CN106706496B - A kind of measuring method of the nanoscale oil-containing pore-size distribution of densification oil/shale oil - Google Patents
A kind of measuring method of the nanoscale oil-containing pore-size distribution of densification oil/shale oil Download PDFInfo
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- 238000009826 distribution Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003079 shale oil Substances 0.000 title claims abstract description 15
- 238000000280 densification Methods 0.000 title claims description 4
- 239000011148 porous material Substances 0.000 claims abstract description 46
- 239000004576 sand Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 8
- 239000011435 rock Substances 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000002474 experimental method Methods 0.000 description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000002336 sorption--desorption measurement Methods 0.000 description 12
- 239000010779 crude oil Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000003775 Density Functional Theory Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010997 low field NMR spectroscopy Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N15/088—Investigating volume, surface area, size or distribution of pores; Porosimetry
- G01N15/0893—Investigating volume, surface area, size or distribution of pores; Porosimetry by measuring weight or volume of sorbed fluid, e.g. B.E.T. method
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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Abstract
The invention discloses a kind of measuring methods of the nanoscale oil-containing pore-size distribution of fine and close oil/shale oil.The measuring method includes the following steps: tight sand sample or shale samples obtain powder sample after crushed, and amount of powder sample carries out sample after organic solvent extracts to extract, and amount of powder sample is as sample before extracting；The pore size distribution curve of sample after sample and sample after extracting carry out sample before pore-size distribution is tested to extract respectively and extract before extracting；The pore-size distribution of sample and the macro hole of micropore-mesopore-of sample after extracting before being fitted to extract respectively to two curves, difference after extracting between the specific pore volume of sample and the specific pore volume for extracting preceding sample is the specific pore volume of oil-containing interstitial space, so far obtains the nanoscale oil-containing pore-size distribution of fine and close oil or shale oil.The present invention compares the total oil content amount for testing measured oil-containing pore-size distribution and rock, and then makes and objectively evaluating to the overall distribution in rock oil-containing aperture.
Description
Technical field
The present invention relates to a kind of measuring methods of the nanoscale oil-containing pore-size distribution of fine and close oil/shale oil.
Background technique
With deepening continuously both at home and abroad to fine and close oil and shale oil work of exploration and development, focus is from initial money
Gradually steering mechanism is studied for source evaluation.Wherein, due to the supporting environment of fine and close oil and shale oil explores it, develop have it is important
Meaning, therefore receive the extensive concern of domestic and foreign scholars.The oil-containing pore-size distribution of fine and close oil and shale oil is its supporting environment
Important component, but have no reasonable analytical plan always, therefore be section's knowledge of a puzzlement domestic and foreign scholars always
One of topic.
Since average pore size is far below common reservoir in tight sand and shale, containing a large amount of nanoscale holes, therefore it is right
The analysis difficulty of its pore-size distribution is larger.It is mainly the following method in the prior art:
Scheme one:
To tight sand/shale samples saturation crude oil or water, nuclear-magnetism T is carried out to the rock sample of different saturation2Spectrum point
Analysis, utilizes T2The difference of spectrum obtains oil-containing pore-size distribution (M.Fleury, Characterization of shales with
low field NMR,in:The International Symposium of Core Analysts,Avignon,France,
8e11 September,SCA2014-014,2014;J.Li,J.Yin,Y.Zhang,S.Lu,W.Wang,J.Li,F.Chen,
Y.Meng,A comparison of experimental methods for describing shale pore
features—A case study in the Bohai Bay Basin of eastern China,International
Journal of Coal Geology,152,Part B(2015)39-49；A.Tinni,E.Odusina,
I.Sulucarnain,C.Sondergeld,C.Rai,NMR Response of Brine,Oil and Methane in
Organic Rich Shales,in:SPE Unconventional Resources Conference,Society of
Petroleum Engineers,2014.).The obtained oil-containing pore-size distribution of the program is the pore-size distribution of saturated oils, not
The pore-size distribution of initial oil, since filling mechanism is different, the two and non-equivalence.
