CN106855547A - The evaluation method and its device of a kind of shale oil maturity - Google Patents
The evaluation method and its device of a kind of shale oil maturity Download PDFInfo
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- CN106855547A CN106855547A CN201611187954.3A CN201611187954A CN106855547A CN 106855547 A CN106855547 A CN 106855547A CN 201611187954 A CN201611187954 A CN 201611187954A CN 106855547 A CN106855547 A CN 106855547A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Abstract
The present invention relates to the evaluation method and its device of a kind of shale oil maturity, the method is comprised the following steps：Take fresh mud shale sample；Crush；Toluene solution is added, using ultrasonic wave extraction；Concentration；Obtain extracting characteristic ion peak after collection of illustrative plates and calculating quality；It is calculated the mass ratio of 1.5 × (methylphenanthrene of 2 methylphenanthrene+3)/mass ratio of (the luxuriant and rich with fragrance methylphenanthrene of+2 methylphenanthrene+3), (2+3)/(1+4+6) methyl mass ratio in the wrong and 2/1 methyl pyrenes；Different fresh mud shale samples are taken to repeat the above steps；The mass ratio in the wrong to (2+3)/(1+4+6) methyl of different samples and the mass ratio of 2/1 methyl pyrenes are returned with Rm, obtain testing regression equation；The mass ratio and the quality of 2/1 methyl pyrenes bent by (2+3)/(1+4+6) methyl are than quantitative assessment shale oil maturity；Then, the evaluation method to shale oil maturity is verified.The method is simple, the characteristics of with direct, low cost, small error.
Description
Technical field
The present invention relates to the unconventionaloil pool shale oil field of oil exploration, more particularly to a kind of shale oil maturity is commented
Valency method and its device.
Background technology
The liquid crude oil remained in hydrocarbon source rock is referred to as shale oil.Unconventional shale oil gas leather is started in world wide
Life, makes substantial progress for shale series of strata oil-gas exploration in North America, and the country also makes a breakthrough for the exploration of shale oil gas, special
It is not shale gas field.But how shale oil field particularly under the background of low oil price, sieves at present still in the exploratory stage
The dessert area of page selection shale oil turns into the Important Problems in scientific and engineering field.The Ba Ken zone of north America region, Ying Tan Shale Regions band
Exploration practices confirm source rock maturity be the shale most important index of series of strata oil-gas exploration.The maturity in Source Rock Evaluation field refers to
Mark is mainly reflectance of vitrinite (Ro), pyrolysis parameters of rock Tmax, clay mineral index, aromatic hydrocarbon BaP isomery body mass ratio, first
Base phenanthrene index, dibenzothiophenes mass ratio, triaromatic sterane mass ratio etc., vitamin E isomer mass ratio etc..
In fact, certain error is usually present in measurement process for the maturity indices of rock and SOLID ORGANIC matter,
Such as Ro allows the deviation for having positive and negative 0.1 in national standard.Additionally, often lacking vitrinite in the lacustrine shale of I type organic matters
There is repressed phenomenon in component, or vitrinite.Aromatic component is widely distributed in mud shale and oil component, in
Low-maturity (Ro<1.2) in the case of, the actual parameter of crude oil and source rock maturity assessment can be turned into, conventional at present
Index is that methylphenanthrene index calculates maturity, formula Rm=0.55MPI1+0.44.But methylphenanthrene parameter is compared to pyrene and chemical combination in the wrong
Thing is easier volatilization, and fractionation is caused so as to cause experiment flow to be easier, and influences maturity result of determination to the greatest extent.
The maturity for evaluating shale oil has important industrial significance in " dessert area " is preferred.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of evaluation method of shale oil maturity, the party
Method can be enriched currently for shale oil maturity assessment index, realize the objective evaluation of shale oil maturity, and method is simple, tool
Have directly, low cost, small error the characteristics of.
