110 atmospheric pressure.
Some specific embodiments according to the present invention, wherein it is digestion solution that step (1), which includes using concentrated nitric acid, in temperature
It is 250-300 DEG C, pressure is under 90-110 atmospheric pressure, and resolution 10-14h obtains digestion solution；Then by digestion solution
Centrifugation, takes upper liquid to be evaporated to obtain solid；Solid is added in concentrated hydrochloric acid again, is heated to 220-230 DEG C, and keep 4-
8h, is evaporated to obtain and is evaporated product；Finally the obtained product that is evaporated is dissolved into 1N nitric acid and obtains the sample containing vanadium isotope.
Some specific embodiments according to the present invention, wherein the oil source rock and/or crude oil sample are hydrocarbon source rock rock-like
Product and/or crude oil sample.
The hydrocarbon source rock, crude oil are respectively from oil field coring well core or periphery outcropping rock sample, normal producing well
Oil sample, including different origins type and differing maturity and oil gas of different nature, rock sample etc..
Some specific embodiments according to the present invention, wherein the reservoir samples of step (1) acquisition are 50-100 microgram.
Because mass spectrum Accurate Determining V isotopics need net V amount in 5-10 microgram, it is therefore desirable to according to V in sample
Content is come the weight for the sample cleared up required for determining.In view of the content of V in hydrocarbon source rock and black shale is higher, ordinary circumstance
The lower rock dust for needing to weigh 50-100 microgram.
In view of having a large amount of organic matter in hydrocarbon source rock and black shale and crude oil, and want to obtain related with oil generation
Isotope process, therefore need to consider following three factors when selecting sample digestion method: firstly, it can be cleared up completely
In organic matter.This is because other magnesium-yttrium-transition metals such as V are adsorbed by organic matter in the sedimentary rock rich in organic matter
's；Second, other than organic matter, Lu Yuan cannot be cleared up and next silicate material.This is because the V only in organic matter is same
Position element composition could characterize it and really be related to oil generation process, and terrigenous clastic substance can interfere or cover the V's in organic matter
Information.Third, organic matter can generate a large amount of gas in digestion process and in turn result in high pressure, therefore consider Specimen eliminating
The reliability of equipment.
Based on above-mentioned 3 points, the resolution that step (1) of the present invention is related to V isotopics in the rock rich in organic matter is set
It is standby be there is Austrian Anton Paar (AntonPaar) company to produce high pressure ashing instrument (High Pressure Asher, referred to as
HPAS)。
50-100 milligrams of rock dusts and 4 milliliters of concentrated nitric acid are attached in the special quartz ampoule of HPAS, using Te Fulun
Film sealing, is encapsulated into HPAS.Under 280 DEG C, 100 atmospheric pressure, 12 hours are run.After equal instruments are cooling, by solution
It is transferred in 15 milliliters of centrifuge tube, high speed centrifugation, all draws out supernatant into 15 milliliters of beaker.Then by sample
Solution is evaporated in heater plate.Then, 2 milliliters of concentrated hydrochloric acids are added, lid is tightened, boil in a covered pot over a slow fire or so 6 hours in heating plate, with
After be evaporated.Finally, sample is dissolved into the 1N nitric acid of Accurate Calibration, ion exchange is waited.
Some specific embodiments according to the present invention, wherein the cation exchange resin of step (2) is AG50W-X12 type
Cation exchange resin；Anion exchange resin is AG1-X8 type anion exchange resin.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography packet using cation exchange resin
It includes using 1N nitric acid as solvent and the sample containing vanadium isotope that step (1) obtains dissolve simultaneously loading, then with 1.2N nitre
Acid is eluted as eluent.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography packet using cation exchange resin
Include and dissolve and loading by the sample containing vanadium isotope that step (1) obtains using 1N nitric acid as solvent, and with 1N nitric acid and
The mixed solution of the HF of 0.1N elutes impurity, then carries out affording cation exchange resin using 1.2N nitric acid as eluent
Cation exchange resin eluent is evaporated to obtain cationic resin column chromatography samples, cationic resin column is chromatographed by eluent
Sample is added to the resin removed in sample in the mixed solution of concentrated nitric acid and concentrated hydrochloric acid；It is evaporated, is obtained after being finally evaporated
Sample is dissolved into 0.01N hydrochloric acid, is ready for anion-exchange resin column chromatography.