Scheme two:
The high maturation shale samples progress carbon dioxide and liquid nitrogen pore-size distribution that extract forward and backward are compared and analyzed, from
And obtain influence (J.Li, S.Zhou, Y.Li, Y.Ma, Y.Yang, C.Li, Effect of of the asphalitine to shale pore-size distribution
organic matter on pore structure of mature lacustrine organic-rich shale:A
case study of the Triassic Yanchang shale,Ordos Basin,China,Fuel,185(2016)
421-431.).The object that the program is studied is high mature shale samples, therefore almost total number is converted into the crude oil in shale
Gas, therefore the research object of the program is not the pore-size distribution of crude oil, the only influence of residual asphalt confrontation shale pore-size distribution.
In addition, pore-size distribution combination oil-containing total amount is not further analyzed for the program, therefore certain pore size range is not obtained
The relationship of interior oil content and total oil content amount.
Summary of the invention
The object of the present invention is to provide a kind of measuring methods of the nanoscale oil-containing pore-size distribution of fine and close oil/shale oil, originally
Invention by being stripped removal crude oil in samples to rock sample, to extract the pore-size distribution of forward and backward tight sand/shale into
Row experiment test, and the two is carried out than analysis, reflect oil-containing pore-size distribution using the difference between the two；In addition, to forward and backward cause is extracted
Close sandstone/shale samples carry out pyrolysis analysis, and then obtain oil-containing total amount.Respective aperture section is included into oil volume and total oil content
Amount compares and analyzes, and finally determines the oil-containing ratio in the aperture section.
The measuring method of the nanoscale oil-containing pore-size distribution of densification oil/shale oil provided by the present invention, including walk as follows
It is rapid:
(1) tight sand sample or shale samples obtain powder sample after crushed, and the part powder sample is had
Solvent extracting, sample after being extracted, the part powder sample is as sample before extracting；
(2) sample after sample before the extracting and the extracting is subjected to pore-size distribution test respectively, obtains the extracting
The pore size distribution curve of sample after the pore size distribution curve of preceding sample and the extracting；
(3) after the pore size distribution curve to sample before the extracting and the extracting pore size distribution curve of sample respectively into
Row fitting obtains micropore-Jie of sample after the pore-size distribution in the macro hole of micropore-mesopore-of sample and the extracting before the extracting
The pore-size distribution in the macro hole in hole-；
The pore-size distribution refers to the relationship between aperture and specific pore volume；
(4) difference after the extracting before the specific pore volume of sample and the extracting between the specific pore volume of sample is to contain oilhole
The specific pore volume in gap space so far obtains the nanoscale oil-containing pore-size distribution of fine and close oil or shale oil.
In above-mentioned measuring method, micropore refers to that aperture is less than the hole of 2nm, mesoporous to refer to that aperture is 2~50nm
Between hole, macro hole refer to aperture be greater than 50nm hole.
In above-mentioned measuring method, in step (1), the granularity of the powder sample can be 80~100 mesh.
In above-mentioned measuring method, in step (1), the solvent that the organic solvent extracting uses can be chloroform, using rope
The mode of family name's extracting；
The time of the organic solvent extracting is not less than 72 hours, sufficiently to remove the crude oil in sample.
In above-mentioned measuring method, before step (2), the method also includes to sample before the extracting and the extracting
Sample carries out following pretreated step afterwards:
Sample after sample before the extracting and the extracting is heated above 100 DEG C, such as 105 DEG C, it is therefore an objective to sufficiently remove
The operation removing water, and being vacuumized simultaneously；
The pretreated process duration is not less than 12 hours；
Pass through the moisture and other impurities in the pretreatment sufficiently removal sample.
