CN107560995A - A kind of fractal characterization method of the organic shale micropore based on CO2 absorption - Google Patents
A kind of fractal characterization method of the organic shale micropore based on CO2 absorption Download PDFInfo
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Abstract
The invention discloses one kind to be based on CO2The fractal characterization method of the organic shale micropore of absorption, belong to unconventionaloil pool exploration and development technical field, calculate the fractal dimension of organic shale micropore using the fractal theory of microporous medium in materials chemistry, utilize CO2Adsorpting data in shale micropore, the analysis that fractal characteristic is carried out by the linearity and non-linearity fit procedure of multi-step calculate, and finally obtain values of fractal dimension;Reliable fundamental analysis parameter is provided to evaluate the otherness of different reservoir pore structure;Available for the calculating without type, the organic shale micropore fractal dimension of different regions, reference data, and the further feature description of guiding reservoir anisotropism are provided for microcellular structure complexity.
Description
Technical field
The invention belongs to unconventionaloil pool exploration and development technical field, and in particular to one kind is based on CO2The organic matter of absorption
The fractal characterization method of shale micropore.
Background technology
The research object of fractal theory irregular has self similarity special for what is be widely present in nature and actual life
The geometric shape of property, and these forms can not be described with traditional European geometry.There is complexity using fractal theory description
The dielectric surface roughness of pore structure, the complexity of porous material and anisotropism are represented by the size of fractal dimension D,
D values are between 2~3, wherein the plane of 2 indication surface flat-satins, the free space of the 3 no solid features of instruction;Therefore, D
Pore structure of the value in 3, porous media is more complicated, and surface is more coarse;Closer to 2, then pore structure tends to be simple.
And the pore structure of same reservoir rock also has typical fractal characteristic, because the development of rich organic shale is a large amount of
Nanoscale hole, or even comprising substantial amounts of micropore (bore dia is less than 2nm), therefore, to the non-equal of shale pore morphology structure
The quantification of matter characterizes particularly critical.In correlation technique, the measurement generally use N of shale Pore genesis2Carry out adsorption experiment,
But N2Molecular activity is low under the conditions of 77K, and experiment generally can not accurately obtain micropore (especially below 1nm) information, therefore, profit
Use N2The model that adsorption experiment calculates fractal dimension is difficult to the fractal dimension for obtaining micropore.
The content of the invention
In view of this, CO is used based on fractal theory the embodiment provides one kind2Calculated for adsorbate organic
The effective ways of matter shale micropore fractal dimension.
In order to overcome the shortcomings of in prior art, the embodiment of the present invention provides one kind and is based on CO2The organic shale of absorption
The fractal characterization method of micropore, comprises the following steps:
(1) organic shale sample is gathered, to being vacuumized after the organic shale sample treatment;
(2) by CO2The organic shale sample is adsorbed under vacuum as adsorbate, and gathers absorption
Data;
(3) the feature energy of adsorption of adsorbate is calculated, and by the balance pressure in the feature energy of adsorption, adsorpting data, full
Substituted into vapour pressure in maximal absorptive capacity formula, obtain maximal absorptive capacity;
(4) equilibrium adsorption capacity in obtained maximal absorptive capacity and adsorpting data is substituted into DR equations, obtains relative inhale
Attached amount;
(5) the balance pressure in the sub-optimal fusion algorithm, adsorpting data and saturated vapour pressure are substituted into feature expression,
Obtain scale parameter value and shape parameter values;
(6) hole chi is calculated by the scale parameter value, shape parameter values, the reciprocal value of feature energy of adsorption and gamma function
Spend distribution function value;
(7) will the pore-size distribution functional value substitute into pore-size distribution function in be calculated characterize organic shale it is micro-
The fractal dimension of hole hole complexity.
Compared with correlation technique, the beneficial effect that the technical scheme of embodiments of the invention offer is brought is:It is of the invention real
The one kind for applying example use is based on CO2The fractal characterization method of the organic shale micropore of absorption, obtained based on fractal theory
The microporous medium fractal dimension computation model arrived, using CO2As adsorbate, organic shale micropore is adsorbed, can be obtained
To the fractal dimension of micropore of the bore dia in the range of 0~2nm, quantification characterizes the structure complexity of organic shale micropore,
And the computation model in correlation technique can only obtain the fractal dimension of mesopore (2~50nm of bore dia) and macropore (50nm), and not
Can quantification;The embodiment of the present invention calculate model can further evaluate the anisotropism of organic shale reservoir, in reservoir hole
It is with a wide range of applications in the fine description of gap.