Some specific embodiments according to the present invention, wherein the oil source rock and/or crude oil sample acquired with 50-100mg
Meter, step (2) carry out in column chromatography being to obtain step (1) using the 1N nitric acid of 1ml as solvent using cation exchange resin
Sample containing vanadium isotope dissolve and loading, and with 19ml elution.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography using cation exchange resin and exists
It further include cleaning cation exchange resin, and the step of with 1N nitric acid balance cation exchanger resin with 6N hydrochloric acid before loading.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography also using cation exchange resin
Sample including obtaining after being evaporated is dissolved in 1N nitric acid, then carries out a cation exchange resin column chromatography, will finally be steamed
The sample obtained after dry is dissolved into 0.01N hydrochloric acid, is ready for anion-exchange resin column chromatography.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography tool using cation exchange resin
Body includes:
Firstly, Accurate Calibration 1N nitric acid and 1.2N nitric acid, prepare 1N HNO3+0.1N HF。
Secondly, 2 milliliters of AG50W-X12 (200-400 mesh) cation exchange resin is attached in bio-rad pipe.With 6N salt
Acid cleaning resin, balances resin with 1N nitric acid.
1 milliliter of 1N nitric acid for having dissolved sample is added on resin column, 1NHNO is used3+ 0.1NHF elutes impurity element.So
19 milliliters of 1.2N nitric acid are added on resin column by substep afterwards, can thus be connected to more pure vanadium.
Sample is evaporated, enriching nitric acid and concentrated hydrochloric acid remove the resin drenched.Sample is dissolved into 1N nitric acid again, is repeated
This ion-exchange step.
Sample is dissolved into 1 milliliter of 0.01N hydrochloric acid, is ready for after cation exchange resin terminates twice by this
Anion exchange resin.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography packet using anion exchange resin
Including using 0.01N hydrochloric acid is solvent by the sample dissolution obtained by cation exchange resin column chromatography and loading, then uses 1N salt
Acid and 6N hydrochloric acid are eluted, and eluent is evaporated to obtain column chromatography samples.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography packet using anion exchange resin
The sample 0.01N dissolving with hydrochloric acid that will be obtained by cation exchange resin column chromatography is included, it is 30w/w%'s that concentration, which is then added,
Then hydrogen peroxide, loading are eluted with 1N hydrochloric acid and 6N hydrochloric acid, eluent is evaporated to obtain column chromatography samples.
Some specific embodiments according to the present invention, wherein the oil source rock and/or crude oil sample acquired with 50-100mg
Meter, step (2) carry out being the sample that will be obtained by cation exchange resin column chromatography in column chromatography using anion exchange resin
Then the hydrogen peroxide that 33 μm of l concentration are 30w/w% is added in the 0.01N dissolving with hydrochloric acid of product 1ml.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography packet using anion exchange resin
After including loading, the dioxygen water elution impurity for being first 1w/w% with 0.01N hydrochloric acid and concentration, then washed with 1N hydrochloric acid and 6N hydrochloric acid
It is de-, eluent is evaporated to obtain column chromatography samples.
Some specific embodiments according to the present invention, wherein the oil source rock and/or crude oil sample acquired with 50-100mg
Meter, step (2) carry out in column chromatography being washed with the 6N hydrochloric acid of the 1N hydrochloric acid of 17ml and 3ml using anion exchange resin
It is de-.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography using anion exchange resin and exists
Further include first cleaning anion exchange resin with 6N hydrochloric acid and 1N nitric acid before loading, then uses 0.01N hydrochloric acid and concentration
Resin is balanced for the hydrogen peroxide of 1w/w%, then loading again.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography also using anion exchange resin
After being evaporated eluent, the solid product 0.01N dissolving with hydrochloric acid obtained after being evaporated repeats an anion exchange
Resin column chromatography, after eluent is evaporated, except the resin drenched, obtains column chromatography samples.
Some specific embodiments according to the present invention, wherein step (2) carries out column chromatography tool using anion exchange resin
Body includes:
First time anion exchange resin
2 milliliters of AG1-X8 (200-400 mesh) anion exchange resin is attached in bio-rad pipe, respectively with 6N hydrochloric acid and
1N nitric acid cleans resin, then uses 0.01N HCl+1%H2O2Balance resin.