In above-mentioned measuring method, in step (2), the pore-size distribution test can be used existing method and carry out, and such as inhale
Attached-detachment assays, nuclear magnetic resonance or Electronic Speculum etc.；
Carbon dioxide adsorption-detachment assays and the experiment of liquid nitrogen adsorption-desorption can be used in the adsorption-desorption experiment, wherein
Carbon dioxide adsorption-detachment assays generally can test microvia (be less than 2nm), and the experiment of liquid nitrogen adsorption-desorption can generally test 2~
Hole between 150nm.
The carbon dioxide adsorption experiment and the experiment of liquid nitrogen adsorption-desorption successively carried out can be used in the present invention, respectively obtains institute
The preceding sample of extracting is stated to carbon dioxide adsorption thermoisopleth and to sample after liquid nitrogen adsorption-desorption isothermal, the extracting to dioxy
Change carbon adsorption thermoisopleth and to liquid nitrogen adsorption-desorption isothermal.
The condition of the carbon dioxide adsorption experiment is as follows:
Temperature is 0 DEG C, and absolute pressure is 0.002~0.1MPa.
The condition of the liquid nitrogen adsorption-desorption experiment is as follows:
Temperature is -195.70 DEG C, and absolute pressure is 0.0006~0.1112MPa.
In above-mentioned measuring method, in step (3), the fitting can be used existing model and carry out；
Such as using carbon dioxide adsorption experiment and liquid nitrogen adsorption-desorption experiment when, can be used NLDFT model, DR model,
BJH model or DFT model are fitted obtained adsorption-desorption isothermal curve.
In above-mentioned measuring method, the method also includes measuring nanoscale aperture oil content as follows:
1) sample before the extracting is pyrolyzed, product S is collected at 300 DEG C1, received during 300~650 DEG C
Collect product S2；
The product S1Predominantly free hydrocarbon；
The product S2Not only include shale samples in heavy hydrocarbon, but also including kerogen in shale samples (Oil source bed) by
The cracked hydrocarbon generated in thermal process；
Sample after the extracting is pyrolyzed, product S is collected during 300~650 DEG C2′；
The product S1With the product S2Quality sum and the product S2' difference be the tight sand sample
Or the oil-containing total amount of the shale samples；
2) the nanoscale aperture oil content of the tight sand sample or the shale samples and the tight sand sample
Or the ratio of the oil-containing total amount of the shale samples is the nanoscale aperture of the tight sand sample or the shale samples
Oil content；
The nanoscale aperture oil content of the tight sand sample or the shale samples is by the fine and close oil or shale oil
Nanoscale oil-containing pore-size distribution and oil density obtain, i.e., respective aperture distributed area is obtained according to nanoscale oil-containing pore-size distribution
Interior total specific pore volume just obtains corresponding oil content with oil density multiplication.
Measuring method of the present invention has the advantages that
The present invention contains oil samples (sample before extracting) and the pore-size distribution without oil samples (sample after extracting) by comparing,
The oil-containing pore-size distribution of rock can objectively be obtained.It is past when due to being tested using pore-size distribution of the different experiments to rock
Toward having some limitations, the pore-size distribution in a certain pore diameter range, such as carbon dioxide adsorption experiment can only be measured, generally
It can only reflect the pore size distribution range of micropore (aperture is less than 2nm), this will lead to the oil-containing aperture only obtained by particular experiment
Distribution has significant limitations.For this problem, the present invention will be tested always containing for measured oil-containing pore-size distribution and rock
Oil mass compares, and then makes and objectively evaluating to the overall distribution in rock oil-containing aperture.
Detailed description of the invention
Fig. 1 is the flow chart of measuring method of the present invention.
Fig. 2 is that the present invention extracts preceding sample and sample after extracting to carbon dioxide adsorption thermoisopleth.
Fig. 3 is that the present invention extracts preceding sample and sample after extracting to liquid nitrogen adsorption-desorption isothermal.
Fig. 4 is the pore-size distribution of sample and sample after extracting before the present invention extracts.
