CN113530510B - Nano-micron support particle composition, nano-micron support particle and hydraulic fracturing method - Google Patents
Nano-micron support particle composition, nano-micron support particle and hydraulic fracturing method Download PDFInfo
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- E—FIXED CONSTRUCTIONS
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- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
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Abstract
The invention provides a nano-micron support particle composition, nano-micron support particles and a hydraulic fracturing method. The nano-micron supported particle composition comprises a liquid solvent, at least one surfactant, a particle forming compound, at least one curing agent and a pH control agent, wherein the pH value of the nano-micron supported particle composition is more than 11.5. The pH value of the nano-micron support particle composition is over 11.5 by controlling the addition amount of the pH control agent, so that nano-micron support particles from a nano level to a micron level can be obtained, the D50 of the nano-micron support particles is 50 nm-100 mu m, and the nano-particles in the nano-micron support particles can play a role in reducing the fluid loss of the fracturing fluid; the micron particles can enter or form cracks with various sizes including micro cracks, so that the micro cracks and other cracks are fully supported, and the micro crack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
Description
Technical Field
The invention relates to the technical field of hydraulic fracturing, in particular to a nano-micron support particle composition, a nano-micron support particle and a hydraulic fracturing method.
Background
Hydraulic fracturing has been an important technique for increasing the production of hydrocarbons in hydrocarbon-bearing formations. In a typical hydraulic fracturing treatment, a hydraulic fracturing fluid containing a solid proppant (such as a linear gel and slick water) is injected into a formation at a sufficiently high pressure to initiate or enlarge a fracture in the reservoir. When the hydraulic fracturing fluid is removed, the packed proppant may hold the fracture open, allowing fluid to flow from the formation through the proppant to the production wellbore. It follows that the proppant is very important because it provides long-term conductivity of the fracture.
Chinese patent application publication No. CN 107109203A discloses a hydraulic fracturing fluid for oilfield applications, the hydraulic fracturing fluid comprising a spherical bead-forming liquid composition characterized by a primary liquid precursor and a secondary liquid precursor, the primary liquid precursor characterized by a micelle-forming surfactant, a bead-forming compound, and a solid-free liquid solvent; and the secondary liquid precursor is characterized by one or more curing agents and one or more co-curing agents. The obtained spherical beads have a particle diameter of 0.1mm to 30mm, and thus cannot support microcracks.
Disclosure of Invention
The invention mainly aims to provide a nano-micron support particle composition, nano-micron support particles and a hydraulic fracturing method, so as to solve the problem that a liquid composition for forming spherical beads in the prior art cannot support microcracks.
To achieve the above object, according to one aspect of the present invention, there is provided a nano-micro supported particle composition comprising a liquid solvent, at least one surfactant, a particle forming compound, at least one curing agent, and a pH controlling agent, the pH of the nano-micro supported particle composition being above 11.5.
Further, the pH controller is sodium hydroxide and/or potassium hydroxide.
Further, the particle forming compound is selected from the group consisting of a resin entity selected from any one of the group consisting of aliphatic epoxides, epoxy functional resins, polyurethane resins, acrylic resins, phenolic resins and ether-aldehyde resins and a diluent selected from any one or more of the group consisting of glycidyl amine epoxides, cycloaliphatic epoxides, acid anhydrides, bisphenol a diglycidyl ether, polyglycidyl ethers, glycidyl ethers, bisphenol F diglycidyl ether.
Further, the surfactant is any one or combination of more of an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant.
Further, the liquid solvent is selected from water, seawater, saline solution and alcohol solvent, and the alcohol solvent is selected from any one or more of ethanol, propanol and butanol.
Further, the curing agent is selected from any one of isophorone diamine, boron trifluoride derivatives, imidazoline, thiol, hydrazide, polyamide, monoethanolamine, benzyldimethylamine, lewis acid, tertiary amine, isophorone, imidazole, sulfide, amide, or derivatives thereof.
Further, in the above-mentioned nano-micro support particle composition, the mass content of the particle forming compound and the curing agent is 10 to 75%, and the mass content of the surfactant is 0.5 to 20%, preferably, the mass content of the particle forming compound and the curing agent is 45 to 65%, and the mass content of the surfactant is 2 to 10%.
Further, the nano-micron supported particle composition also comprises a tackifier, preferably the tackifier is selected from calcium carbonate nanoparticles, silicate nanoparticles or a water-soluble polymer containing polyacrylamide or polyvinyl alcohol, and the viscosity of the nano-micron supported particle composition is preferably 10 to 60cPs.
According to another aspect of the present invention, there is provided a nano-micro supported particle formed by curing a nano-micro supported particle composition, the nano-micro supported particle composition being any one of the nano-micro supported particle compositions described above, the nano-micro supported particle having a D50 of 50nm to 100 μm.
