CN110412106A - Carry out the method for OIL SOURCE CORRELATION with molybdenum isotope - Google Patents
Carry out the method for OIL SOURCE CORRELATION with molybdenum isotope Download PDFInfo
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- CN110412106A CN110412106A CN201910608051.5A CN201910608051A CN110412106A CN 110412106 A CN110412106 A CN 110412106A CN 201910608051 A CN201910608051 A CN 201910608051A CN 110412106 A CN110412106 A CN 110412106A
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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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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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
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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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
Abstract
The invention discloses a kind of methods for carrying out OIL SOURCE CORRELATION with molybdenum isotope.Method includes the following steps: in S100, crude oil molybdenum element separation and concentration；The separation and concentration of molybdenum element in S200, hydrocarbon source rock；The content of S300, test analysis molybdenum element；S400, the stable isotope composition for testing and analyzing molybdenum；S500, by the analysis to molybdenum isotope in known DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity hydrocarbon source rock and crude oil and source rock of different nature, establish δ97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate；S600, index plate is known according to sentencing for foundation, determines unknown oil sources source and the origin cause of formation.The present invention sentences with molybdenum isotope and knows Oil-gas source and the origin cause of formation, by quickly determining Oil-gas origin, provides technology and theoretical direction for exploration target determination.
Description
Technical field
The invention belongs to oil-gas exploration technical fields, and in particular to a kind of side for carrying out OIL SOURCE CORRELATION with molybdenum isotope
Method.
Background technique
Organic geochemistry research is primarily upon the composition of organic matter, structure, origin and evolution in geologic body, surveys in oil gas
In spy field, especially Oil-gas origin is most important with OIL SOURCE CORRELATION, is related to exploration target assessment preferred, oil-gas reservoir with well location
Therefore scale and the regularity of distribution etc. are highly valued.Conventional method is to use the indexs such as biomarker, carbon isotope, is determined
Oil-gas origin and source, utilization of succeeding in most area or oil gas field.But some complex areas, for example, tower
In tub, oil gas is to always exist dispute from Cambrian system or the Ordovician system.Therefore, it is necessary to new index system is researched and developed,
Determine Oil-gas origin.
Molybdenum is easily adsorbed and is chelated by organic matter, therefore molybdenum is easily enriched in hydrocarbon source rock, and enters oil gas during at hydrocarbon, with
Oil gas is migrated, therefore molybdenum has important with processes such as organic matter formation, thermal maturity hydrocarbon, migration and accumulations in deposition
Tracer value.Molybdenum in the hydrocarbon source rock and oil gas of different craton areas, different origins type and different heat evolution stages stablizes same position
Prime information has certain difference, can carry out sentencing knowledge to Oil-gas origin with these differences, instruct oil-gas exploration.
Summary of the invention
Based on background above technology, the present invention provides a kind of method for carrying out OIL SOURCE CORRELATION with molybdenum isotope.The present invention
The current blank sentenced with molybdenum isotope and know Oil-gas source and the origin cause of formation has been filled up to survey by quickly determining Oil-gas origin for oil gas
It visits target and offer technology and theoretical direction is provided.
In order to achieve the goal above, the invention adopts the following technical scheme:
One aspect of the present invention provides a kind of method for carrying out OIL SOURCE CORRELATION with molybdenum isotope, and this method includes following step
It is rapid:
The separation and concentration of molybdenum element in S100, crude oil；
The separation and concentration of molybdenum element in S200, hydrocarbon source rock；
The content of S300, test analysis molybdenum element；
S400, the stable isotope composition for testing and analyzing molybdenum；
S500, by known DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity hydrocarbon source rock and crude oil of different nature and hydrocarbon
The analysis of molybdenum isotope, establishes δ in source rock97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate；
The mass fractionation of molybdenum is the molybdenum isotope separation and concentration of the different quality number in redox reaction in differential responses
In object；Non-mass fractionation is that the fractionation of molybdenum isotope in some reactions is not influenced mainly by qualitative factor.
S600, index plate is known according to sentencing for foundation, determines unknown oil sources source and the origin cause of formation, instructs exploration deployment.