Fig. 5 is oil-containing graph of pore diameter distribution in the nano-pore of the invention measured.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The present embodiment is with Damintun Depression E2s4 LFor section shale samples, pore-size distribution is by carbon dioxide and liquid
N2 adsorption detachment assays measure, and flow chart is as shown in Figure 1.
Step 1: sample pretreatment
Shale samples surface is cleaned, and by sample comminution to 80~100 mesh, powder dress sample is divided into two parts, to wherein
A sample carries out soxhlet type using chloroformic solution, and extracting continues 72 hours or more, sufficiently to remove the crude oil in sample.
So far, the preceding powdered samples with after extracting of extracting are respectively obtained.
Step 2: carbon dioxide and liquid nitrogen adsorption experiment
It chooses respectively and extracts forward and backward shale samples powder, carry out carbon dioxide and liquid nitrogen absorption/detachment assays.
Sample is pre-processed first, be heated to 105 DEG C and is vacuumized simultaneously, it is small that preprocessing process continues 12
When more than, sufficiently to remove the moisture and other impurities in sample.
Carbon dioxide adsorption experiment is carried out to sample after pretreatment, this experiment uses Micromeritics ASAP-
2460 instruments, experimental temperature are 0 DEG C, and experiment relative pressure is 5.00 × 10-4~2.89 × 10-2(absolute pressure is about
0.002~0.1MPa), obtain adsorption isothermal curve (as shown in Figure 2).
It is tested followed by liquid nitrogen adsorption/desorption, still uses Micromeritics ASAP-2460 instrument, experimental temperature
It is -195.70 DEG C, relative pressure is 0.005~1.0 (absolute pressure is about 0.0006~0.1112MPa), is adsorbed/is taken off
Attached thermoisopleth (as shown in Figure 3).
It can be seen from Fig. 2 and Fig. 3 on the whole, no matter for adsorption isotherm or desorption isotherm, sample has been extracted
Adsorbance be all larger than the adsorbance for not extracting sample, illustrate that the presence of crude oil in samples hinders the entrance of gas.
Step 3: seeking pore-size distribution using NLDFT model
Non-localized density functional theory (NLDFT) can make accurate aperture point to porous media within the scope of larger aperture
Cloth evaluates (P.I.Ravikovitch, G.L.Haller, A.V.Neimark, Density functional theory model
for calculating pore size distributions:pore structure of nanoporous
catalysts,Adv Colloid Interfac,76(1998)203-226.).Therefore, the present embodiment is by taking NLDFT as an example to
Extracting and the shale samples not extracted carry out pore-size distribution evaluation.
NLDFT principle CO obtained to experiment is based on using 2460 software of MicroActive for ASAP2、N2It inhales
Attached/desorption isotherm is fitted, and obtains the micropore for having extracted and not extracted sample respectively (based on CO2Adsorption isotherm) and be situated between
The macro hole in hole-(is based on N2Adsorption-desorption isothermal) pore-size distribution.
In NLDFT, the pore-size distribution of porous media can pass through the fitting to absorption/desorption isotherm and measured value is calculated
It seeks.Measured absorption/desorption isotherm the N (P) of experiment can be expressed as follows (P.I.Ravikovitch, G.L.Haller,
A.V.Neimark,Density functional theory model for calculating pore size
distributions:pore structure of nanoporous catalysts,Adv Colloid Interfac,76
(1998)203-226；C.Lastoskie, K.E.Gubbins,N.Quirke,Pore-Size Distribution
Analysis of Microporous Carbons-a Density-Functional Theory Approach,J
PhysChem-Us,97(1993)4786-4796.；P.Tarazona, Free-Energy Density Functional for
Hard-Spheres,Phys Rev A,31(1985)2672-2679；P. Tarazona,U.M.B.Marconi,R.Evans,
Phase-Equilibria of Fluid Interfaces and Confined Fluids-Nonlocal Versus
Local Density Functionals, MolPhys, 60 (1987) 573-595.):
In formula, HminAnd HmaxThe minimum value and maximum value in respectively analyzed aperture, f (H) are the pore-size distribution letter of sample
Number, ρ (P, H) be pressure be P (MPa) when, aperture be H (nm) hole in averag density of the Adsorbate Gas in hole.
