CN104697902B - The method for determining rock wettability in electric field - Google Patents

The method for determining rock wettability in electric field Download PDF

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CN104697902B
CN104697902B CN201310665262.5A CN201310665262A CN104697902B CN 104697902 B CN104697902 B CN 104697902B CN 201310665262 A CN201310665262 A CN 201310665262A CN 104697902 B CN104697902 B CN 104697902B
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electric field
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rock
test liquid
sample cell
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CN104697902A (en
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周明辉
孙文杰
宋新民
马德胜
王强
罗文利
刘波
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China Petroleum and Natural Gas Co Ltd
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Abstract

The present invention relates to a kind of method for determining sample rock wettability in electric field, methods described includes:A. sample rock, environmental liquids and test liquid are collectively formed into three-phase system in sample cell;B. when not applying electric field the initial wetting property of observing samples rock and contact corner characteristics;C. after electric field is applied to the three-phase system in sample cell by battery lead plate, change of the observation test liquid in the contact angle of sample rock surface.By the method for the present invention can the real time measure test liquid in the electric field change in the wetability of sample rock surface, wherein the intensity of electric field, waveform are adjustable and can change over time.Compared with prior art determines the method that electrical effect influences on rock wettability, method of the invention accurately can study and observe electric field for the influence of rock wettability to find the optimal wetability of recovery ratio and current field condition.

Description

The method for determining rock wettability in electric field
Technical field
The present invention relates to it is a kind of determine electric field in rock wettability method, and in particular to it is a kind of can be in variable electric field It is middle to observe and record the method that liquid changes in rock surface contact angle.
Background technology
When drop is attached to the surface of solids, because wetability is different and different droplet profiles occurs, drop is in solid-liquid Angle between the tangent line and surface of engagement edge is referred to as contact angle, and the wetability of solid is generally represented with contact angle.Wetting Property is one of critical nature of reservoir rock in oil-gas field development, and petroleum industry generally acknowledges that it has a major impact to recovery ratio. D.G.Kessel (1987) thinks that recovery ratio can be improved by changing wetability, and its economic benefit differs 1-2 times.Qin Jishun etc. 《Physics of oil layer》Also the mechanism of wetability influence recovery ratio is explicitly pointed out in (publishing house of University of Petroleum, in June, 2004) is Work agent under different wetabilitys(It is used to the water or gas of displacement rock Crude Oil)Drive the mechanism difference for washing crude oil.Cause This, people are attempting to find the method for improving recovery ratio by studying and changing wetability always.
So far, existing a large amount of scholar's research change the method for wetability, mainly surfactant method.There is a small amount of Person(For example, Aggour, M.A., 1992)Think reservoir rock have DC current by when, its wetability has certain change, but Mechanism explanation is not provided.Also there are many scholars simultaneously by the way of the aqueous rock core of the oil-containing into core holding unit is powered (Including direct current and alternating current)Obtain the experimental result for improving oil recovery.But due to these research physical size compared with Greatly, it is difficult to observe the change of wetability, and direct-electrifying causes electric osmose, electrophoresis and electrolysis, it is impossible to intuitively reflect electric field Contribution of the lower wetability change of effect for recovery ratio.
In addition, someone is (for example, Zhang Renxiong, Sui Shaoqiang:Direct current treatment oil reservoir improves recovery ratio experimental study, Henan stone Oil, 1997,2:21-23) propose, in rock(Rock core)Two ends directly add electrode, by direct current or alternating current through oil-containing Oil and water in the rock of water, this instrument sample is by the larger interference for flowing through electric current, for research electric field rather than electric current shadow Loud work is very unfavorable.Therefore, not any method can individually determine shadow of the extra electric field to wetability at present Ring.It is accurate to study and observe electric field for the influence of rock wettability to find in order to exclude interference caused by direct-electrifying The optimal wetability of recovery ratio and current field condition, it is necessary to which a kind of new measuring method is provided.
The content of the invention
Disturb, observed simultaneously in variable electric field caused by can excluding direct-electrifying it is an object of the invention to provide one kind The method that record liquid changes in rock surface contact angle.
