CN112296348A - Hydrophobic noble metal nano tracer liquid, preparation method and application - Google Patents
Hydrophobic noble metal nano tracer liquid, preparation method and application Download PDFInfo
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Abstract
The invention relates to a hydrophobic precious metal nanometer tracer solution, a preparation method and application, and relates to the technical field of shale oil gas development; wherein the tracer liquid comprises a hydrophobic dispersion and noble metal nanoparticles dispersed in the hydrophobic dispersion; the noble metal nano particles are dispersed and modified by adopting a hydrophobic solvent; the invention also discloses a preparation method and application of the tracer liquid. The tracer liquid adopts noble metal nanoparticles dispersed by a hydrophobic solvent as a tracer agent, and has a better affinity effect with a hydrophobic matrix such as organic matters in shale, so that the noble metal nanoparticles are uniformly retained in hydrocarbon wet pores of the shale and are clearly identified through a scanning electron microscope, and the migration information of fluid in the micro-nano pores of the shale is visually acquired.
Description
The invention relates to the technical field of shale gas development, in particular to a hydrophobic precious metal nanometer tracer solution, a preparation method and application.
Background
Shale pores are both important hydrocarbon reservoir spaces and the most important hydrocarbon migration pathways. Because the nanometer pores can restrict and control the storage and occurrence of the shale oil, the research on the fluid migration rule in the shale pores has important theoretical and practical significance for resource quantity evaluation, shale gas exploitation benefit improvement and the like. Most studies in the literature currently focus on the size, distribution, number shape, and connectivity of rock nanopores and do not involve the exploration of oil and gas migration channels in the pores. The migration channel and the route of oil and gas have important influence on oil and gas exploitation. The task of huqihong is that in the text of wettability, pore connectivity and fluid-tracer migration of shale oil reservoir layer in Dongyngxiu Shahechuu group, polar (such as brine) and nonpolar (such as n-decane) tracers are selected and used for self-absorption tests and diffusion tests of rock capillary tubes, and tracer element imaging is carried out by using a laser ablation-inductive coupling-plasma mass spectrometer method (LA-ICP-MS), so that the distribution rule and migration rate of the tracers in the spontaneous imbibition process are respectively obtained. It does not indicate the "via" hydrocarbon migration path and pore type and size by the fluid. Therefore, a new nano-marking method is needed for indicating shale oil micro migration channels.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hydrophobic precious metal nano tracer solution, which is preferentially attracted and attached to a shale hydrophobic matrix after entering a pore structure of shale, so that a scanning electron microscope image can more clearly reflect a fluid channel in the shale, and further path information for indicating shale oil-gas storage is provided.
The invention also provides a preparation method for preparing the hydrophobic noble metal nano tracer solution.
The invention also provides a shale oil micro migration channel identification method based on the hydrophobic precious metal nano tracer liquid, which adopts the precious metal nano tracer liquid with hydrophobicity as a tracer, combines the performance that precious metal nano particles can be easily identified under a scanning electron microscope and can realize spontaneous imbibition with shale pores to enter a shale sample, traces a flow channel of a fluid entering the shale sample, and solves the problem that the existing tracer agent is difficult to clearly reflect the migration path of the fluid.
The technical scheme for solving the technical problems in the embodiment of the application is as follows: a hydrophobic noble metal nano tracer liquid, which comprises a hydrophobic dispersion liquid and noble metal nano particles dispersed in the hydrophobic dispersion liquid; the noble metal nanoparticles are modified with a hydrophobic dispersion.
In the tracer liquid, the noble metal nanoparticles are dispersed and modified by adopting a hydrophobic dispersion liquid to obtain a hydrophobic noble metal nanoparticle dispersion liquid, so that the hydrophobic noble metal nanoparticles enter the shale pores along with the fluid and are easily attached to a hydrophobic matrix in the shale pore structure, the hydrophobic noble metal nanoparticles are retained and then displayed during scanning electron microscope imaging, and the flow path of the fluid in the shale pores is identified.
Further, the noble metal nanoparticles are any one of gold nanoparticles, silver nanoparticles, palladium nanoparticles and platinum nanoparticles; preferably gold nanoparticles. The particle size of the noble metal nano-particles is 10-20 nm.