33 microlitre of 30% hydrogen peroxide is added in the 0.01N hydrochloric acid dissolved with sample, sample is added on resin column.Then use
15 milliliters of 0.01N HCl+1%H2O2Clean impurity.Finally sample is connect with 17 milliliters of 1N hydrochloric acid and 3 milliliters of 6N hydrochloric acid.
Sample is evaporated, and conversion medium and then is once dissolved into 1 milliliter of 0.01N hydrochloric acid, and the friendship of next step anion is carried out
Change resin.
Second of cation exchange resin
Second of anion exchange resin dosage only has 0.1 milliliter, therefore the acid amount of clear resin halves, balance acid
It reduces.Finally sample is connected in 1.7 milliliters of 1N hydrochloric acid and 0.3 milliliter of 6N hydrochloric acid.Solution is evaporated, except the resin drenched,
Then examination with computer can be saved.
Some specific embodiments according to the present invention, wherein step (3) be the column chromatography samples that are obtained to step (2) into
Row MC-ICP-MS detection, is formed and content results with the vanadium isotope obtained in sample.
MC-ICP-MS be German Thermal Fisher company production Neptune Plus.V isotope assay makes
With middle high-resolution (resolution ratio is greater than 5000) and Jet sample introduction cone and NiX- type interception cone.
In order to obtain more accurate V signal intensity,51The receiving cup of V is with 1010Ω amplifier, and50V is with 1011Ω amplification
Device.In Accurate Determining51V and50While V,52Cr,53Cr,48Ti and49Ti signal is also in other Faraday cups 1011The inspection of Ω amplifier
It surveys.
Sample, AA and BDH standard substance are dissolved into 2% nitric acid, are that V concentration reaches 0.8ppm.V isotope assay is to make
It is the Aridus II of CETAC company production with dry method sample introduction.50The signal strength of V in 0.4V or so,51The signal of V is strong
Degree is in 160V or so.40 cycles and 6 blocks of specific measurement.
Some specific embodiments according to the present invention, wherein step (4) include by DIFFERENT DEPOSITIONAL ENVIRONMENTS, it is different at
The composition for the vanadium isotope that ripe degree hydrocarbon source rock and step (3) detection obtain and the analysis of content results, establish different origins class
Codomain, the dividing value parameter of the vanadium isotope ratio of type oil gas sum up the vanadium mass fractionation and non-mass point of different type oil gas
Information characteristics are evaporated, foundation, which is sentenced, knows index plate, and the oil source rock and/or crude oil sample obtained using stepout well passes through vanadium isotope
Analysis, can determine Oil-gas source and the origin cause of formation.Instruct exploration deployment.
Wherein, the vanadium isotope of the crude oil and oil source rock in step (4) terrestrial facies source is -1~0 ± 0.15 ‰, marine facies source
Crude oil and oil source rock vanadium isotope -2~-1 ± 0.12 ‰, therefore vanadium isotope can be used as terrestrial facies at -1 ‰
The division limits in source or marine facies source.
The detection method of vanadium isotope includes following condition in oil and gas reservoir of the present invention:
1. laboratory condition
This requirement of experiment is carried out in Superclean Lab.Superclean Lab overall cleanliness factor is km grade, laboratory operation platform
The cleanliness of draught cupboard is hundred meter levels.
2. reagent
Hydrofluoric acid, nitric acid and the hydrochloric acid used in experimentation are all Thermal Fisher Scientific ortho acid warps
The high-purity concentrated acid obtained after low temperature distillation twice.
The ultrapure hydrogen peroxide of volumetric concentration 30% picks up from AUECC company.
All water used in experiment flow are all the ultrapure waters (18.2 Ω cm) of this Laboratory Production.
Detailed description of the invention
Fig. 1 is the vanadium isotope numerical value figure of embodiment 1.
Specific embodiment
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
Embodiment 1
Acquisition Bohai gulf basin terrestrial facies oil and oil source rock respectively, Tarim Basin marine facies oil and oil source rock, by following process
It separates and detects:
1. laboratory condition
This requirement of experiment is carried out in Superclean Lab.Superclean Lab overall cleanliness factor is km grade, laboratory operation platform
The cleanliness of draught cupboard is hundred meter levels.
2. reagent
Hydrofluoric acid, nitric acid and the hydrochloric acid used in experimentation are all Thermal Fisher Scientific ortho acid warps
The high-purity concentrated acid obtained after low temperature distillation twice.