In order to achieve the above object, the invention provides a kind of evaluation method of shale oil maturity, the method include with
Lower step：
Step A：Take different fresh mud shale samples；
Step B：Above-mentioned reducing mechanism is respectively adopted by sample comminution at least 200 mesh, take the sample after crushing be put into it is flat
Bottom flask is stand-by；
Step C：Toluene solution is separately added into, using ultrasonic wave extraction, obtains extracting solution；
Step D：Concentration extraction solution, concentrate solution is concentrated to give using above-mentioned Rotary Evaporators respectively；
Step E：Concentrate solution is put into cell bottle respectively, is dried in fume hood, obtain concentrate；
Step F：A small amount of n-hexane dissolution concentrate is separately added into, is scanned with GC-MS full scan patterns, obtain difference
Collection of illustrative plates；
Step G：Respectively extract characteristic ion peak m/z178, quality is integrated and calculated to phenanthrene, respectively extract feature from
Sub- peak m/z192, integrates and calculates quality respectively to 3- methylphenanthrenes, 2- methylphenanthrenes, 9- methylphenanthrenes and 1- methylphenanthrenes, extracts respectively
Characteristic ion peak m/z242,2- methyl in the wrong to 1- methyl is bent, 3- methyl is bent, 4- methyl is bent and 6- methyl is bent and integrates respectively and count
Quality is calculated, characteristic ion peak m/z216 is extracted respectively, 1- methyl pyrene and 2- methyl pyrene are integrated and calculate quality respectively；
Step H：It is calculated the quality of 1.5 × (2- methylphenanthrene+3- methylphenanthrenes)/(phenanthrene+2- methylphenanthrene+3- methylphenanthrenes)
Than as MPI1 is calculated the mass ratio of (2- methyl is bent+3- methyl and bent)/(1- methyl is bent+4- methyl+6- methyl in the wrong and bent)
With the mass ratio of 2- methyl pyrene/1- methyl pyrenes, (2- methyl is bent+3- methyl and bent)/(1- methyl is bent+4- methyl+6- methyl in the wrong and bent)
Mass ratio be referred to as (2-+3-)/(1-+4-+6-) methyl mass ratio in the wrong, the mass ratio of 2- methyl pyrene/1- methyl pyrenes is referred to as
It is the mass ratio of 2-/1- methyl pyrenes；
Step I：To (2-+3-)/(1-+4-+6-) methyl of above-mentioned all of fresh mud shale sample mass ratio in the wrong and
The equivalent maturity Rm (Rm=0.55MPI1+0.44) of methylphenanthrene is returned, and obtains the first experiment regression equation；
To the mass ratio and the equivalent maturity Rm of methylphenanthrene of 2-/1- methyl pyrenes of above-mentioned all of fresh mud shale sample
(Rm=0.55MPI1+0.44) returned, obtained the second experiment regression equation.
According to above three equation, the mass ratio bent by (2-+3-)/(1-+4-+6-) methyl or 2-/1- methyl pyrenes
Quality is than quantitative assessment shale oil maturity Rm；
Step J：Evaluation method to shale oil maturity is verified.
In the above-mentioned methods, it is preferable that take 45 kinds of fresh mud shale samples in step A altogether, 45 kinds of (2- of sample are obtained
+ 3-)/(1-+4-+6-) methyl mass ratio in the wrong and 2-/1- methyl pyrenes mass ratio, then returned with Rm respectively, obtain
First experiment regression equation Rch=0.105Rm+0.599 (Rch, methyl bends equivalent maturity indices)；Obtain the second experiment recurrence
Equation Rpy=0.352Rm+0.570 (Rpy, the equivalent maturity indices of methyl pyrene).
In the above-mentioned methods, it is preferable that in step A, mud shale sample includes core and/or outcrop samples.Core or
Outcrop samples are the interference for removing drilling fluid and weathered layer, the fresh and clean sample of acquisition.
In the above-mentioned methods, it is preferable that in step B, the sample after stand-by crushing be 10-100g, more preferably 20g,
In step C, the addition of toluene solution is 20-200mL, preferably 100mL, and in step D, the amount of concentrate solution is 3-10mL,
Preferably 5mL.
In the above-mentioned methods, must be prevented from sample during step B crushing sample to be contaminated, the particularly friendship of sample room
Fork pollution.
In the above-mentioned methods, it is preferable that in step C, toluene solution is the pure level of analysis, ultrasound described in each extraction process
Time be each 15min, be repeated 3 times, be not less than 5MHz using the extraction frequency of ultrasonic wave.
In the above-mentioned methods, it is preferable that filtering is needed in step D, before merging, the filter paper that filtering is used includes chloroform
The absorbent cotton or test paper crossed, to ensure that amalgamation liquid does not have solid powder to enter.