It is described the invention provides a kind of method for determining sample rock wettability in electric field in order to realize the purpose Method includes:
A. sample rock, environmental liquids and test liquid are collectively formed into three-phase in the sample cell being made up of insulating materials System;
B. when not applying electric field observing samples rock initial wetting property and contact angle;
C. after electric field is applied to the three-phase system in sample cell by the battery lead plate on the outside of sample cell, observation test Change of the liquid in the contact angle of sample rock surface.
In the method for the invention, the sample cell has the sample pond body and sample cell lid for constituting closed vessel, described Sample rock is positioned over the bottom of sample pond body, and the test liquid is attached to the surface of the sample rock, the environment liquid Body is full of whole sample cell.
In the method for the invention, the battery lead plate is to be located above and below two electrode plate of sample cell respectively, from And obtain the electric field perpendicular to test liquid Yu sample rock contact face;Or, the battery lead plate is to be located at a sample cell left side respectively Side and two electrode plates of right flank, so as to obtain the electric field parallel to test liquid and sample rock contact face.
In the method for the invention, the electric field be steady electric field or by power supply and waveform generator control can power transformation .
In the method for the invention, at least one change in the intensity of the electric field, waveform and frequency.
In the method for the invention, the environmental liquids and the test liquid all do not have electric conductivity, or wherein extremely It is how a kind of conductive.
In the method for the invention, step b and step c carry out the observation by video camera under sheen light source.
In the method for the invention, the power supply is dc source, and voltage is 0~1000V.
In the method for the invention, the frequency is 0~100kHz.
In the method for the invention, the sample rock is sandstone, carbonate rock and mud stone containing oil and/or water.
By means of the invention it is also possible to the influence of accurate recording and observation electric field to rock specimens wettability in itself, from And recovery ratio is improved during for large scale mining foundation is provided.
By means of the invention it is also possible to ensure that liquid-rock system physics, the stabilization of chemical property, make research side Method is more stablized and credible.
By method of the invention, it is possible to directly influence of the observation electric field to rock wettability on a microscopic scale, this It can not be realized in conventional petroleum reservoir electrical effect research instrument.
By the method for the present invention, the feature that waveform generator has widened selectable electric field is introduced, will only have one in the past The steady electric field of dimension variable, i.e. electric-field intensity, which is changed into, possesses four-dimensional variable, including electric-field intensity, direction of an electric field, electric field waveform With the variable electric field of electric field frequency, can electric field is for the influence of rock wettability under Study of Multivariable, extend instrument should With scope, more fully current field condition parameter can be obtained for optimum dampener implementations.
Brief description of the drawings
Fig. 1 is the integrally-built schematic diagram for the device that the inventive method is used.
Fig. 2 is the detailed construction schematic diagram of sample and component on sample stage.
Each reference is in figure:1. video camera, 2. sheen light sources, 3. work bases, 4. sample stages, 5. sample cells, 6. Sample cell lid, 7. power supplys, 8. waveform generators, 9. battery lead plates, 10. environmental liquids, 11. test liquids, 12. sample rocks.
Fig. 3 is the figure of the relation between the electric-field intensity and contact angle determined in the embodiment of the present invention 1.
Embodiment
Wetability is one of critical nature of reservoir rock in oil-gas field development, is to influence the important indicator of recovery ratio.Have Research, which shows to be powered, can change the wettability of rock, but by the electric current flowed through when prior art is powered to rock can be to liquid Body-rock system produces various influences, influences, can't send out such as uneven voltage drop, electric osmose, electrophoresis and electrolytic effect Now be powered the definite influence on rock wetness, it is impossible to which accurate grasp improves the energization ginseng of recovery ratio in actually exploitation work Number.The method of rock wettability can solve this problem in the measure electric field that the present invention is provided.
The method of rock wettability includes in the measure electric field of the present invention:
A. sample rock, environmental liquids and test liquid are collectively formed into three-phase system in sample cell;
B. when not applying electric field the initial wetting property of observing samples rock and contact corner characteristics;
C. after electric field is applied to the three-phase system in sample cell by battery lead plate, observation test liquid is in sample rock table The change of the contact angle in face.
The sample rock can be various rocks, for example, sandstone, carbonate rock and mud stone containing oil and/or water.
The environmental liquids can be the liquid for simulating the water in mining environment, different with mining environment change, for example, Sodium-chloride water solution.