Further, the hydrophobic dispersion liquid is one or more of n-heptane, n-octane, n-nonane and n-decane. The hydrophobic dispersion liquid provides a stable dispersion system for the noble metal nano particles, provides hydrophobic property for the noble metal nano fluid, and does not influence the imaging display of the noble metal nano particles in a scanning electron microscope. The hydrophobic dispersion liquid is preferably a mixed dispersion liquid in which the mass ratio of n-octane to n-decane is 1: 2.4.
The invention also discloses a preparation method of the hydrophobic noble metal nano tracer solution, which specifically comprises the following steps:
s1) adding noble metal salt and oleylamine into toluene for dissolving, heating and refluxing for 5-8 h under the protection of nitrogen, and cooling to room temperature to obtain a reaction solution;
s2) adding ethanol into the reaction solution, and obtaining modified noble metal nano-particles after centrifugal separation;
s3) adding the modified precious metal nanoparticles prepared in the step S2) into the dispersion liquid, and performing ultrasonic dispersion for 30-60 min to obtain 5mg/mL of nano tracer liquid.
Further, in the step S1), the molar concentration of the noble metal salt added into the toluene is 0.005-0.1 mol/L; the volume ratio of the toluene to the oleylamine is 20-50: 1. Preferably, the molar concentration of the noble metal salt in the toluene is 0.01mol/L, and the volume ratio of the toluene to the oleylamine is preferably 25: 1.
Further, in the step S1), the temperature of the heating reflux is 75-110 ℃.
The invention also discloses a shale oil micro migration channel identification method based on the nano tracer liquid, which applies the hydrophobic precious metal nano tracer liquid to a fluid migration channel in a shale pore, and specifically comprises the following steps:
A1) preparing a shale sample, and drying the prepared shale sample for later use;
A2) preparing tracer fluid containing hydrophobic noble metal nano particles into the tracer fluid with the concentration of the modified noble metal nano particles being 0.2 mg/mL-1.0 mg/mL; immersing the shale sample into a tracing fluid, and cleaning the tracing fluid attached to the surface of the shale sample after spontaneous imbibition is carried out for 24-48 h;
A3) and carrying out electron microscope scanning imaging on the shale sample by adopting a scanning electron microscope.
Further, the shale sample is of a cubic structure with a polished surface.
Further, the shale sample is dried for 12-24 hours at the temperature of 60-120 ℃.
In the technical scheme, the hydrophobic precious metal nanoparticles enter the pores of the shale sample along with the fluid and are transported along with the flow of the fluid, and the hydrophobic precious metal nanoparticles are easily adsorbed on the surfaces of the pores in the shale sample because most of the matrix in the pores of the shale is hydrophobic. And then carrying out electron microscope scanning on the shale sample soaked in the fluid through an electron scanning electron microscope to obtain a distribution diagram of the noble metal nanoparticles in the shale sample, namely obtaining a migration path of shale oil in a pore structure of the shale sample.
The shape of the shale sample passing through is cubic; the shale sample with higher surface flatness is obtained by grinding and polishing, and the size, the shape and the distribution of the nano-aperture in the shale sample can be observed under back scattering electron imaging. After the shale sample is imbibed, the tracer liquid on the surface of the shale sample needs to be cleaned, so that the condition that the tracer liquid adsorbed on the surface of the shale sample influences the observation of a scanning electron microscope on the noble metal nanoparticles in the pores in the shale sample is avoided.
And further, analyzing the element composition of the flow channel of the tracer liquid by utilizing X-ray energy spectrum analysis to obtain the matrix composition and type of the hydrocarbon wet pores of the shale sample.
The invention has the beneficial effects that: according to the hydrophobic precious metal nano tracer liquid for identifying the shale oil micro migration channel, hydrophobic precious metal nano particles and dispersion liquid are adopted to form nano fluid with uniformly dispersed hydrophobic precious metal nano particles, so that a tracer with hydrophobicity and good dispersion effect is obtained, and the tracer can be uniformly adsorbed and distributed in shale pores by hydrophobic matrixes in the shale pores after entering a shale sample; and the pore structure in the shale sample can be clearly shown under a scanning electron microscope, and the migration information of the fluid in the shale micro-nano pores can be visually expressed.
According to the preparation method of the tracer, the noble metal salt is directly reduced by the reducing agent to prepare the noble metal nanoparticles, and the noble metal nanoparticles are dispersed in the hydrophobic dispersion liquid, so that the nanoparticles are uniformly dispersed, and the noble metal nanoparticles are prevented from being agglomerated and grown due to instability in the preparation and dispersion processes of the noble metal nanoparticles; meanwhile, the preparation step is omitted, and the yield is improved; the prepared noble metal nanoparticles are dispersed by the hydrophobic dispersion liquid, so that the noble metal nanoparticles can be directly used to have better dispersion effect, and a fluid migration channel of a pore in shale can be accurately and clearly identified, thereby avoiding the influence on the tracing effect caused by the agglomeration or uneven dispersion of the nanoparticles due to the break of the system balance when the noble metal nanoparticles are diluted or dispersed in the fluid.