Assuming that the crack type hole in shale all has specific geometry, and can be contacted with Adsorbate Gas.It is huge
Canonical assemblage can preferably describe the macroscopic property in shale pore system, wherein chemical potential μ (J/mol), temperature T (K)
With volume V (cm3) be designated.Density Distribution (ρL) can be minimized and be sought by potential-energy function Ω:
Ω[ρL(r)]=F [ρL(r)]-∫drρL(r)[μ-Vext(r)] (2)
In formula, F is Helmholtz free energy (J), ρL(r)(g/cm3) it is gas in the hole in specified aperture in position r
Density integrates pore volume for formula 2.VextIt (J) is surface potential energy, by the effect gesture of gas-gas and gas solids
It can be determined.
According to the Density Distribution of gas in different pore size, the integration type of formula 1 can obtain pore-size distribution by Optimization Solution
Function f (H).In solution procedure, minimum realization is carried out by the error sum of squares to calculated value and experiment value, f (H) is asked
Solution:
In formula, E is the average value of error sum of squares, npFor the points of adsorption isotherm, nHFor in numerical integration process mesoporous
The number in diameter size subinterval.
Using principles above, micropore and mesoporous-is obtained by carbon dioxide adsorption data and liquid nitrogen absorption/desorption data respectively
The pore-size distribution in macro hole, and the two is docked, obtain the pore-size distribution (as shown in Figure 4) in the macro hole of micropore-mesopore-.
Step 4: nano-pore oil-containing pore-size distribution is sought
As shown in Figure 4, on the whole, in respective aperture section, the specific pore volume for having extracted sample, which is generally greater than, does not extract sample
The specific pore volume of product illustrates that the crude oil in sample occupies interstitial space.Using the difference of the two specific pore volume, for corresponding aperture
Section subtracts the specific pore volume for not extracting sample using the specific pore volume for having extracted sample, obtains the specific pore volume of oil-containing interstitial space,
As a result as shown in Figure 5.
Step 5: nano-pore oil content is sought
Pyrolysis Experiment is carried out to the sample for having extracted and not extracted respectively, experiment is carried out by Rock-Eval instrument.For
The sample not extracted measures free hydrocarbon (S at 300 DEG C in Pyrolysis Experiment1), during 300~650 DEG C, measure S2, S2
It not only had included the heavy hydrocarbon in shale samples, but also the cracking generated in thermal histories including kerogen in shale samples (Oil source bed)
Hydrocarbon.For the sample extracted, in Pyrolysis Experiment, S is measured during 300~650 DEG C2', due to chloroform process
The crude oil in sample, therefore S are eliminated2' in only include kerogen cracking hydrocarbon.From S1And S2The sum of in subtract S2'
Obtain the crude oil total amount in sample.
In the present embodiment, S1For 6.57mg/g, S2For 42.43mg/g, S2' it is 35.85mg/g, oil-containing total amount is
13.15mg/g。
Meanwhile to micropore and it is mesoporous in oil-containing specific pore volume sum up, can be obtained micropore and it is mesoporous in oil-containing it is total
Specific pore volume, (this example Central Plains oil density is 0.84g/cm with oil density3) be multiplied, its oil content, the present embodiment can be obtained
In its value be 1.8mg/g.
By to micropore and it is mesoporous in oil content compared with total oil content amount, it is known that micropore and it is mesoporous in oil content
Only the 13.7% of oil-containing total amount illustrates in the sample that most crude oil preservations are in macro aerial greater than 50nm.