The test liquid can be the crude oil of hydrocarbons, such as association of sample rock.The environmental liquids with it is described Test liquid is two kinds of not miscible different liquid.
The three-phase system is the system being made up of rock, environmental liquids and test liquid three-phase.
The wettability is the ability that surface of solids liquid is sprawled.The wetability of solid is represented with contact angle, when drop drop In the surface of solids, wetability difference may occur in which different shape.Drop is between the tangent line and surface at solid-liquid contact edge Angle is referred to as contact angle.Generally speaking, contact angle is smaller, and wetability is stronger;Contact angle is bigger, and wetability is weaker.For certain For liquid, it is considered that contact angle is wetting in 0 to 75 degree, 75 degree to 105 degree are neutral wetting, and 105 to 180 degree be not moisten It is wet.Specifically, for the simultaneous oil of rock surface and water, now the contact angle sum of oil and water is 180 degree.If The contact angle of water is soaked between being spent 0 to 75 for water, is neutral wetting between 75 degree to 105 degree, 105 between 180 degree To be glossy wet.It is neutral wetting between 75 degree to 105 degree if the contact angle of oil is glossy wet between being spent 0 to 75, 105 between 180 degree for water soak.
The electric field can be direction of an electric field and the constant steady electric field of intensity or direction of an electric field and Strength Changes Variable electric field.
In the method for the invention, the battery lead plate can be located at sample cell both sides and opposing parallel placement respectively, so that Form the electric field by sample cell.
In sample cell, rock is located at sample cell bottom, and test liquid is attached to sample rock surface, and environmental liquids are full of Whole sample cell, sample cell lid constitutes closed vessel with sample cell.When battery lead plate is located at sample cell level above and below respectively When staggered relatively, the electric field perpendicular to test liquid and sample rock contact face can be obtained.When battery lead plate is located at sample cell respectively When left surface and right flank and vertically opposite placement, the electric field parallel to test liquid and sample rock contact face is obtained.Or Four electrode plates, the upper and lower, left and right of sample cell can be individually positioned in a manner described, and needing to convert electric field side by person To when to corresponding battery lead plate be powered.
The electric field that the present invention is used can be steady electric field, or the variable electric field controlled by power supply and waveform generator. At least one wherein in the intensity of electric field, waveform and frequency can change, so as to study the electric field of different parameters to rock The influence of stone wettability.
The power supply of the present invention can be dc source or AC power, and voltage can be 0~1000V, by specific Demand and Power Supplies Condition are determined.It can for example change in the range of 1-900V, preferably 50-800V scopes, more preferably 100-500V Scope.
The waveform generator of the present invention can be fm waveform generator or amplitude modulation waveform generator.
The intensity of electric field determines that the business of electrical potential difference and physical distance determines between battery lead plate according to experiment demand in the assay It is fixed, for example can be in 1-106Change in the range of V/m, preferably 10-106V/m scopes, more preferably 103-106V/m scopes.
The waveform of electric field can be sinusoidal waveform, square-wave waveform or triangular waveform in the assay, but be not limited to above-mentioned waveform.
The frequency of electric field is determined by real needs and selected waveform generator in the assay, can be in 0~100kHz Interior change, preferably 50~90kHz scopes, more preferably 100~50kHz scopes.
The environmental liquids and the test liquid all do not have electric conductivity, or wherein at most a kind of conductive. Such as when test liquid is crude oil without electric conductivity, environmental liquids can be that (electrical conductivity is for conductive salt solution 10-1000 μ S/cm scopes, more preferably 100-800 μ S/cm scopes), or (electrical conductivity is the low-down pure water of electric conductivity 5-10 μ S/cm scopes, more preferably 7-9 μ S/cm scopes).
Apply in the present invention before and after electric field to the observation of rock wetness and contact angle by video camera under sheen light source Carry out.The video camera can use any video camera, as long as can record rock wetness when electric field change and connect The change of feeler.The sheen light source is different from the visible ray of direct projection, is a kind of visible ray of diffusion, producing method be General visible source(Filament)The resistant to elevated temperatures translucent plastic of external application is blocked.