The tracing method disclosed by the application adopts the hydrophobic modified precious metal nanoparticles as the tracer, and can form a better adsorption effect with the hydrophobic matrix in the shale, so that the modified precious metal nanoparticles are uniformly retained in the pores of the shale, and are clearly identified through a scanning electron microscope, and the migration information of the fluid in the micro-nano pores of the shale is visually acquired.
Drawings
FIG. 1 is a TEM image of a gold nanotrap fluid prepared in some embodiments of the present invention;
fig. 2 is a TEM image of a silver nanopattern fluid prepared in some embodiments of the present invention;
FIG. 3 is a graph comparing wetting angle of pure water dispersions of gold nanoparticles, n-decane dispersions, and water prepared in some examples of the invention;
FIG. 4 is a graph comparing wetting angle of pure water dispersions, n-decane dispersions, and water of silver nanoparticles prepared in some examples of the present invention;
fig. 5 is an SEM image of tracers prepared in some examples of the present invention after adsorption on different types of pores, where fig. 5(a) is intra-granular pores (pyrite); FIG. 5(B) shows interparticle pores; FIG. 5(C) is a crack; fig. 5(D) shows organic pores.
FIG. 6 is an SEM image of a tracer disclosed in the present invention after adsorption on clay;
FIG. 7 is an SEM image of gold nanotrap fluid flowing through the pores of a shale as disclosed herein;
fig. 8 is a photograph of a spectral surface scan of a gold nanopattern fluid through the pores of a shale as disclosed herein.
Detailed Description
The principles and features of the present application are described below in conjunction with the following examples, which are set forth merely to illustrate the present invention and are not intended to limit the scope of the present application.
The application discloses a hydrophobic noble metal nano tracer solution, which comprises a dispersion solution and noble metal nano particles dispersed in the dispersion solution; the noble metal nano-particles are dispersed and modified by adopting a hydrophobic solvent.
In some embodiments, the noble metal nanoparticles are any one of gold nanoparticles, silver nanoparticles, palladium nanoparticles, platinum nanoparticles; preferably gold nanoparticles. The particle size of the noble metal nano-particles is 10-20 nm.
In some embodiments, the dispersion is one or more of n-heptane, n-octane, n-nonane, and n-decane. The dispersion liquid provides a stable dispersion system for the noble metal nano particles, provides hydrophobic property for the noble metal nano fluid, and does not influence the imaging display of the noble metal nano particles in a scanning electron microscope. The hydrophobic dispersion liquid is preferably n-octane and n-decane; more preferably, a mixed dispersion liquid having a mass ratio of n-octane to n-decane of 1:2.4 is used.
The invention also discloses a preparation method of the hydrophobic noble metal nano tracer solution, which specifically comprises the following steps:
s1) adding precious metal salt and oleylamine into toluene to dissolve, obtaining a mixed solution with the precious metal salt concentration of 0.005-0.1 mol/L and the toluene-oleylamine volume ratio of 20-50: 1, heating to 75-110 ℃ under the protection of nitrogen, refluxing for 5-8 h, and cooling to room temperature to obtain a reaction solution;
s2) adding ethanol into the reaction solution, and obtaining modified noble metal nano-particles after centrifugal separation;
s3) adding the modified noble metal nanoparticles prepared in the step S2) into the dispersion liquid, and performing ultrasonic dispersion for 30-60 min to obtain 5mg/mL of nano tracer liquid.
Preferably, the molar concentration of the noble metal salt in the toluene is 0.01mol/L, and the volume ratio of the toluene to the oleylamine is preferably 25: 1.
The invention also discloses a shale oil micro migration channel identification method based on the nano tracer liquid, which applies the hydrophobic precious metal nano tracer liquid to a fluid migration channel in a shale pore, and specifically comprises the following steps:
A1) grinding and polishing to obtain a cubic shale sample with a smooth surface, and drying the prepared shale sample for later use;
A2) preparing tracer fluid containing hydrophobic noble metal nano particles into the tracer fluid with the concentration of the modified noble metal nano particles being 0.2 mg/L-1.0 mg/L; immersing the shale sample into a tracing fluid, and cleaning the tracing fluid attached to the surface of the shale sample after spontaneous imbibition is carried out for 24-48 h;
A3) and performing electron microscope scanning imaging on the soaked shale sample by adopting a scanning electron microscope to obtain a scanning electron microscope image of the hydrophobic precious metal nanoparticles in the shale sample.