In above method, the hydrocarbon source rock and crude oil are respectively from oil field coring well core or periphery outcropping rock sample
The oil sample of product, normal producing well, including different origins type and differing maturity and crude oil of different nature, rock
Sample etc..
Preferably, the δ97Mo (‰)-Oil Reservoir Types, which are sentenced, to be known in index plate, the δ of coal measures crude oil97Mo (‰) range is
1.04 ‰~1.58 ‰, the δ of source rocks in coal measures97Mo (‰) range is 0.78 ‰~1.41 ‰, the δ of Marine Crude Oil97Mo (‰) model
Enclosing is 0.17 ‰~0.64 ‰, the δ of Marine Hydrocarbon Source Rocks97Mo (‰) range is 0.01 ‰~0.77 ‰, the δ of CONTINENTAL CRUDE97Mo
(‰) range is -0.46 ‰~-0.14 ‰, the δ of nonmarine source rock97Mo (‰) range is -0.79 ‰~-0.08 ‰.
It is described in detail below for each step:
The separation and concentration of molybdenum element in S100, crude oil.
Preferably, S100 is specifically included:
The preparation of S110, crude oil sample；
The separating-purifying of molybdenum in S120, crude oil sample.
It is further preferred that the preparation of S110 crude oil sample includes:
S111, fresh crude oil is taken, sequentially adds petroleum ether and ethyl alcohol is miscible, heated, obtains preliminary sample；Wherein,
Petroleum ether and ethyl alcohol are the preferable organic solvents of organic matter effect in dissolving crude oil.
Preferably, the ratio of crude oil, petroleum ether and ethyl alcohol are as follows: (6~8g): 14~16mL:14~16mL.More preferably such as
(6~8g): 15mL:15mL.
Preferably, the temperature of heating is 75~85 DEG C, and the time is 11~13 hours.It is highly preferred that the temperature of heating is 80
DEG C, the time is 12 hours.
Such as in an embodiment of the present invention, this step specifically includes:
Fuel-displaced well head from production well site, takes fresh crude oil sample 20g or so；6~8g of fresh crude oil is weighed to burn in quartz
In cup, petroleum ether 15mL is added, shakes up so that crude oil is substantially miscible with petroleum ether, addition dehydrated alcohol 15mL, in electricity after shaking up
80 DEG C of hot plate are heated 12 hours.
S112, fresh crude oil is weighed again, repeat S111 process.
S113, after standing the preliminary sample prepared twice at normal temperature, top oil sample is extracted respectively and is mixed, nothing is added
Water-ethanol heats after shaking up, and crude oil sample to be tested is made.
Preferably, 22~24 hours are stood, 60~70 DEG C are heated 16~18 hours.It is highly preferred that 24 hours are stood,
60 DEG C are heated 18 hours.
It carries out miscible being while to shorten heating time to allow organic component sufficiently to dissolve in two times in this embodiment.
It is further preferred that the separating-purifying of molybdenum element includes: in S120 crude oil sample
1) crude oil sample is cleared up；
2) sample after clearing up is dissolved in HNO3In HF, heating is reacted, until sample is completely dissolved；After reaction
It is evaporated to wet salt, then uses HNO3Extra HF is removed, HCl is eventually adding, is evaporated as powder；
3) purified with Chelx100 resin and TSK-8HG resin twin columns method to Mo sample, be to be situated between with 7mol/LHCl
Confrontation molybdenum element is separated, and the molybdenum solution purified is evaporated, and is converted into 2%HNO3Medium, it is to be measured.
Preferably, the solvent of the resolution is methylene chloride, digestive reagent HNO3-H2O2Acid system.
In S120, the separation of crude oil molybdenum element uses organic solvent dichloromethane sample dissolution, CH2Cl2It can be sufficiently molten
Petroleum is solved, so that each component is uniformly dispersed in crude oil, sufficiently contacts to improve oxidation efficiency with digestive reagent, obtains repeatability
Preferable monitoring result, digestive reagent then select HNO3-H2O2Acid system, to reach H in removal crude oil2S and organic matter impurity
Effect.