In the above-mentioned methods, it is preferable that in step D, the bath temperature of concentration is less than 60 DEG C.
In the above-mentioned methods, it is preferable that in step F, concentrate described in adding the n-hexane dissolution of 10 μ L is mixed
Solution is closed, 1 μ L mixed solutions is taken and it is scanned, obtain collection of illustrative plates.
In the above-mentioned methods, it is preferable that above-mentioned GC-MS analysis conditions are：Carrier gas is 99.999%He；Flow rate of carrier gas is
1mL/min；Chromatographic column is HP-5MS (60m × 0.25mm × 0.25 μm)；300 DEG C of gasification injector temperature；Heating schedule is 80
DEG C constant temperature 1min, 3 DEG C/min rise to 310 DEG C, constant temperature 16min；Ionization mode is EI, 70eV；Data acquisition modes be full scan/
Selection ion (SCAN/SIM).
In the above-mentioned methods, it is preferable that in step G, either manually or automatically integral mode obtains methyl to the integration
Bend the chromatogram area of pictural surface with methyl pyrene and calculate mass ratio, more preferably integration is evened up in base.
In the above-mentioned methods, it is preferable that the calculating of the integration includes using spectrum analysis software.
In the above-mentioned methods, the quantitative assessment process of shale oil maturity includes parameter quality than calculating and building recurrence side
Journey, wherein, calculate and analysis is all conventional analysis software, including MicrosoftExcel, Spass etc..
In the above-mentioned methods, it is preferable that the verification step in step J includes：Different fresh shale oil samples are taken in addition
Product, repeat the above steps A to step H respectively, obtains (2-+3-)/(1-+4-+6-) methyl mass ratio, 2-/1- methyl pyrenes in the wrong
Mass ratio, MPI1, then, be calculated Rm, Rch and Rpy, and calculate relative error.
The evaluation method of shale oil maturity of the invention can be used for Ro<The evaluation of 1.2% shale oil maturity.
The present invention also provides a kind of system for above-mentioned shale oil maturity assessment, and the system includes：
Sample comminution apparatus：Obtain the mud shale sample that experiment needs；
Extraction element：Obtain pyrene containing methyl and methyl aromatic component in the wrong in mud shale sample；
Experimental provision：For obtaining methyl pyrene and methyl spectrogram in the wrong；
Analytical equipment：Spectrum analysis software realizes integration and calculates mass ratio.
In said apparatus, it is preferable that the sample comminution apparatus include jaw crusher and/or ball mill pulverizer；Institute
Stating extraction element includes ultrasonic wave extraction instrument, boiling flask and Rotary Evaporators；The experimental provision includes gas chromatography-mass spectrum
It is used in conjunction instrument and its attached carrier gas gas path device.
Shale oil maturity is evaluated with the equivalent maturity Rm of methylphenanthrene in the prior art, but methylphenanthrene is readily volatilized, surveys
Determine unstable result, and methyl is bent and methyl pyrene is not volatile, measurement result stabilization.The present invention to (2-+3-) of different samples/
(1-+4-+6-) methyl mass ratio in the wrong, the mass ratio of 2-/1- methyl pyrenes with Rm return and obtain testing regression equation respectively,
Therefore, it can replace methylphenanthrene equivalent with the mass ratio of (2-+3-)/(1-+4-+6-) methyl mass ratio in the wrong, 2-/1- methyl pyrenes
Maturity Rm evaluates shale oil maturity.
Evaluation method provided by the present invention shows huge application prospect, the low-maturity stage in can effectively realizing
Ro<1.2% shale oil maturity assessment, and it is abundant currently for shale oil maturity assessment index, realize shale oil maturity
Objective evaluation, method is simple, low cost, error are small.The device is simple to operate, it is actual, reproducible to meet, and it is fixed to can be used for
Amount is evaluated.Compared to traditional assay method, the present invention can quickly realize that advantage is obvious.
Brief description of the drawings
Fig. 1 is the flow chart of the evaluation method of shale oil maturity of the present invention.
Fig. 2 is structural representation of the present invention for the device of shale oil maturity assessment.