In some embodiments, the shale sample is dried at a temperature of 120 ℃ for 12h in step a 1).
The above tracers are prepared by the following specific examples.
Example 1
In a 100mL flask, 1mmol of HAuCl4·4H2O (chloroauric acid) and 5mL of oleylamine were added to 50mL of toluene, dissolved by stirring, heated to 65 ℃ under nitrogen protection, and reacted under reflux for 6h, and then the reaction solution was cooled to room temperature. Measuring 50mL of ethanol, adding the ethanol into the reaction solution for multiple times, centrifuging at the rotating speed of 6000rpm for 3min, discarding the supernatant to obtain a precipitate, and ultrasonically dispersing the precipitate in n-decane again to obtain the gold nano tracer solution.
Example 2
In a 100mL flask, 0.5mmol of AgNO was added3Adding (silver nitrate) and 2mL oleylamine into 50mL of toluene, stirring to dissolve, heating to 110 ℃ under the protection of nitrogen, reacting and refluxing for 6h, and then cooling the reaction liquid to room temperature. Weighing 50mL of ethanol, adding the ethanol into the reaction solution for multiple times, centrifuging at the rotating speed of 6000rpm for 3min, discarding the supernatant to obtain a precipitate, and ultrasonically dispersing the precipitate in n-heptane again to obtain the silver nano tracer solution.
The tracer solutions prepared in examples 1 and 2 above were morphologically characterized using a HitachiHU-11B microscope (Japan) operated at 200kV, and the characterization results are shown in FIGS. 1 and 2. As can be seen from the figure, the noble metal nanoparticles are well dispersed in the dispersion liquid and have uniform particle size, the average particle size of the gold nanoparticles is 15nm, and the average particle size of the silver nanoparticles is about 11.5 nm.
In order to verify the hydrophobic property of the nano tracer solution, the contact angles of the nano particles dispersed by the hydrophobic solvent and the noble metal nano particles prepared by the aqueous dispersion liquid and pure water are compared, and the test results are shown in fig. 3 and 4. Wetting angles theta of the water-dispersed gold nanoparticles and the n-decane-dispersed gold nanoparticles with water are 76.3 degrees and 102.6 degrees respectively; wetting angles theta of the water-dispersed silver nanoparticles and the n-decane-dispersed silver nanoparticles to water are 62.7 degrees and 106.9 degrees, respectively, so that the wettability of the hydrophobic solvent-dispersed noble metal nanoparticles to water is larger than 90 degrees, the noble metal nanoparticles are not wetted to water, and the noble metal nanoparticles have hydrophobicity.
The application also discloses a shale oil micro migration channel identification method, which comprises the steps of dispersing prepared precious metal nanoparticles in a hydrophobic solvent to obtain a nano tracing fluid, immersing a shale sample which is polished, polished and dried into the fluid, and enabling the precious metal nanoparticles to permeate into shale pores of the shale sample to realize the marking of a shale pore structure fluid channel; and identifying and imaging the noble metal nanoparticles infiltrated into the shale sample by a scanning electron microscope.
The specific implementation is as follows:
taking a stratum shale raw material to be detected, polishing the stratum shale raw material into a cube with the side length of 5mm and the thickness of 2mm, polishing the surface of the cube by using abrasive paper, and polishing the cube to obtain a shale sample with a smooth surface. And drying the polished shale sample at 120 ℃ for 12h to obtain the pretreated shale sample. Adding the tracer liquid into the fluid to prepare the fluid with the concentration of the noble metal nanoparticles of 0.4 mg/mL-1.0 mg/mL, immersing the shale sample into the prepared fluid, taking out the fluid after the fluid is infiltrated into the shale sample, cleaning the fluid on the surface of the shale sample, and then scanning the shale sample by using a scanning electron microscope to obtain an SEM image of the shale sample.