For example, S120 is specifically included in the embodiment of the present invention:
1) 1g crude oil sample is accurately weighed in high-pressure sealed counteracting tank, with 2mL CH2Cl2Abundant dissolving crude oil, then again
The dense HNO of 5mL is added3-H2O2Digestive reagent clears up 5min under 200 DEG C of high temperature, is settled to 30mL with high purity water after cooling, will determine
The drying kitchen that appearance sample is placed in 600 DEG C removes organic matter for 24 hours.
2) HNO of 2mL 2mol/L is added3It with the HF of 4mL 0.5mol/L, closes the lid, sample dissolution is put into baking oven
220 DEG C of reaction 48h；It can be repeated until sample is completely dissolved, cooling is taken out, and is evaporated to wet salt for 200 DEG C in heating plate；Again
With the HNO of 2mL 2mol/L3Extra HF is removed, removes HF 3 times repeatedly clean, 5mL 6mol/L HCl is eventually adding, steams
It does as powder.This step vapors away ingredient volatile in sample, then removes organic matter.
3) purified with Chelx100 resin and TSK-8HG resin twin columns method to Mo sample, be with 7mol/L HCl
Medium separates molybdenum element, and the molybdenum solution purified is evaporated, and is converted into 2%HNO3Medium, it is to be measured, wait S300 and
The constituent content mensure and isotope analysis of S400.It is converted into 2%HNO3Medium specifically: the HNO of 8mol/L is added3About 20 μ L
2%HNO is converted by sample3Medium；2%HNO is converted by sample3Medium is to meet the acid medium requirement of instrument test.
The separation and concentration of molybdenum element in S200, hydrocarbon source rock.
Preferably, S200 is specifically included:
S210, the selection of rock sample and broken sample, obtain the sample powder of hydrocarbon source rock；
The separating-purifying of molybdenum element in S220, sample powder.
Preferably, S210 includes:
S211, rock sample is chosen；
S212, broken sample, grinding obtain sample powder.
In embodiments of the present invention, the process of S210 preparation sample powder includes:
1) choose rock sample: observation rock sample surface it is whether fresh, by rate of decay, take a picture describe sample letter
It ceases in typing sample table.Sample is enclose with clean cloth, then plank is covered on sample top bottom surface, beats plank with steel hammer and smashes
Sample, the four sides for choosing 5g or so after sample broke is fresh, without quartz vein, the sample particle without worm channel construction, with disposable pincers
Sub-folder takes sample to be put into sample sack and record and takes number.
2) broken sample: two identical grinding pots are chosen, one of them is put into agate ball, a) in the grinding pot for having agate ball
Be added quartz sand half mulching agate ball, two grinding pots are tightened be placed on crusher fix with 1300r/min revolving speed turn 3 points
Clock, after remove and pour out quartz powder, whether observation grinding pot interior surface clean, if not continuing to this step completely.
B) it is put into grinding pot with the sample in disposable pliers clamping sample sack, tightens to be placed on crusher and fix 1300r/min
Revolving speed turns 3 minutes, after remove sample powder be poured on disposable paper, and with table inside disposable tissues wiping grinding pot
Face and agate ball pour out sample powder as far as possible, and sample powder is then poured into record number in sample sack.C) grinding is washed
Tank repeats step a) 2-3 times (must confirm that grinding pot interior surface is clean).Then the broken of next sample is successively carried out
Sample work.
Preferably, the separating-purifying of molybdenum element includes: in S220 sample powder
1) sample powder is added HCl and carries out resolution reaction in high-pressure digestion tank；It is centrifuged after reaction with deionized water
Cleaning；
2) it by after the sample drying after eccentric cleaning, clays into power；
3) purified with Chelex-100 resin to Mo sample, separate molybdenum element；
The HNO of 2mol/L is used first3Solution is completely dissolved sample powder, with the HNO of 6mol/L3Solution and deionized water
Resin is cleaned, then washs the isobar of molybdenum with the mixed solution of 0.02mol/L HCl and 0.2mol/L HF, then use
The NH of 8mol/L3Molybdenum element in solution collection of ions exchanger resin, the molybdenum solution purified is evaporated to be dissolved with nitric acid again, most
The HNO of 0.3mol/L is dissolved a sample in eventually3Solution, it is to be measured, wait the constituent content mensure and isotope point of S300 and S400
Analysis.