Fig. 3 be (2-+3-)/(1-+4-+6-) methyl bend, the mass ratio of 2-/1- methyl pyrenes respectively with the experiment recurrence side of Rm
The rectilinear of journey.
Fig. 4 is 45 relative error distribution maps of sample in embodiment 2.
Fig. 5 is the luxuriant and rich with fragrance collection of illustrative plates obtained in embodiment 3.
Fig. 6 is the collection of illustrative plates of methylphenanthrene obtained in embodiment 3.
Fig. 7 is the methyl obtained in embodiment 3 collection of illustrative plates in the wrong.
Fig. 8 is the collection of illustrative plates of methyl pyrene obtained in embodiment 3.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Embodiment 1
The present embodiment provides a kind of system for shale oil maturity assessment, and the system includes：
Sample comminution apparatus：The crushing sample that experiment needs is obtained, being combined using jaw crusher and ball mill pulverizer is made
With；
Extraction element：Obtain pyrene containing methyl and methyl aromatic component in the wrong, the extraction element of use in mud shale sample
Including comprising ultrasonic wave extraction instrument, boiling flask and Rotary Evaporators；
Experimental provision：Using GC-MS full scan patterns, for obtaining methyl pyrene and methyl spectrogram in the wrong, methyl pyrene is realized
With the identification that methyl bends series compound；
Analytical equipment：Using spectrum analysis software Chemstation, realize that integration and mass ratio are calculated.The present invention is used for
The structural representation of the device of shale oil maturity assessment is as shown in Figure 2.
Above-mentioned GC-MS analysis conditions are：Carrier gas is 99.999%He；Flow rate of carrier gas is 1mL/min；Chromatographic column is HP-5MS
(60m×0.25mm×0.25μm)；300 DEG C of gasification injector temperature；Heating schedule is 80 DEG C of constant temperature 1min, and 3 DEG C/min rises to
310 DEG C, constant temperature 16min；Ionization mode is EI, 70eV；Data acquisition modes are full scan/selection ion (SCAN/SIM).
Embodiment 2
The present embodiment provides a kind of evaluation method of shale oil maturity, long to Ordos Basin Triassic Yanchang Formation by 7
Shale oil carries out analysis.The method is comprised the following steps：
Step A：45 samples of the fresh Ordos Basin Triassic Yanchang Formation shale oil of page 7 long are gathered respectively, point
Do not remove the marginal portion of drilling fluid dip-dye；
Step B：Jaw crusher and ball mill pulverizer is respectively adopted by above-mentioned sample comminution to 200 mesh, weighs 20g and is put into
It is stand-by in boiling flask；
Step C：100mL toluene solutions are separately added into, using ultrasonic wave extraction, obtain extracting solution, be repeated 3 times；
Step D：Merge respectively and extract solution, 5mL is concentrated into using Rotary Evaporators, obtain concentrate solution；
Step E：The concentrate solution of above-mentioned 5mL is put into cell bottle respectively, is dried in fume hood, obtain concentrate；
Step F：Add the n-hexane of 10 μ L to dissolve above-mentioned concentrate respectively and obtain mixed solution, take the μ of the mixed solution 1
L, is acquired with GC-MS full scan patterns, obtains different collection of illustrative plates；
Step G：Respectively extract characteristic ion peak m/z178, quality is integrated and calculated to phenanthrene, respectively extract feature from
Sub- peak m/z192, integrates and calculates quality respectively to 3- methylphenanthrenes, 2- methylphenanthrenes, 9- methylphenanthrenes and 1- methylphenanthrenes, methylphenanthrene
Collection of illustrative plates, extracts characteristic ion peak m/z242 respectively, and, 2- methyl in the wrong to 1- methyl is bent, 3- methyl is bent, 4- methyl is bent and 6- methyl is bent
Substrate is carried out respectively even up to integrate and calculating quality, characteristic ion peak m/z216 is extracted respectively, to 1- methyl pyrene and 2- methyl pyrenes