Shale samples with different shale pore structures respectively containing intraparticle pores, interparticle pores, cracks and organic matter pores are subjected to scanning electron microscope imaging after absorbing fluid containing tracer liquid, and the obtained scanning electron microscope images are shown in fig. 5 and 6. Fig. 5(a) is an SEM image of the tracer after the tracer has migrated through the shale pores of the type of intraparticle pores, fig. 5(B) is an SEM image of the tracer after the tracer has migrated through the shale pores of the type of interparticle pores, fig. 5(C) is an SEM image of the tracer after the tracer has migrated through the shale pores of the type of fractures, and fig. 5(D) is an SEM image of the tracer after the tracer has migrated through the shale pores of the type of organic pores. As can be seen, a number of bright spots appear in the various types of pore structures, demonstrating the flow of fluid through these locations, identifying the migration paths of the fluid within these pore structures.
Wherein, fig. 6 is an SEM image of the fluid after flowing through clay mineral in the shale sample, and it can be clearly seen from the image that a large number of distinct bright spots appear, which proves that the fluid added with tracer flows through these positions, and identifies the migration channel of the fluid. Because the injected nano tracer liquid contains gold element, the nano tracer liquid is high-brightness under the scanning electron microscope, and can be directly observed under the scanning electron microscope, as shown in fig. 7, because the content of the gold element in the rock is extremely small, if the enrichment of the gold element is found in a certain area, the area is determined as a pore channel area through which the nano tracer liquid flows, and thus, the gold element distribution in the area is analyzed, and the characteristics of the shale hydrocarbon wet pore channel can be obtained.
The present document also analyzes the elemental composition of the flow channel using X-ray energy spectroscopy (EDS) analysis, which yields an EDS map as shown in fig. 8. By analyzing the element distribution of different positions of the fluid channel through an EDS diagram, the matrix composition and the type of the hydrocarbon wet pores can be identified according to different element compositions of different matrixes.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A hydrophobic noble metal nano tracer liquid, which is characterized by comprising a hydrophobic dispersion liquid and noble metal nano particles dispersed in the hydrophobic dispersion liquid; the noble metal nanoparticles are modified with a hydrophobic dispersion.
2. The hydrophobic noble metal nanotrap fluid according to claim 1, wherein said noble metal nanoparticles are any one of gold nanoparticles, silver nanoparticles, palladium nanoparticles, platinum nanoparticles.
3. The hydrophobic noble metal nanotranstracer fluid of claim 1, wherein the hydrophobic dispersion is one or more of n-heptane, n-octane, n-nonane, and n-decane.
4. A preparation method of the tracer liquid as described in claims 1-3, characterized by comprising the following steps:
s1) adding noble metal salt and oleylamine into toluene for dissolving, heating and refluxing for 5-8 h under the protection of nitrogen, and cooling to room temperature to obtain a reaction solution;
s2) adding ethanol into the reaction solution, and obtaining noble metal nano particles after centrifugal separation;
s3) adding the precious metal nanoparticles prepared in the step S2) into the dispersion liquid, and performing ultrasonic dispersion for 30-60 min to obtain 5mg/mL of nano tracer liquid.
5. The method according to claim 4, wherein in step S1), the molar concentration of the noble metal salt added to the toluene is 0.005 to 0.1 mol/L; the volume ratio of the toluene to the oleylamine is 20-50: 1.
6. The method according to claim 5, wherein the heating reflux temperature in step S1) is 75-110 ℃.
7. A shale oil micro migration channel identification method based on a nano tracer liquid is characterized by comprising the following steps:
A1) preparing a shale sample, and drying the prepared shale sample for later use;
A2) preparing the tracer fluid of any one of claims 1-3 or the tracer fluid prepared according to any one of claims 4-6 into a tracer fluid with a concentration of noble metal nanoparticles of 0.2mg/mL to 1.0 mg/mL; immersing the shale sample into a tracing fluid, and cleaning the tracing fluid attached to the surface of the shale sample after spontaneous imbibition is carried out for 24-48 h;
A3) and carrying out electron microscope scanning imaging on the shale sample by adopting a scanning electron microscope.
8. The tracing method of claim 7, wherein the shale sample is a cubic structure with a polished surface.
9. The tracing method of claim 7, wherein the shale sample is dried at a temperature of 60-120 ℃ for 12-24 h.
10. The method of claim 7, wherein the matrix composition and type of hydrocarbon wet porosity of the shale sample is determined by analyzing the elemental composition of the tracer fluid flow channel using X-ray spectroscopy.
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| CN115993666A (en) * | 2023-03-23 | 2023-04-21 | 成都理工大学 | Preparation method and application of oil-based silicon-coated DNA tracer |
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