In embodiments of the present invention, the separating-purifying of molybdenum includes: in S220 sample powder
1) sample powder of 1g or so is weighed in 20mL high-pressure digestion tank, is added 20mL 3mol/L's with liquid-transfering gun
HCl closes the lid, it is allowed sufficiently to react, and standing is cleaned with deionized water afterwards for 24 hours, washes and is once put into 3200r/min's
Centrifuge is centrifuged ten minutes, is at least cleaned 4 times, is cleaned until being no longer acidity.This step selects HCl sample dissolution, because
Many carbonate, hydroxide, various sulfide etc. can be by dissolving with hydrochloric acid.
2) 75 DEG C of baking oven reaction 12-20h are put into, drying is clayed into power with weighing spoon and weighs 6mg.
3) purified with chelating resin Chelex-100 to Mo sample, separate molybdenum element, prepare 2mol/ first
The HNO of L3Solution is completely dissolved sample powder, with the HNO of 6mol/L3Solution and deionized water clean ion exchange resin, so
The isobar of molybdenum, then the NH with 8mol/L are washed with the mixed solution of 0.02mol/L HCl and 0.2mol/L HF afterwards3It is molten
Molybdenum element in liquid collection of ions exchanger resin is evaporated the HNO for using 2mol/L again in 150 DEG C of baking ovens3Solution dissolution finally will
Sample is dissolved in the HNO of 0.3mol/L3Solution, it is to be measured, wait the constituent content mensure and isotope analysis of S300 and S400.
The content of S300, test analysis molybdenum element.
The contents for receiving icp ms MC-ICP-MS measurement molybdenum element are used in S300 more.
The test of the content of molybdenum element of the present invention specifically includes:
1) it in 150 DEG C or more of baking oven, dries sample 2 hours, to remove the absorption water of sample surfaces.
2) 5g sample is accurately weighed, is placed in 800 DEG C of high temperature furnace and carries out ashing processing, treated, and residue is added
5mL nitric acid.It is placed on electric hot plate, 250 DEG C of constant temperature, dissolves by heating.If there is muddy object, the sulphur of appropriate 0.5mol/L is added
Acid removal.
3) ammonium chloride that appropriate 2mol/L is added can remove the Ca ion in sample.
4) high-purity HCl and each 5mL of high-purity HF is added, covers and steel bushing is closed, be put into baking oven 200 DEG C, constant temperature 48 hours.
It is evaporated on electric hot plate after cooling, adds the high-purity HCl of 3mL and steam to wet salt (remove remaining HF).
5) it is then always digested in tetraacethyl diaminoethanes and solution is made to be shown as acid, molybdenum is measured with this
Total content.With the content of postdigestive sample measurement ferro element, receive icp ms MC-ICP-MS with more
It is measured.
S400, the stable isotope composition for testing and analyzing molybdenum.
Preferably, test and analyze the steady of molybdenum using the icp ms MC-ICP-MS that receive in S400 more
Determine isotopics.
1) will cleaning and cutting sample comminution and burn 10 hours at 200 DEG C -300 DEG C, in the HCl-HF- of double distillations
HNO3Mixture in digest, then carry out second in chloroazotic acid and digest.
2) purified with chelating resin Chelex-100 to molybdenum isotope sample.By sample Nu after purification
The double focusing multiple-collector plasma source mass spectrometry instrument Nu Plasma HR of Instruments company production is measured.Use DSN-
100 type films go to dissolve into plasma.
3) the nitric acid cleaning sample of 0.5mol/L, 5min are used；Standard specimen, 3min are cleaned with the nitric acid of 0.05mol/L again.
4) it is measured using MC-ICP-MS high-precision measuring isotope, carries out instrument matter using sample-standard specimen interior extrapolation method
Amount discriminates against correction, and thousand point deviations of the molybdenum isotope ratio result measured with sample relative to standard specimen indicate.
S500, by known DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity hydrocarbon source rock and the former same position of oil and gas molybdenum
The analysis of element, establishes δ97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate.Establishing δ97Mo (‰)-Oil Reservoir Types sentence knowledge indicatrix
When version, it is thus necessary to determine that codomain, the dividing value parameter of the molybdenum isotope ratio of different origins type oil reservoir sum up different type oil reservoir
Molybdenum mass fractionation and non-mass be fractionated information characteristics.