The sample cell is the closed vessel being made up of sample pond body and sample cell lid, and sample pond body and sample cell lid are exhausted Edge material.Sample pond body and sample cell lid can be with transparent materials, such as glass or transparent resin, but are not limited to both the above.Make For another selection, the face at least towards video camera and light source of the sample pond body is transparent material.
The reservoir rock that the method for the present invention can be used in any oil gas field, can be used for the rock core of oil-containing and water, or Only aqueous or oil-containing rock core, such as sandstone, carbonate rock and mud stone containing oil and/or water.
The method of the present invention can pass through the following measure device realization shown in Fig. 1, the measure device:Record system, branch Hold system, sample cell, electric field generation system.In the apparatus, the record system includes video camera and sheen light source, the branch Holding system includes work base and sample stage, and the sample cell has the sample pond body and sample cell lid for constituting closed vessel, institute Stating electric field generation system includes power supply, waveform generator and battery lead plate.In test, sample rock is positioned over the sample pond body Bottom, test liquid is attached to the surface of the sample rock, and environmental liquids are full of the whole sample pond body, sample cell lid Closed vessel is constituted with sample cell, just to video camera before sample cell, just to sheen light source, two pairs of electrodes behind sample cell Plate is respectively on the outside of the top and bottom of sample cell and/or on the outside of the face of left and right, and two pairs of electrodes plate is provided by power supply through waveform generator Positive and negative pole tension.
The example of sample cell on the sample rock (12) wherein held in sample cell (5) as shown in Fig. 2 be attached with test fluid Body (11), remaining sample cell (5) interior space is filled with environmental liquids (10), and the sample cell (5) of capping sample cell lid (6) is outside to be set There is battery lead plate (9)
Compared with the method for traditional direct-electrifying research oil-bearing rock change of properties, the invention has the advantages that:
1. fluid to be measured and solid sample do not have electric current to pass through, reduce in system due to uneven voltage caused by electric current Reduce the influence to internal electric field.
2. fluid to be measured and solid sample do not have electric current to pass through, eliminate direct-electrifying and cause electric osmose, electrophoresis and electrolysis effect The interference answered, it is ensured that system physics, the stabilization of chemical property, makes research method more stablize and credible.
3. the present invention can directly observe influence of the electric field to rock wettability on a microscopic scale, this is in conventional oil It can not be realized in reservoir electrical effect research method.
4. the feature of selectable electric field has been widened in the introduction of waveform generator, will only have one-dimensional variable, i.e. electric field in the past The steady electric field of intensity, which is changed into, possesses four-dimensional variable, including electric-field intensity, direction of an electric field, electric field waveform and electric field frequency can Changed electric field, for the influence of rock wettability, can extend the application of method by electric field under Study of Multivariable.
Using the method for the present invention, the influence of electric field to rock wetness in itself is observed in the case of exclusive PCR, from And can determine to improve wettability and the parameter of oil recovery, provide support for actual extensive recover the oil.
The present invention is explained in more detail referring to specific example, provide these examples be for purposes of explanation, And it is not intended to limit the present invention.
Embodiment 1
Choose the initial oil water bearing sand of Chinese Yumen Oilfield L oil reservoirs for sample rock be shaped as long 16mm, width 12mm, High 8mm cuboid.The output crude oil 0.05mL for choosing the oil reservoir is test liquid.The simulated formation water for choosing the oil reservoir is ring Border liquid, the solvent of the simulated formation water is distilled water, and solute formula is as follows:Sodium acid carbonate 1.461g/L, sodium sulphate 0.017g/L, Magnesium dichloride hexahydrate 1.653g/L, calcium chloride 0.788g/L, potassium chloride 0.033g/L, sodium chloride 8.058g/L.Sample Product pond(Cover after sample cell lid)External dimensions is 25mm(It is long)、20mm(It is wide)、23mm(It is high), material is optical glass.Electrode Board size is identical with the face of the sample cell of institute parallel contact, and thickness is 1mm, and material is copper, is placed in the outside of sample cell top and bottom. DC power output voltage is constant 100V.
Before applying an electric field, the wettability of rock using test liquid rock surface contact angle meter as 95.2 °, apply Crude oil is changed into 83.3 ° to electric field (now field strength is 4348V/m between two-plate) in the contact angle of rock surface afterwards, and contact angle is reduced 11.9°.After electric-field intensity is further improved, contact angle and wettability do not change.Therefore, for the rock sample, profit is changed Moist optimum electric field intensity is within 4348V/m.