Brief description of the drawings
Fig. 1 is the fractal characterization method flow schematic diagram of the embodiment of the present invention one;
Fig. 2 be the Longma small stream group shale samples of the embodiment of the present invention two lnV withLinear fit relation schematic diagram;
Fig. 3 be the Niutitang group shale samples of the embodiment of the present invention two lnV withLinear fit relation schematic diagram;
Fig. 4 is the lnJ (x) and lnx of the Longma small stream group shale samples of the embodiment of the present invention two linear fit relation schematic diagram;
Fig. 5 is the lnJ (x) and lnx of the Niutitang group shale samples of the embodiment of the present invention two linear fit relation schematic diagram.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is further described.
Embodiment one
Fig. 1 is refer to, the embodiment of the present invention provides one kind and is based on CO2The fractal characterization side of the organic shale micropore of absorption
Method, comprise the following steps:
(1) (1) collection organic shale sample, to being vacuumized after the organic shale sample treatment;After processing
Organic shale sample be the mesh of particle diameter 10~20 particulate.
(2) by CO2The organic shale sample is adsorbed under vacuum as adsorbate, and gathers absorption
Data;CO2Purity be more than 99.9999%;
(3) the feature energy of adsorption of adsorbate is calculated, and by the balance pressure in the feature energy of adsorption, adsorpting data, full
Substituted into vapour pressure in maximal absorptive capacity formula, obtain maximal absorptive capacity;
Specifically, will be combined to obtain the maximal absorptive capacity formula with absorption potential after DR equation linear fits;The feature
Energy of adsorption is calculated by the rule-of-thumb relation between the inverse of organic shale sample micropore size and feature energy of adsorption;Institute
Stating DR equations, absorption potential, maximal absorptive capacity formula, rule-of-thumb relation is respectively:
X=15z+2852.5z3+0.014z-1-0.75 (4)
θ is sub-optimal fusion algorithm (i.e. micropore packing density);
V is equilibrium adsorption capacity --- cm3/g;
V0For maximal absorptive capacity --- cm3/g;
β is affinity coefficient;
A is absorption potential --- kJ/mol;
R is mol gas constant --- 8.314J/ (molK);
T is absolute temperature --- K;
P is balance pressure --- MPa;
p0For saturated vapor pressure --- MPa;
E0For feature energy of adsorption --- the kJ/mol of standard adsorption matter;
Z is E0Inverse --- mol/kJ;
Further, the affinity coefficient β is adsorbate CO2Parachor PcWith the parachor P of standard adsorption matter0
The ratio between;Standard adsorption matter is benzene, using CO2Affinity coefficient as adsorbate is different from the affinity coefficient of standard adsorption matter, leads to
Parachor approximate calculation is crossed, i.e.,
(4) equilibrium adsorption capacity in obtained maximal absorptive capacity and adsorpting data is substituted into DR equations, obtains relative inhale
Attached amount;
(5) the balance pressure in the sub-optimal fusion algorithm, adsorpting data and saturated vapour pressure are substituted into feature expression,
Obtain scale parameter value and shape parameter values;
Specifically, the feature expression adsorbs integral equation by heterogeneous microporous solids and combines normalization distribution function
Nonlinear fitting is carried out with, the absorption potential to obtain;The heterogeneous microporous solids absorption integral equation, normalization distribution letter
Number, feature expression are respectively:
ρ is scale parameter --- kJ/mol;
V is form parameter;
Γ (x) is gamma function;
When micro-pore diameter is in the range of 0.45nm~2nm, calculated using formula (7);
(6) hole chi is calculated by the scale parameter value, shape parameter values, the reciprocal value of feature energy of adsorption and gamma function
Spend distribution function value;
Specifically, the pore-size distribution functional value calculating formula by formula (4), (6) and its with normalize distribution function
Relational expression obtain;The pore-size distribution function and the relational expression for normalizing distribution function, pore-size distribution functional value
Calculating formula is respectively;
(7) will the pore-size distribution functional value substitute into pore-size distribution function in be calculated characterize organic shale it is micro-
The fractal dimension of hole hole complexity.