S600, index plate is known according to sentencing for foundation, determines unknown oil sources source and the origin cause of formation, instructs exploration deployment.
Sentenced after knowing index plate using the method for the present invention foundation, it can be by carrying out molybdenum isotope point to new well crude oil sample
Analysis, determines Oil-gas source and the origin cause of formation, instructs subsequent exploration deployment.
Detailed description of the invention
Fig. 1 is the δ that the embodiment of the present invention is established97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate.
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 embodiment of the present invention is specifically described by taking Bohai gulf basin oil reservoir as an example, specific method the following steps are included:
S111, the fuel-displaced well head from production well site, take fresh crude oil sample 20g or so；6~8g of fresh crude oil is weighed in stone
In English beaker, petroleum ether 15mL is added, shakes up so that crude oil is substantially miscible with petroleum ether, addition dehydrated alcohol 15mL, after shaking up
It is heated 12 hours at 80 DEG C of electric hot plate.
S112,6~8g of fresh crude oil is weighed again in quartz beaker, repeat S110 process.
S113, after the preliminary sample prepared twice is stood 24 hours at normal temperature, top oil sample is extracted respectively and is mixed
It closes, dehydrated alcohol 20mL is added, heated 18 hours after shaking up at 60 DEG C of electric hot plate, crude oil sample to be tested is made.
The separating-purifying of molybdenum element in S120, crude oil sample:
1) 1g crude oil sample is accurately weighed in high-pressure sealed counteracting tank, with 2mL CH2Cl2Abundant dissolving crude oil, then again
The dense HNO of 5mL is added3-H2O2Digestive reagent clears up 5min under 200 DEG C of high temperature, is settled to 30mL with high purity water after cooling, will determine
The drying kitchen that appearance sample is placed in 600 DEG C removes organic matter for 24 hours.
2) HNO of 2mL 2mol/L is added3It with the HF of 4mL 0.5mol/L, closes the lid, sample dissolution is put into baking oven
220 DEG C of reaction 48h；It can be repeated until sample is completely dissolved, cooling is taken out, and is evaporated to wet salt for 200 DEG C in heating plate；Again
With the HNO of 2mL 2mol/L3Extra HF is removed, removes HF 3 times repeatedly clean, 5mL 6mol/L HCl is eventually adding, steams
It does as powder.
3) purified with Chelx100 resin and TSK-8HG resin twin columns method to Mo sample, be with 7mol/L HCl
Medium separates molybdenum element, and the molybdenum solution purified is evaporated, and is converted into 2%HNO3Medium, it is to be measured.It is converted into 2%HNO3
Medium specifically: the HNO of 8mol/L is added3Sample is converted 2%HNO by about 20 μ L3Medium；2%HNO is converted by sample3It is situated between
Matter is to meet the acid medium requirement of instrument test.
S210, source rock sample powder is prepared:
1) choose rock sample: observation rock sample surface it is whether fresh, by rate of decay, take a picture describe sample letter
It ceases in typing sample table.Sample is enclose with clean cloth, then plank is covered on sample top bottom surface, beats plank with steel hammer and smashes
Sample, the four sides for choosing 5g or so after sample broke is fresh, without quartz vein, the sample particle without worm channel construction, with disposable pincers
Sub-folder takes sample to be put into sample sack and record and takes number.2) broken sample: two identical grinding pots are chosen, one of them is put into Ma
Quartz sand half mulching agate ball a) is added in the grinding pot for having agate ball, two grinding pots are tightened and are placed on crusher for Nao ball
On fix and turned 3 minutes with 1300 revolving speeds, after remove and pour out quartz powder, whether observation grinding pot interior surface clean,
If not continuing to this step completely.B) it is put into grinding pot with the sample in disposable pliers clamping sample sack, tightens and be placed on
1300r/min revolving speed is fixed on crusher to turn 3 minutes, after remove sample powder be poured on disposable paper, and with one
Secondary property paper handkerchief wiping grinding pot interior surface and agate ball pour out sample powder as far as possible, and sample powder is then poured into sample
Record number in product bag.C) grinding pot is washed, step a) 2-3 times (must confirm that grinding pot interior surface is clean) is repeated.So
The broken sample work of next sample is successively carried out afterwards.