Claims (5)
1. a kind of measuring method of the nanoscale oil-containing pore-size distribution of densification oil/shale oil, includes the following steps:
(1) tight sand sample or shale samples obtain powder sample after crushed, and the part powder sample carries out organic molten
Agent extracting, sample after being extracted, the part powder sample is as sample before extracting；
(2) sample after sample before the extracting and the extracting is subjected to pore-size distribution test respectively, obtains sample before the extracting
The pore size distribution curve of sample after the pore size distribution curve of product and the extracting；
(3) pore size distribution curve of sample is intended respectively after the pore size distribution curve to sample before the extracting and the extracting
It closes, the micropore-mesopore-for obtaining sample after the pore-size distribution in the macro hole of micropore-mesopore-of sample and the extracting before the extracting is macro
The pore-size distribution in hole；
The pore-size distribution refers to the relationship between aperture and specific pore volume；
(4) difference after the extracting before the specific pore volume of sample and the extracting between the specific pore volume of sample is that oil-containing hole is empty
Between specific pore volume, so far obtain the nanoscale oil-containing pore-size distribution of fine and close oil or shale oil.
2. measuring method according to claim 1, it is characterised in that: in step (1), the granularity of the powder sample is 80
~100 mesh.
3. measuring method according to claim 1 or 2, it is characterised in that: in step (1), the organic solvent extracting is adopted
Solvent is chloroform；
The time of the organic solvent extracting is not less than 72 hours.
4. measuring method according to claim 3, it is characterised in that: before step (2), the method also includes to described
Sample carries out following pretreated step after extracting preceding sample and the extracting:
The operation that sample after sample before the extracting and the extracting is heated above 100 DEG C and vacuumized simultaneously；
The pretreated process duration is not less than 12 hours.
5. measuring method according to claim 4, it is characterised in that: the method also includes measuring nanoscale aperture as follows
The step of oil content:
1) sample before the extracting is pyrolyzed, product S is collected at 300 DEG C1, collect and produce during 300~650 DEG C
Object S2；
Sample after the extracting is pyrolyzed, product S is collected during 300~650 DEG C2′；
The product S1With the product S2Quality sum and the product S2' difference be the tight sand sample or institute
State the oil-containing total amount of shale samples；
2) the nanoscale aperture oil content of the tight sand sample or the shale samples and the tight sand sample or institute
The ratio for stating the oil-containing total amount of shale samples is the nanoscale aperture oil-containing of the tight sand sample or the shale samples
Rate；
The nanoscale aperture oil content of the tight sand sample or the shale samples is received by the fine and close oil or shale oil
Meter level oil-containing pore-size distribution and oil density obtain.
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| CN107907461B (en) * | 2017-11-03 | 2020-01-14 | 中国石油化工股份有限公司 | Research method for main occurrence pore diameter range of shale oil |
| CN108458960B (en) * | 2018-03-27 | 2019-10-29 | 中国石油大学(华东) | The hydrogeneous component of rich organic matter mud shale, porosity and the evaluation method in aperture |
| CN109856176B (en) * | 2019-03-27 | 2022-03-08 | 中国石油大学(华东) | NMR and LTNA-based compact reservoir full-size pore quantitative characterization method |
| CN113670787A (en) * | 2020-05-14 | 2021-11-19 | 中国石油天然气股份有限公司 | Method for testing pore diameters of micropores and mesopores of organic matters and other minerals in shale |
| CN112304837B (en) * | 2020-06-24 | 2021-06-25 | 成都理工大学 | Method for judging shale oil reservoir organic matter microscopic occurrence structure |
| CN114428043A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Porous medium pore size distribution characterization method and electronic equipment |
| CN113970512B (en) * | 2021-01-05 | 2024-05-28 | 中国石油天然气股份有限公司 | Method for determining free hydrocarbon enrichment pore size range |
| CN117571582A (en) * | 2024-01-16 | 2024-02-20 | 中国地质大学（武汉） | Method for determining porosity occupied by light hydrocarbon and heavy hydrocarbon in shale oil reservoir |
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