Field strength-contact angle the graph of a relation for the multiple spot that the present embodiment is determined is shown in Fig. 3.
Comparative example 1
Using sample rock same as Example 1 and test liquid, test liquid is added dropwise on the surface of sample rock After upper, the both sides up and down of rock sample in sample cell are placed in the battery lead plate in embodiment 1, are dipped in environmental liquids, and with phase Same electric power output voltage is constant 100V.Environmental liquids are conductive, it is impossible to determine the wettability before and after being powered and contact The change at angle, this shows, the electric current such as common survey method that battery lead plate is immersed in environmental liquids directly flows through sample rock Method can not measure influence of the electric field to contact angle/wetability.
Embodiment 2
Sample rock is:The initial oil water bearing sand of Yumen Oilfield L oil reservoirs.
Test liquid is:The output crude oil 0.05mL of the oil reservoir.
Environmental liquids are:The simulated formation water of the oil reservoir is environmental liquids, and the solvent of the simulated formation water is distilled water, Solute formula is as follows:Sodium acid carbonate 1.461g/L, sodium sulphate 0.017g/L, Magnesium dichloride hexahydrate 1.653g/L, calcium chloride 0.788g/L, potassium chloride 0.033g/L, sodium chloride 8.058g/L.
Sample cell is same as Example 1, applies the direct current that voltage is 80V, the electric field of application is 3478V/m.
Before applying an electric field, the wettability of rock using test liquid rock surface contact angle meter as 97.5 °, apply Contact angle is changed into 90.3 ° after electric field 3478V/m, and contact angle reduces 7.2 °.Electric-field intensity further improve after contact angle and Wettability does not change (field strength of multiple spot-contact angle relation is not shown).Therefore, for the rock sample, wetability is changed Optimum electric field intensity within 3478V/m.
Comparative example 2
Using sample rock same as Example 2 and test liquid, test liquid is added dropwise on the surface of sample rock After upper, the both sides up and down of rock sample in sample cell are placed in the battery lead plate in embodiment 2, are dipped in environmental liquids, and with phase Same electric power output voltage is constant 80V.Environmental liquids are conductive, it is impossible to determine the wettability and contact angle before and after being powered Change, this shows, the electric current such as common survey method that battery lead plate is immersed in environmental liquids is directly flowed through to the side of sample rock Method can not measure influence of the electric field to contact angle/wetability.
Embodiment 3
Sample rock is:The initial oil water bearing sand of Yumen Oilfield L oil reservoirs.
Test liquid is:The output crude oil 0.05mL of the oil reservoir.
Environmental liquids are:The simulated formation water of the oil reservoir is environmental liquids, and the solvent of the simulated formation water is distilled water, Solute formula is as follows:Sodium acid carbonate 1.461g/L, sodium sulphate 0.017g/L, Magnesium dichloride hexahydrate 1.653g/L, calcium chloride 0.788g/L, potassium chloride 0.033g/L, sodium chloride 8.058g/L.
Sample cell is same as Example 1, applies the alternating current that voltage is 100V, the electric field of application is 4348V/m, and frequency is 50Hz, waveform is sine wave.
Before applying an electric field, the wettability of rock using test liquid rock surface contact angle meter as 98.1 °, apply Electric field (voltage is 100V alternating current, and the electric field of application is 4348V/m, and frequency is 50Hz, and waveform is sine wave) contact angle afterwards Be changed into 81.2 °, contact angle reduces 16.9 °.Contact angle and wettability do not change (multiple spot after electric-field intensity is further improved Field strength-contact angle relation it is not shown).Therefore, for the rock sample, the optimum electric field intensity for changing wetability exists Within 4348V/m.And compared with embodiment 1, under conditions of phase same electric field, 50Hz sinusoidal ac changes wetability Effect is better than direct current.
Comparative example 3
Using sample rock same as Example 3 and test liquid, test liquid is added dropwise on the surface of sample rock After upper, the both sides up and down of rock sample in sample cell are placed in the battery lead plate in embodiment 3, are dipped in environmental liquids, and with phase Same electric power output voltage is constant 100V alternating current, and the electric field of application is 4348V/m, and frequency is 50Hz, and waveform is sine Ripple.Environmental liquids are conductive, it is impossible to determine the wettability before and after being powered and the change of contact angle, this shows, by battery lead plate The electric current such as common survey method in immersion environmental liquids directly flow through sample rock method can not measure electric field to contact angle/ The influence of wetability.