Specifically, the relational expression of the pore-size distribution function and micropore size is:
J (x)=σ x2-D (10)
LnJ (x)=(2-D) lnx+ln σ (11)
D is fractal dimension, D ∈ [2,3).
Further,xmax、xminThe bound of pore radius, nm are represented respectively.
The embodiment of the present invention is based on CO2The fractal characterization method of the organic shale pore structure of reservoir of absorption, profit
Use CO2Adsorpting data in shale micropore, point of fractal characteristic is carried out by the linearity and non-linearity fit procedure of multi-step
Analysis calculates, and finally obtains values of fractal dimension;Available for the meter without type, the organic shale micropore fractal dimension of different regions
Calculate, reference data, and the further feature description of guiding reservoir anisotropism are provided for microcellular structure complexity.
Embodiment two
Using the fractal characterization method of the embodiment of the present invention one, to the Longma in south China marine organic matters shale reservoir
The underground shale samples micropore of small stream group shale (JYX-1) and Niutitang group shale (CYX-1) calculates fractal dimension.
(1) CO is gathered2The data of absorption, related data is substituted into formula (3), respectively obtain the fitting side of two groups of samples
Journey and maximal absorptive capacity, reference picture 2, Fig. 3, table 1;
The fit equation and maximal absorptive capacity of 1 two groups of shale micropore samples of table
(2) sub-optimal fusion algorithm is calculated according to obtained maximal absorptive capacity, mark sheet is passed through using sub-optimal fusion algorithm, absorption potential
Scale parameter ρ, form parameter υ is calculated up to formula (7), is shown in Table 2;
The calculating data of the parameter ρ of table 2 and ν
(3) rule of thumb z values are calculated in relational expression (4), J (x) are obtained after ρ, ν, z are substituted into formula (9), according to formula
(10), (11) can obtain that values of fractal dimension is calculated, and characterize the complexity of organic shale micropore, see Fig. 4, figure
5th, table 3, hole corresponding to straightway are the micropore that pore diameter range is more than 0.45nm.
The organic shale micropore fractal dimension of table 3 calculates
It can be seen that in table 3, the micropore structure of Longma small stream group shale is compared with Niutitang group shale micropore pore structure more
It is complicated.
Herein, the involved noun of locality such as forward and backward, upper and lower is to be located at parts in accompanying drawing in figure and zero
The mutual position of part is intended merely to the clear of expression technology scheme and conveniently come what is defined.It should be appreciated that the noun of locality
Use should not limit the claimed scope of the application.
In the case where not conflicting, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (8)
1. one kind is based on CO2The fractal characterization method of the organic shale micropore of absorption, it is characterized in that, comprise the following steps:
(1) organic shale sample is gathered, to being vacuumized after the organic shale sample treatment;
(2) by CO2The organic shale sample is adsorbed under vacuum as adsorbate, and gathers adsorpting data;
(3) the feature energy of adsorption of adsorbate is calculated, and the balance pressure in the feature energy of adsorption, adsorpting data, saturation are steamed
Air pressure is substituted into maximal absorptive capacity formula, obtains maximal absorptive capacity;
(4) equilibrium adsorption capacity in obtained maximal absorptive capacity and adsorpting data is substituted into DR equations, obtains sub-optimal fusion algorithm;
(5) the balance pressure in the sub-optimal fusion algorithm, adsorpting data and saturated vapour pressure are substituted into feature expression, obtained
Scale parameter value and shape parameter values;
(6) hole yardstick point is calculated by the scale parameter value, shape parameter values, the reciprocal value of feature energy of adsorption and gamma function
Cloth functional value;
(7) the pore-size distribution functional value is substituted into pore-size distribution function to be calculated and characterizes organic shale micropore hole
The values of fractal dimension of gap structure complexity.
2. one kind according to claim 1 is based on CO2The fractal characterization method of the organic shale micropore of absorption, its feature
It is that in step (1), the organic shale sample after processing is the particulate of the mesh of particle diameter 10~20.