The ultrapure hydrogen peroxide of volumetric concentration 30% picks up from AUECC company.
All water used in experiment flow are all the ultrapure waters (18.2 Ω cm) of this Laboratory Production.
3. Specimen eliminating
Mass spectrum Accurate Determining V isotopics need net V amount in 5-10 microgram, it is therefore desirable to according to the content of V in sample
To determine the weight of the required sample cleared up.In view of the content of V in hydrocarbon source rock and black shale is higher, need under normal circumstances
Weigh the rock dust of 50-100 microgram.
In view of having a large amount of organic matter in hydrocarbon source rock and black shale and crude oil, and want to obtain related with oil generation
Isotope process, therefore need to consider following three factors when selecting sample digestion method: firstly, it can be cleared up completely
In organic matter.This is because other magnesium-yttrium-transition metals such as V are adsorbed by organic matter in the sedimentary rock rich in organic matter
's；Second, other than organic matter, Lu Yuan cannot be cleared up and next silicate material.This is because the V only in organic matter is same
Position element composition could characterize it and really be related to oil generation process, and terrigenous clastic substance can interfere or cover the V's in organic matter
Information.Third, organic matter can generate a large amount of gas in digestion process and in turn result in high pressure, therefore consider Specimen eliminating
The reliability of equipment.
Based on above-mentioned 3 points, this digesting equipment for being related to V isotopics in the rock rich in organic matter is that have Austria
The high pressure of land productivity Anton Paar (AntonPaar) company production is ashed instrument (High Pressure Asher, referred to as HPAS).
50-100 milligrams of rock dusts and 4 milliliters of concentrated nitric acid are attached in the special quartz ampoule of HPAS, using Te Fulun
Film sealing, is encapsulated into HPAS.Under 280 DEG C, 100 atmospheric pressure, 12 hours are run.After equal instruments are cooling, by solution
It is transferred in 15 milliliters of centrifuge tube, high speed centrifugation, all draws out supernatant into 15 milliliters of beaker.Then by sample
Solution is evaporated in heater plate.Then, 2 milliliters of concentrated hydrochloric acids are added, lid is tightened, boil in a covered pot over a slow fire or so 6 hours in heating plate, with
After be evaporated.Finally, sample is dissolved into the 1N nitric acid of Accurate Calibration, ion exchange is waited.
4. ion exchange process
(1) cation exchange resin (carrying out twice)
Firstly, Accurate Calibration 1N nitric acid and 1.2N nitric acid, prepare 1NHNO3+0.1NHF。
Secondly, 2 milliliters of AG50W-X12 (200-400 mesh) cation exchange resin is attached in bio-rad pipe.With 6N salt
Acid cleaning resin, balances resin with 1N nitric acid.
1 milliliter of 1N nitric acid for having dissolved sample is added on resin column, 1NHNO is used3+ 0.1NHF elutes impurity element.So
19 milliliters of 1.2N nitric acid are added on resin column by substep afterwards, can thus be connected to more pure vanadium.
Sample is evaporated, enriching nitric acid and concentrated hydrochloric acid remove the resin drenched.Sample is dissolved into 1N nitric acid again, is repeated
This ion-exchange step.
Sample is dissolved into 1 milliliter of 0.01N hydrochloric acid, is ready for after cation exchange resin terminates twice by this
Anion exchange resin.
(2) anion exchange resin (carrying out twice)
2 milliliters of AG1-X8 (200-400 mesh) anion exchange resin is attached in bio-rad pipe, respectively with 6N hydrochloric acid and
1N nitric acid cleans resin, then uses 0.01NHCl+1%H2O2Balance resin.
33 microlitre of 30% hydrogen peroxide is added in the 0.01N hydrochloric acid dissolved with sample, sample is added on resin column.Then use
15 milliliters of 0.01NHCl+1%H2O2Clean impurity.Finally sample is connect with 17 milliliters of 1N hydrochloric acid and 3 milliliters of 6N hydrochloric acid.
Sample is evaporated, and conversion medium and then is once dissolved into 1 milliliter of 0.01N hydrochloric acid, and the friendship of next step anion is carried out
Change resin.