Substrate is carried out respectively even up to integrate and calculating quality, obtain the data of each parameter as shown in table 1 and continued 1；
Step H：The matter of 1.5 × (2- methylphenanthrene+3- methylphenanthrenes)/(phenanthrene+2- methylphenanthrene+3- methylphenanthrenes) is calculated respectively
Amount ratio, as MPI1 is calculated the quality of (2-+3-)/(1-+4-+6-) methyl mass ratio in the wrong and 2-/1- methyl pyrenes respectively
Than as shown in table 1 and continued 1；
Step I：The mass ratio and the equivalent maturity of methylphenanthrene that 45 kinds of (2-+3-) of sample/(1-+4-+6-) methyl are bent
Rm is returned, and obtains the first experiment regression equation Rch=0.105Rm+0.599；To 45 kinds of matter of 2-/1- methyl pyrenes of sample
Amount obtains the second experiment regression equation Rpy=0.352Rm+0.570 than being returned with the equivalent maturity Rm of methylphenanthrene, wherein,
Rm=0.55MPI1+0.44；
According to foregoing three equations, the mass ratio bent by (2-+3-)/(1-+4-+6-) methyl or 2-/1- methyl pyrenes
Quality is than quantitative assessment shale oil maturity；
Step J：Evaluation method to shale oil maturity is verified：4 parts of (basins of fresh shale oil samples are taken in addition
Interior middle part B237-1 wells and C92-2 wells, basin western part H38-2 and lake basin the north H15-1 wells shale oil), above-mentioned step is repeated respectively
Rapid A to step H, obtains (2-+3-)/(1-+4-+6-) methyl mass ratio, mass ratio, the MPI1 of 2-/1- methyl pyrenes in the wrong, so
Afterwards, Rm, Rch and Rpy are calculated, and calculate relative error, obtain the data of each parameter as shown in table 2 and continued 2, shale oil
The flow chart of the evaluation method of maturity is as shown in Figure 1.
Relative error computing formula is respectively：
Relative error 1：(Rch-Rm)/Rm × 100%；
Relative error 2：(Rpy-Rm)/Rm × 100%.
As shown in table 1 and continued 1,45 average relative errors of sample 1 are 2.61%；45 the average relative of sample are missed
It is 5.03% to differ from 2, as shown in Figure 4.The equivalent maturity that Rch and Rpy is calculated is consistent with the evaluation result of Rm, and evaluation result can
Lean on, calculate difference between maturity and Rm and meet national standard requirement 10%.
Experiment proves 7 shale oil maturity assessment long, two New Sets (2-+3-)/(1-+4-+6-) methyl mass ratio in the wrong
There is preferable linear dependence with methylphenanthrene parameter with the mass ratio of 2-/1- methyl pyrenes, as shown in figure 3, methyl can be replaced
Luxuriant and rich with fragrance parameter maturity Rm, as the efficiency index of shale oil maturity assessment.Contrasted by with the equivalent maturity Rm of methylphenanthrene, first
Base is bent equivalent maturity indices Rch and the equivalent maturity Rpy of methyl pyrene and is respectively less than 10%, major part with Rm maturity relative errors
Relative error is respectively less than 5%, it was confirmed that the validity and feasibility of the method.
Embodiment 3
The present embodiment provides a kind of evaluation of Ordos Basin Triassic Yanchang Formation 7 shale oil X79 sample maturity degree long
Method, the method is comprised the following steps：
Step A：The fresh Ordos Basin Triassic Yanchang Formation 7 shale oil X79 samples long of collection, remove drilling well immersion
The marginal portion of dye；
Step B：Using jaw crusher and ball mill pulverizer by above-mentioned sample comminution to 200 mesh, weigh 20g be put into it is flat
It is stand-by in flask；
Step C：100mL toluene solutions are added, using ultrasonic wave extraction, obtains extracting solution, be repeated 3 times；
Step D：Merge and extract solution, 5mL is concentrated into using Rotary Evaporators, obtain concentrate solution；
Step E：The concentrate solution of above-mentioned 5mL is put into cell bottle, is dried in fume hood, obtain concentrate；
Step F：Add the above-mentioned concentrate of n-hexane dissolution of 10 μ L to obtain mixed solution, take the μ L of the mixed solution 1, use
GC-MS full scan patterns are acquired, and obtain collection of illustrative plates, and collection collection of illustrative plates is as shown in Figure 5-Figure 8；