The separating-purifying of molybdenum in S220, sample powder:
1) sample powder of 1g or so is weighed in 20mL high-pressure digestion tank, is added 20mL 3mol/L's with liquid-transfering gun
HCl closes the lid, it is allowed sufficiently to react, and standing is cleaned with deionized water afterwards for 24 hours, washes and is once put into 3200r/min's
Centrifuge is centrifuged ten minutes, is at least cleaned 4 times, is cleaned until being no longer acidity.
2) 75 DEG C of baking oven reaction 12-20h are put into, drying is clayed into power with weighing spoon and weighs 6mg.
3) purified with chelating resin Chelex-100 to Mo sample, separate molybdenum element, prepare 2mol/ first
The HNO of L3Solution is completely dissolved sample powder, with the HNO of 6mol/L3Solution and deionized water clean ion exchange resin, so
The isobar of molybdenum, then the NH with 8mol/L are washed with the mixed solution of 0.02mol/L HCl and 0.2mol/L HF afterwards3It is molten
Molybdenum element in liquid collection of ions exchanger resin is evaporated the HNO for using 2mol/L again in 150 DEG C of baking ovens3Dissolution, finally by sample
It is dissolved in the HNO of 0.3mol/L3Solution, it is to be measured.
The content of S300, test analysis molybdenum element:
1) it in 150 DEG C or more of baking oven, dries sample 2 hours, to remove the absorption water of sample surfaces.
2) 5g sample is accurately weighed, is placed in 800 DEG C of high temperature furnace and carries out ashing processing, treated, and residue is added
5mL nitric acid.It is placed on electric hot plate, 250 DEG C of constant temperature, dissolves by heating.If there is muddy object, the sulphur of appropriate 0.5mol/L is added
Acid removal.
3) ammonium chloride that appropriate 2mol/L is added can remove the Ca ion in sample.
4) high-purity HCl and each 5mL of high-purity HF is added, covers and steel bushing is closed, be put into baking oven 200 DEG C, constant temperature 48 hours.
It is evaporated on electric hot plate after cooling, adds the high-purity HCl of 3mL and steam to wet salt (remove remaining HF).
5) it is then always digested in tetraacethyl diaminoethanes and solution is made to be shown as acid, molybdenum is measured with this
Total content.With the content of postdigestive sample measurement ferro element, receive icp ms MC-ICP-MS with more
It is measured.
S400, the stable isotope composition for testing and analyzing molybdenum:
(1) will cleaning and cutting sample comminution and burn 10 hours at 200 DEG C -300 DEG C, in the HCl- of double distillations
HF-HNO3Mixture in digest, then carry out second in chloroazotic acid and digest.
(2) purified with chelating resin Chelex-100 to molybdenum isotope sample.Sample after purification is used
The double focusing multiple-collector plasma source mass spectrometry instrument Nu Plasma HR of NuInstruments company production is measured.With
DSN-100 type film goes to dissolve into plasma.
(3) the nitric acid cleaning sample of 0.5mol/L, 5min are used；Standard specimen, 3min are cleaned with the nitric acid of 0.05mol/L again.
(4) it is measured using MC-ICP-MS high-precision measuring isotope, carries out instrument using sample-standard specimen interior extrapolation method
Quality discriminates against correction, and thousand point deviations of the molybdenum isotope ratio result measured with sample relative to standard specimen indicate.
S500, by known DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity hydrocarbon source rock and the former same position of oil and gas molybdenum
The analysis of element, establishes codomain, the dividing value parameter of the molybdenum isotope ratio of different origins type oil reservoir, sums up different type oil reservoir
Molybdenum mass fractionation and non-mass be fractionated information characteristics, establish δ97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate.