Second of anion exchange resin dosage only has 0.1 milliliter, therefore the acid amount of clear resin halves, balance acid
It reduces.Finally sample is connected in 1.7 milliliters of 1N hydrochloric acid and 0.3 milliliter of 6N hydrochloric acid.Solution is evaporated, except the resin drenched,
Then examination with computer can be saved.
5. vanadium determines isotope test
MC-ICP-MS be German Thermal Fisher company production Neptune Plus.V isotope assay makes
With middle high-resolution (resolution ratio is greater than 5000) and Jet sample introduction cone and NiX- type interception cone.
In order to obtain more accurate V signal intensity,51The receiving cup of V is with 1010Ω amplifier, and50V is with 1011Ω amplification
Device.In Accurate Determining51V and50While V,52Cr,53Cr,48Ti and49Ti signal is also in other Faraday cups 1011The inspection of Ω amplifier
It surveys.
Sample, AA and BDH standard substance are dissolved into 2% nitric acid, are that V concentration reaches 0.8ppm.V isotope assay is to make
It is the Aridus II of CETAC company production with dry method sample introduction.50The signal strength of V in 0.4V or so,51The signal of V is strong
Degree is in 160V or so.40 cycles and 6 blocks of specific measurement.
Obtaining vanadium isotope value is respectively:
The crude oil in Bohai gulf basin terrestrial facies source and the vanadium isotope of oil source rock are -1~0 ± 0.15 ‰；
The crude oil in Tarim Basin marine facies source and the vanadium isotope of oil source rock are -2~-1 ± 0.12 ‰.This two groups of numerical value
It is very identical in the origin cause of formation with practical Oil-gas source, it can determine that this method is effective, compensate for the deficiency of conventional method.
As shown in Figure 1, the vanadium isotope data of marine facies oil are -2.2~-0.9 ‰, the vanadium isotope data of terrestrial facies oil for -
0.85~0.2 ‰.And the crude oil in Bohai gulf basin terrestrial facies source and the vanadium isotope of oil source rock are -1~0 ± 0.15 ‰；In tower
Tub marine facies source crude oil and oil source rock vanadium isotope -2~-1 ± 0.12 ‰.This two groups of numerical value and practical oil gas come
Data derived from the origin cause of formation are very identical, can determine that this method is effective, compensate for the deficiency of conventional method.Therefore vanadium isotope
At -1 ‰, it can be used as the division limits in terrestrial facies source or marine facies source.
Claims (17)
1. a kind of method analyzed using vanadium isotope Oil-gas origin and source, wherein the method includes walking as follows
It is rapid:
(1) it extracts: the oil source rock of acquisition and/or crude oil sample being extracted, the sample containing vanadium is obtained；
(2) ion exchange: the sample containing vanadium that step (1) is obtained carries out column chromatography using cation exchange resin, and will
Anion exchange resin is reused by the sample that cation exchange resin column chromatography obtains and carries out column chromatography, obtains column chromatography sample
Product；
(3) the vanadium isotope composition in the column chromatography samples obtained to step (2) and content detect；
(4) composition and content results of the vanadium isotope obtained using step (3) detection to Oil-gas origin in oil and gas reservoir and is come
It is analyzed in source.
2. according to the method described in claim 1, wherein, step (1) is to pass through the reservoir that will be acquired using concentrated nitric acid as digestion solution
Sample is cleared up to extract the sample containing vanadium isotope using digestion solution.
3. according to the method described in claim 2, wherein, it is 250-300 DEG C that step (1) resolution, which is in temperature, and pressure is
Under 90-110 atmospheric pressure, 10-14h is cleared up.
4. according to the method described in claim 1, wherein, step (1) is 250- in temperature including the use of concentrated nitric acid being digestion solution
300 DEG C, pressure is under 90-110 atmospheric pressure, and resolution 10-14h obtains digestion solution；Then digestion solution is centrifuged, is taken
Upper liquid is evaporated to obtain solid；Solid is added in concentrated hydrochloric acid again, 220-230 DEG C is heated to, and keep 4-8h, is evaporated
It obtains being evaporated product；Finally the obtained product that is evaporated is dissolved into 1N nitric acid and obtains the sample containing vanadium isotope.
5. according to the method described in claim 1, wherein, the reservoir samples are hydrocarbon source rock rock sample and/or crude oil sample.
6. according to the method described in claim 1, wherein, the cation exchange resin of step (2) is AG50W-X12 type cation
Exchanger resin；Anion exchange resin is AG1-X8 type anion exchange resin.