Step G：Characteristic ion peak m/z178 is extracted after obtaining collection of illustrative plates, quality is integrated and calculated to phenanthrene, extract feature
Quasi-molecular ions m/z192, integrates and calculates quality respectively to 3- methylphenanthrenes, 2- methylphenanthrenes, 9- methylphenanthrenes and 1- methylphenanthrenes, methylphenanthrene
Collection of illustrative plates, extract characteristic ion peak m/z242, to 1- methyl bend, 2- methyl bend, 3- methyl bend, 4- methyl bend and 6- methyl bend point
Substrate is not carried out evening up to integrate and calculating quality, extract characteristic ion peak m/z216,1- methyl pyrene and 2- methyl pyrenes are entered respectively
Row substrate is evened up and integrates and calculate quality, obtains the data of each parameter as shown in table 3 and continued 3；
Step H：It is calculated the ratio of 1.5 × (2- methylphenanthrene+3- methylphenanthrenes)/(phenanthrene+2- methylphenanthrene+3- methylphenanthrenes)
0.62, (2-+3-)/(1-+4-+6-) methyl ratio in the wrong are 0.59 for the ratio of 2.03,2- methyl pyrene/1- methyl pyrenes；
Step I：According to Rm=0.55MPI1+0.44 and experiment regression equation Rch=0.105Rm+0.599, Rpy=
0.352Rm+0.570, is calculated Rm=0.78, Rch=0.81, Rpy=0.78；
Relative error in X79 samples is respectively 3.62% and 0.5%, works well.Rch and Rpy calculate it is equivalent into
It is ripe degree, evaluation result reliability consistent with the evaluation result of Rm, therefore, (2-+3-)/(1-+4-+6-) methyl bend mass ratio with
The mass ratio of 2-/1- methyl pyrenes can replace methylphenanthrene parameter to calculate maturity Rm, used as the effective of shale oil maturity assessment
Index.
Claims (10)
1. a kind of evaluation method of shale oil maturity, the method is comprised the following steps：
Step A：Take different fresh mud shale samples；
Step B：At least 200 mesh are crushed to respectively, it is stand-by；
Step C：Toluene solution is separately added into, using ultrasonic wave extraction, obtains extracting solution；
Step D：The extraction solution is concentrated respectively, obtains concentrate solution；
Step E：The concentrate solution is dried respectively obtains concentrate；
Step F：Concentrate described in n-hexane dissolution is separately added into, is scanned with GC-MS full scan patterns, obtain different figures
Spectrum；
Step G：Characteristic ion peak m/z178 being extracted respectively, quality being integrated and calculated to phenanthrene, characteristic ion peak is extracted respectively
M/z192, is integrated and calculates quality respectively to 3- methylphenanthrenes, 2- methylphenanthrenes, 9- methylphenanthrenes and 1- methylphenanthrenes, and feature is extracted respectively
Quasi-molecular ions m/z242,2- methyl in the wrong to 1- methyl is bent, 3- methyl is bent, 4- methyl is bent and 6- methyl is bent and integrates respectively and calculate matter
Amount；Characteristic ion peak m/z216 is extracted respectively, and 1- methyl pyrene and 2- methyl pyrene are integrated and calculate quality respectively；
Step H：The quality of 1.5 × (2- methylphenanthrene+3- methylphenanthrenes)/(phenanthrene+2- methylphenanthrene+3- methylphenanthrenes) is calculated respectively
Than as MPI1 is calculated the mass ratio of (2-+3-)/(1-+4-+6-) methyl mass ratio in the wrong and 2-/1- methyl pyrenes；
Step I：The mass ratio and methyl in the wrong to (2-+3-)/(1-+4-+6-) methyl of above-mentioned all of fresh mud shale sample
Luxuriant and rich with fragrance equivalent maturity Rm is returned, and obtains the first experiment regression equation；Mass ratio to 2-/1- methyl pyrenes of different samples and
The equivalent maturity Rm of methylphenanthrene is returned, and obtains the second experiment regression equation, wherein, Rm=0.55MPI1+0.44；
According to above three equation, the mass ratio and the quality of 2-/1- methyl pyrenes bent by (2-+3-)/(1-+4-+6-) methyl
Than quantitative assessment shale oil maturity；
Step J：Evaluation method to shale oil maturity is verified.