Typical Bohai gulf basin sample is acquired respectively, detects the composition and content of hydrocarbon source rock and the molybdenum isotope in crude oil；
According to testing result, the codomain and dividing value parameter for establishing the molybdenum isotope ratio of different origins type sum up different type oil
The molybdenum mass fractionation and non-mass of gas are fractionated information characteristics, and foundation, which is sentenced, knows index plate, determine Oil-gas source and the origin cause of formation, and guide
Exploration deployment.Wherein in each reservoir sample of Bohai gulf basin molybdenum isotope δ97Mo (‰) data result such as the following table 1:
The δ of molybdenum isotope in each reservoir sample of 1 Bohai gulf basin of table97Mo (‰) data
Codomain, the dividing value parameter that the molybdenum isotope ratio of different origins type oil reservoir is determined according to 1 data of table, sum up not
The molybdenum mass fractionation and non-mass of same type oil reservoir are fractionated information characteristics, the δ measured97The value Coal-formed oil of Mo (‰) be 1.32 ‰,
1.10 ‰, terrestrial facies oil is -0.38 ‰, -0.42 ‰, and marine facies oil is 0.52 ‰, 0.64 ‰.Carry out the multiple test point of Multi-example
Analysis, it is as shown in Figure 1 that knowledge index plate is sentenced in foundation.
In δ97Mo (‰)-Oil Reservoir Types, which are sentenced, to be known in index plate, the δ of coal measures crude oil97Mo (‰) range be 1.04 ‰~
1.58 ‰, the δ of source rocks in coal measures97Mo (‰) range is 0.78 ‰~1.41 ‰, the δ of Marine Crude Oil97Mo (‰) range is
0.17 ‰~0.64 ‰, the δ of Marine Hydrocarbon Source Rocks97Mo (‰) range is 0.01 ‰~0.77 ‰, the δ of CONTINENTAL CRUDE97Mo (‰) model
Enclosing is -0.46 ‰~-0.14 ‰, the δ of nonmarine source rock97Mo (‰) range is -0.79 ‰~-0.08 ‰.
S600, sentenced according to Fig. 1 of foundation and know index plate, that is, can determine unknown oil sources source and the origin cause of formation, instruct exploration portion
Administration.
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 (15)
1. a kind of method for carrying out OIL SOURCE CORRELATION with molybdenum isotope, which is characterized in that method includes the following steps:
The separation and concentration of molybdenum element in S100, crude oil；
The separation and concentration of molybdenum element in S200, hydrocarbon source rock；
The content of S300, test analysis molybdenum element；
S400, the stable isotope composition for testing and analyzing molybdenum；
S500, by known DIFFERENT DEPOSITIONAL ENVIRONMENTS, differing maturity hydrocarbon source rock and crude oil and source rock of different nature
The analysis of middle molybdenum isotope, establishes δ97Mo (‰)-Oil Reservoir Types, which are sentenced, knows index plate；
S600, index plate is known according to sentencing for foundation, determines unknown oil sources source and the origin cause of formation.
2. the method according to claim 1, wherein the δ97Mo (‰)-Oil Reservoir Types, which are sentenced, to be known in index plate,
The δ of coal measures crude oil97Mo (‰) range is 1.04 ‰~1.58 ‰, the δ of source rocks in coal measures97Mo (‰) range be 0.78 ‰~
1.41 ‰, the δ of Marine Crude Oil97Mo (‰) range is 0.17 ‰~0.64 ‰, the δ of Marine Hydrocarbon Source Rocks97Mo (‰) range is
0.01 ‰~0.77 ‰, the δ of CONTINENTAL CRUDE97Mo (‰) range is -0.46 ‰~-0.14 ‰, the δ of nonmarine source rock97Mo(‰)
Range is -0.79 ‰~-0.08 ‰.
3. the method according to claim 1, wherein the hydrocarbon source rock and crude oil are respectively from oil field coring well
The oil sample of core or periphery outcropping rock sample, normal producing well.
4. the method according to claim 1, wherein S100 is specifically included:
The preparation of S110, crude oil sample；
The separating-purifying of molybdenum element in S120, crude oil sample.