7. according to the method described in claim 1, wherein, step (2) using cation exchange resin carry out column chromatography include with
The sample containing vanadium isotope that step (1) obtains dissolve simultaneously loading for solvent by 1N nitric acid, then with 1.2N nitric acid work
It is eluted for eluent.
8. according to the method described in claim 7, wherein, step (2) using cation exchange resin carry out column chromatography include with
The sample containing vanadium isotope that step (1) obtains dissolve simultaneously loading for solvent by 1N nitric acid, and with 1N nitric acid and 0.1N
The mixed solution of HF elute impurity, then carry out affording cation exchange resin using 1.2N nitric acid as eluent and elute
Cation exchange resin eluent is evaporated to obtain cationic resin column chromatography samples by liquid, by cationic resin column chromatography samples
It is added to the resin removed in sample in the mixed solution of concentrated nitric acid and concentrated hydrochloric acid；It is evaporated, the sample obtained after being finally evaporated
It is dissolved into 0.01N hydrochloric acid, is ready for anion-exchange resin column chromatography.
9. method according to claim 7 or 8, wherein step (2) carries out column chromatography upper using cation exchange resin
It further include cleaning cation exchange resin, and the step of with 1N nitric acid balance cation exchanger resin with 6N hydrochloric acid before sample.
10. according to method described in claim 7~9 any one, wherein step (2) is carried out using cation exchange resin
Column chromatography further includes that the sample obtained after being evaporated is dissolved in 1N nitric acid, then carries out a cation exchange resin column chromatography,
The sample obtained after being finally evaporated is dissolved into 0.01N hydrochloric acid, is ready for anion-exchange resin column chromatography.
11. according to the method described in claim 1, wherein, step (2) using anion exchange resin carry out column chromatography include with
0.01N hydrochloric acid is the sample dissolution that solvent will be obtained by cation exchange resin column chromatography and loading, then with 1N hydrochloric acid and
6N hydrochloric acid is eluted, and eluent is evaporated to obtain column chromatography samples.
12. according to the method for claim 11, wherein step (2) carries out column chromatography using anion exchange resin and includes
The sample 0.01N dissolving with hydrochloric acid that will be obtained by cation exchange resin column chromatography, it is the double of 30w/w% that concentration, which is then added,
Then oxygen water, loading are eluted with 1N hydrochloric acid and 6N hydrochloric acid, eluent is evaporated to obtain column chromatography samples.
13. method according to claim 11 or 12, wherein step (2) carries out column chromatography using anion exchange resin
After loading, the dioxygen water elution impurity for being first 1w/w% with 0.01N hydrochloric acid and concentration, then carried out with 1N hydrochloric acid and 6N hydrochloric acid
Elution, eluent is evaporated to obtain column chromatography samples.
14. method described in 1~13 any one according to claim 1, wherein step (2) using anion exchange resin into
Row column is chromatographed before loading, is further included first cleaning anion exchange resin with 6N hydrochloric acid and 1N nitric acid, is then used 0.01N
The hydrogen peroxide that hydrochloric acid and concentration are 1w/w% balances resin, then loading again.
15. method described in 1~14 any one according to claim 1, wherein step (2) using anion exchange resin into
Row column chromatography further includes the solid product 0.01N dissolving with hydrochloric acid obtained after being evaporated after being evaporated eluent, is repeated primary
Anion-exchange resin column chromatography, after eluent is evaporated, except the resin drenched, obtains column chromatography samples.
16. according to the method described in claim 1, wherein, step (3) is that the column chromatography samples obtained to step (2) carry out MC-
ICP-MS detection, is formed and content results with the vanadium isotope obtained in sample.
17. according to the method described in claim 1, wherein, step (4) includes by DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity
The composition for the vanadium isotope that hydrocarbon source rock and step (3) detection obtain and the analysis of content results, establish different origins type of oil
Codomain, the dividing value parameter of the vanadium isotope ratio of gas, the vanadium mass fractionation and non-mass fractionation for summing up different type oil gas are believed
Feature is ceased, foundation, which is sentenced, knows index plate, and the oil source rock and/or crude oil sample obtained using stepout well is analyzed by vanadium isotope,
It can determine Oil-gas source and the origin cause of formation, instruct exploration deployment.
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