Embodiment 4
Sample rock is:The initial oil water bearing sand of Yumen Oilfield L oil reservoirs.
Test liquid is:The output crude oil 0.05mL of the oil reservoir.
Environmental liquids are:The simulated formation water of the oil reservoir is environmental liquids, and the solvent of the simulated formation water is distilled water, Solute formula is as follows:Sodium acid carbonate 1.461g/L, sodium sulphate 0.017g/L, Magnesium dichloride hexahydrate 1.653g/L, calcium chloride 0.788g/L, potassium chloride 0.033g/L, sodium chloride 8.058g/L.
Sample cell is same as Example 1, applies the alternating current that voltage is 80V, the electric field of application is 3478V/m, and frequency is 50Hz, waveform is sine wave.
Before applying an electric field, the wettability of rock using test liquid rock surface contact angle meter as 97.7 °, apply Electric field (voltage is 80V alternating current, and the electric field of application is 3478V/m, and frequency is 50Hz, and waveform is sine wave) contact angle afterwards It is changed into 84.1 °, contact angle reduces 13.6 °.Contact angle and wettability do not change (multiple spot after electric-field intensity is further improved Field strength-contact angle relation is not shown).Therefore, for the rock sample, the optimum electric field intensity of wetability is changed in 3478V/ Within m.And compared with embodiment 2, under conditions of phase same electric field, the effect of 50Hz sinusoidal ac change wetability is good In direct current.
Comparative example 4
Using sample rock same as Example 4 and test liquid, test liquid is added dropwise on the surface of sample rock After upper, the both sides up and down of rock sample in sample cell are placed in the battery lead plate in embodiment 4, are dipped in environmental liquids, and with phase Same electric power output voltage is 80V alternating current, and the electric field of application is 3478V/m, and frequency is 50Hz, and waveform is sine wave.Ring Border liquid is conductive, it is impossible to determine the wettability before and after being powered and the change of contact angle, this shows, battery lead plate is immersed into ring The method that the electric currents such as the common survey method in the liquid of border directly flow through sample rock can not measure electric field to contact angle/wetability Influence.

Claims (10)

1. a kind of method for determining sample rock wettability in electric field, methods described includes:
A. sample rock, environmental liquids and test liquid are collectively formed into three-phase body in the sample cell being made up of insulating materials System;
B. when not applying electric field observing samples rock initial wetting property and contact angle;
C. after electric field is applied to the three-phase system in sample cell by the battery lead plate on the outside of sample cell, test liquid is observed In the change of the contact angle of sample rock surface.
2. the method for claim 1, wherein the sample cell has the sample pond body and sample cell for constituting closed vessel Lid, the sample rock is positioned over the bottom of sample pond body, and the test liquid is attached to the surface of the sample rock, described Environmental liquids are full of whole sample cell.
3. the method for claim 1, wherein the battery lead plate is to be located at the above and below two blocks of electricity of sample cell respectively Pole plate, so as to obtain the electric field perpendicular to test liquid and sample rock contact face;Or, the battery lead plate is to be located at sample respectively Two electrode plates of product pond left surface and right flank, so as to obtain the electric field parallel to test liquid and sample rock contact face.
4. the method for claim 1, wherein the electric field is steady electric field or controlled by power supply and waveform generator Variable electric field.
5. method as claimed in claim 4, wherein, at least one in intensity, waveform and the frequency of the variable electric field becomes Change.
6. the method for claim 1, wherein the environmental liquids have conduction with most a kind of in the test liquid Property.
7. the method for claim 1, wherein step b and step c carry out the sight by video camera under sheen light source Survey.
8. method as claimed in claim 4, wherein, the power supply is dc source, and voltage is 0~1000V.
9. method as claimed in claim 5, wherein, the frequency is 0~100kHz.
10. the method for claim 1, wherein the sample rock contains oil and/or water, and the sample rock is Sandstone, carbonate rock or mud stone.
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