5. according to the method described in claim 4, it is characterized in that, the preparation of S110 crude oil sample includes:
S111, fresh crude oil is taken, sequentially adds petroleum ether and ethyl alcohol is miscible, heated, obtains preliminary sample；
S112, fresh crude oil is weighed again, repeat S111 process；
S113, after standing the preliminary sample prepared twice at normal temperature, top oil sample is extracted respectively and is mixed, anhydrous second is added
Alcohol heats after shaking up, and crude oil sample to be tested is made.
6. according to the method described in claim 5, it is characterized in that, in S111, the ratio of crude oil, petroleum ether and ethyl alcohol are as follows: (6
~8g): 14~16mL:14~16mL.
7. according to the method described in claim 5, the temperature of heating is 75~85 DEG C it is characterized in that, in S111, the time 11
~13 hours.
8. according to the method described in claim 5,60~70 DEG C are heated it is characterized in that, standing 22~24 hours in S113
16~18 hours.
9. according to the method described in claim 4, it is characterized in that, the separating-purifying of molybdenum element includes: in S120 crude oil sample
1) crude oil sample is cleared up；
2) sample after clearing up is dissolved in HNO3In HF, heating is reacted, until sample is completely dissolved；It is evaporated after reaction
To wet salt, then use HNO3Extra HF is removed, HCl is eventually adding, is evaporated as powder；
3) purified with Chelx100 resin and TSK-8HG resin twin columns method to Mo sample, using 7mol/L HCl as medium
Molybdenum element is separated, the molybdenum solution purified is evaporated, and is converted into 2%HNO3Medium, it is to be measured.
10. according to the method described in claim 9, digestive reagent is it is characterized in that, the solvent of the resolution is methylene chloride
HNO3-H2O2Acid system.
11. the method according to claim 1, wherein S200 is specifically included:
S210, the selection of rock sample and broken sample, obtain the sample powder of hydrocarbon source rock；
The separating-purifying of molybdenum element in S220, sample powder.
12. according to the method for claim 11, which is characterized in that S210 includes:
S211, rock sample is chosen；
S212, broken sample, grinding obtain sample powder.
13. according to the method for claim 11, which is characterized in that the separating-purifying packet of molybdenum element in S220 sample powder
It includes:
1) sample powder is added HCl and carries out resolution reaction in high-pressure digestion tank；It is centrifuged after reaction with deionized water clear
It washes；
2) it by after the sample drying after eccentric cleaning, clays into power；
3) purified with Chelex-100 resin to Mo sample, separate molybdenum element；
The HNO of 2mol/L is used first3Solution is completely dissolved sample powder, with the HNO of 6mol/L3Solution and deionized water cleaning
Then resin washs the isobar of molybdenum with the mixed solution of 0.02mol/L HCl and 0.2mol/L HF, then uses 8mol/L
NH3Molybdenum element in solution collection of ions exchanger resin, the molybdenum solution purified is evaporated to be dissolved with nitric acid again, finally by sample
Product are dissolved in the HNO of 0.3mol/L3Solution, it is to be measured.
14. the method according to claim 1, wherein receiving inductively coupled plasma constitution using in S300 more
The content of spectrometer MC-ICP-MS measurement molybdenum element, comprising the following steps:
1) sample is dried to remove the absorption water of sample surfaces；
2) 5g sample is accurately weighed, ashing processing is carried out；Treated, and 5mL nitric acid is added in residue, is placed on electric hot plate, constant temperature
It 250 DEG C, dissolves by heating；If there is muddy object, the sulfuric acid removal of appropriate 0.5mol/L is added；
3) the Ca ion in the ammonium chloride removal sample of 2mol/L is added；
4) high-purity HCl and each 5mL of high-purity HF is added, covers and steel bushing is closed, be put into baking oven 200 DEG C, constant temperature 48 hours；It is cooling
It is evaporated on electric hot plate afterwards, adds the high-purity HCl of 3mL and steam to wet salt；
5) it is then always digested in tetraacethyl diaminoethanes and solution is made to be shown as acid, always containing for molybdenum is measured with this
Amount；With the content of postdigestive sample measurement ferro element, carried out with the icp ms MC-ICP-MS that receive more
Measurement.
15. the method according to claim 1, wherein receiving inductively coupled plasma constitution using in S400 more
Spectrometer MC-ICP-MS tests and analyzes the stable isotope composition of molybdenum.
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