2. the method for claim 1, wherein in step A, 45 kinds of fresh mud shale samples are taken, in obtaining step I
Described first tests regression equation is：Rch=0.105Rm+0.599, obtaining the second experiment regression equation is：Rpy=
0.352Rm+0.570。
3. method as claimed in claim 1 or 2, wherein, in step A, the mud shale sample includes core and/or sample of appearing
Product；Preferably, the core or outcrop samples are the interference for removing drilling fluid and weathered layer, the fresh and clean sample of acquisition
Product.
4. the method as any one of claim 1-3, wherein, in step B, the sample after stand-by crushing is 10-
100g, preferably 20g；
In step C, the addition of the toluene solution is 20-200mL, preferably 100mL；
In step D, the amount of the concentrate solution is 3-10mL, preferably 5mL.
5. the method as any one of claim 1-4, wherein, in step C, the toluene solution is the pure level of analysis, often
The time of ultrasound is each 15min in secondary extraction process, is repeated 3 times, and 5MHz is not less than using the extraction frequency of ultrasonic wave.
Preferably, in step D, the extraction solution needs filtering, and the filter paper for using that filters includes taking off that chloroform is crossed
Fat cotton or test paper；
Preferably, the bath temperature of the concentration is less than 60 DEG C.
6. the method as any one of claim 1-5, wherein, in step F, add 10 μ L n-hexane dissolution concentrates to obtain
To mixed solution, take 1 μ L mixed solutions and it is scanned, obtain collection of illustrative plates；
Preferably, the analysis condition of the GC-MS is：Carrier gas is 99.999%He；Flow rate of carrier gas is 1mL/min；Chromatographic column is
HP-5MS 60m×0.25mm×0.25μm；300 DEG C of gasification injector temperature；Heating schedule is 80 DEG C of constant temperature 1min, 3 DEG C/min
Rise to 310 DEG C, constant temperature 16min；Ionization mode is EI, 70eV；Data acquisition modes are full scan/selection ion.
7. the method as any one of claim 1-6, wherein, the verification step in step J includes：Difference is taken in addition
Fresh shale oil samples, repeat the above steps A to step H respectively, obtains (2-+3-)/(1-+4-+6-) methyl quality in the wrong
Than mass ratio, the MPI1 of, 2-/1- methyl pyrenes, then, Rm, Rch and Rpy are calculated, and calculate relative error.
8. the method as any one of claim 1-7, wherein, the method is used for Ro<1.2% shale oil maturity
Evaluate.
9. a kind of system for implementing the method any one of claim 1-8, the system includes：
Sample comminution apparatus：Obtain the mud shale sample that experiment needs；
Extraction element：Obtain pyrene containing methyl and methyl aromatic component in the wrong in mud shale sample；
Experimental provision：For obtaining methyl pyrene and methyl spectrogram in the wrong；
Analytical equipment：Spectrum analysis software realizes integration and calculates mass ratio.
10. system as claimed in claim 9, wherein, the sample comminution apparatus include jaw crusher and/or ball mill grinding
Machine；The extraction element includes ultrasonic wave extraction instrument, boiling flask and Rotary Evaporators；The experimental provision includes gas phase color
Spectrum-mass spectrum is used in conjunction instrument and its attached carrier gas gas path device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104678018A (en) * | 2015-02-13 | 2015-06-03 | 中国石油天然气股份有限公司 | Crude oil mass fracture maturity evaluation method |
| CN104749341A (en) * | 2015-03-05 | 2015-07-01 | 中国石油天然气股份有限公司 | Method for judging effectiveness of carbonate rock source |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104678018A (en) * | 2015-02-13 | 2015-06-03 | 中国石油天然气股份有限公司 | Crude oil mass fracture maturity evaluation method |
| CN104749341A (en) * | 2015-03-05 | 2015-07-01 | 中国石油天然气股份有限公司 | Method for judging effectiveness of carbonate rock source |
Non-Patent Citations (3)
| Title |
|---|
| MEIJUN LI等: "Identification and distribution of chrysene,methylchrysenes and their isomers in crude oils and rock extracts", 《ORGANIC GEOCHEMISTRY》 * |
| 崔景伟: "冀北凹陷高于庄组与洪水庄组在岩心、露头中多赋存态生物标志物的对比", 《沉积学报》 * |
| 沈忠民等: "川西坳陷煤系烃源岩成熟度特征及成熟度指标对比研究", 《矿物岩石》 * |
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