3. one kind according to claim 1 is based on CO2The fractal characterization method of the organic shale micropore of absorption, its feature
It is that in step (3), will be combined to obtain the maximal absorptive capacity formula with absorption potential after DR equation linear fits;The feature is inhaled
It is attached to be calculated by the rule-of-thumb relation between the inverse of organic shale sample micropore size and feature energy of adsorption;It is described
DR equations, absorption potential, maximal absorptive capacity formula, rule-of-thumb relation are respectively:
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X=15z+2852.5z3+0.014z-1-0.75 (4)
θ is sub-optimal fusion algorithm (i.e. micropore packing density);
V is equilibrium adsorption capacity --- cm3/g;
V0For maximal absorptive capacity --- cm3/g;
β is affinity coefficient;
A is absorption potential --- kJ/mol;
R is mol gas constant;
T is absolute temperature --- K;
P is balance pressure --- MPa;
p0For saturated vapor pressure --- MPa;
E0For feature energy of adsorption --- the kJ/mol of standard adsorption matter;
Z is E0Inverse --- mol/kJ.
4. one kind according to claim 1 or 3 is based on CO2The fractal characterization method of the organic shale micropore of absorption, it is special
Sign is, in step (3), the affinity coefficient β is adsorbate CO2The ratio between the parachor of parachor and standard adsorption matter.
5. one kind according to claim 1 is based on CO2The fractal characterization method of the organic shale micropore of absorption, its feature
It is that in step (5), the feature expression adsorbs integral equation by heterogeneous microporous solids and combines normalization distribution function
Nonlinear fitting is carried out with, the absorption potential to obtain;The heterogeneous microporous solids absorption integral equation, normalization distribution letter
Number, feature expression are respectively:
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ρ is scale parameter --- kJ/mol;
V is form parameter;
Γ (x) is gamma function.
6. one kind according to claim 1 is based on CO2The fractal characterization method of the organic shale micropore of absorption, its feature
Be, in step (6), the pore-size distribution functional value calculating formula by formula (4), (6) and its with normalization distribution function
Relational expression obtains;Relational expression, the pore-size distribution functional value calculating formula of the pore-size distribution function and normalization distribution function
Respectively:
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7. one kind according to claim 1 or 6 is based on CO2The fractal characterization method of the organic shale micropore of absorption, it is special
Sign is, in step (7), the relational expression of the pore-size distribution function and micropore size is:
J (x)=σ x2-D (10)
Ln J (x)=(2-D) ln x+ln σ (11)
D is fractal dimension, D ∈ [2,3).
8. one kind according to claim 1 is based on CO2The fractal characterization method of the organic shale micropore of absorption, its feature
It is, in step (7),xmax、xminThe bound of pore radius, nm are represented respectively.
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CN111398122A (en) * | 2020-04-03 | 2020-07-10 | 中国矿业大学 | Comprehensive characterization method for heterogeneity characteristics of full-scale pore structure of shale |
CN111563695A (en) * | 2020-05-21 | 2020-08-21 | 中国地质大学(武汉) | Rapid evaluation method for shale pore structure |
CN112345429A (en) * | 2020-11-02 | 2021-02-09 | 北京科技大学 | Method and device for acquiring non-uniform geological parameters of unconventional oil and gas reservoir |
CN112986089A (en) * | 2019-12-16 | 2021-06-18 | 河南理工大学 | Tectonic coal multi-scale pore structure representation and fractal dimension calculation method |
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CN108446526A (en) * | 2018-05-22 | 2018-08-24 | 中国地质大学(武汉) | The prediction technique of shale adsorbance based on adsorpting characteristic curve and characteristic equation |
CN108446526B (en) * | 2018-05-22 | 2020-06-26 | 中国地质大学(武汉) | Shale adsorption capacity prediction method based on adsorption characteristic curve and characteristic equation |
CN109827881A (en) * | 2019-02-26 | 2019-05-31 | 西南石油大学 | Rock hydration degree characterizing method and system |
CN109827881B (en) * | 2019-02-26 | 2022-05-31 | 西南石油大学 | Rock hydration degree characterization method and system |
CN112986089A (en) * | 2019-12-16 | 2021-06-18 | 河南理工大学 | Tectonic coal multi-scale pore structure representation and fractal dimension calculation method |
CN111398122A (en) * | 2020-04-03 | 2020-07-10 | 中国矿业大学 | Comprehensive characterization method for heterogeneity characteristics of full-scale pore structure of shale |
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CN114371187A (en) * | 2021-12-17 | 2022-04-19 | 成都理工大学 | Shale pore quantitative structure complexity measuring method, system, medium and equipment |
CN114371187B (en) * | 2021-12-17 | 2023-11-03 | 成都理工大学 | Shale pore quantitative structure complexity determination method, system, medium and equipment |
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