Furthermore, the D50 of the nano-micron support particles is 10-95 μm.
Further, the density of the nano-micron support particles is less than or equal to 1.50g/ml.
According to a further aspect of the present invention, there is provided a hydraulic fracturing method comprising injecting a hydraulic fracturing fluid into a subterranean formation for fracturing, the hydraulic fracturing fluid comprising an emulsion formed from any one of the compositions of nano-micron support particles or any one of the nano-micron support particles described above.
By applying the solution of the present invention, the particle-forming compound and the curing agent in the above composition are mixed together to form the oil phase in an oil/water emulsion, and the "oil" droplets become nano-micro particles with deformability that effectively prevents the nano-micro particles from being crushed when the cracks try to close after the injection is stopped. Because the nano-micron particle supporting composition contains the pH control agent, the pH value of the nano-micron particle supporting composition is over 11.5 by controlling the addition amount of the pH control agent, nano-micron supporting particles from nano level to micron level can be obtained, the D50 of the nano-micron particle supporting composition is 50 nm-100 microns, and the nano-particles in the obtained nano-micron supporting particles can play a role in reducing the fluid loss of fracturing fluid; the micron particles can enter cracks with various sizes including micro cracks or be formed in the cracks with various sizes including the micro cracks, so that the micro cracks and other cracks are fully supported, and the micro crack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram showing a mixed primary proppant of nano-micron proppant particles;
FIG. 2 shows an image of the nano-micron support particles obtained in example 1;
FIG. 3 shows a graph of the size distribution of the nano-micron support particles obtained in example 1;
FIG. 4 shows an image of the nano-micron support particles obtained in example 2;
fig. 5 shows the size distribution diagrams of the spherical particles obtained in comparative examples 1 to 4.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
As analyzed in the background of the present application, the present application provides a nano-micro proppant particle composition, a nano-micro proppant particle, and a hydraulic fracturing method, in order to solve the problem that a liquid composition for forming spherical beads in the prior art is difficult to form spherical beads in situ in a fracture or that previously formed spherical beads are difficult to reach a micro fracture, and thus the liquid composition is difficult to exert a sufficient propping effect on the fracture.
In an exemplary embodiment of the present application, a nano-micro supported particle composition is provided, the nano-micro supported particle composition comprising a liquid solvent, at least one surfactant, a particle forming compound, at least one curing agent, and a pH control agent, the pH of the nano-micro supported particle composition being above 11.5.
The particle-forming compound and the curing agent in the above composition are mixed together to form an oil phase in an oil/water emulsion, and the "oil" droplets become nano-micro particles with deformability that is effective to prevent the nano-micro particles from being crushed when the cracks attempt to close after the injection has ceased. Because the nano-micron particle supporting composition contains the pH control agent, the pH value of the nano-micron particle supporting composition is enabled to be more than 11.5 by controlling the adding amount of the pH control agent, nano-micron supporting particles from a nano level to a micron level can be obtained, the D50 of the nano-micron particle supporting composition is 50 nm-100 microns, and the nano-particles in the obtained nano-micron supporting particles can play a role in reducing the fluid loss of fracturing fluid; the micron particles can enter cracks with various sizes including micro cracks or be formed in the cracks with various sizes including the micro cracks, so that the micro cracks and other cracks are fully supported, and the micro crack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
The pH controlling agent used in the present application is mainly for adjusting the pH of the nano-micro support particle composition, and any base capable of adjusting the pH may be considered as being used in the present application as long as it does not affect the particle formation, and in order to simplify the composition system of the nano-micro support particle composition in the present application to make the composition more stable and save the cost, it is preferable that the pH controlling agent is sodium hydroxide and/or potassium hydroxide.
The components of the particle-forming compounds of the present application may be cured under conditions to form deformable particles, and therefore prior art components such as resins, diluents, etc. capable of curing at the pH values described above are contemplated for use herein, preferably the particle-forming compounds are selected from the group consisting of resin entities selected from any one of the group consisting of aliphatic epoxies, epoxy functional resins, polyurethane resins, acrylic resins, phenolic resins, and etheraldehyde resins, and diluents selected from any one or more of the group consisting of glycidylamine epoxies, cycloaliphatic epoxies, anhydrides, bisphenol a diglycidyl ether, polyglycidyl ether, glycidyl ether, bisphenol F diglycidyl ether.
The surfactant of the present application will distribute at the oil-water interface to stabilize the oil-water emulsion, and the preferred surfactant or combination of surfactants will have chemical properties and HLB values matched to the oil-water system to stabilize the emulsion to form nano-micro particles, and the preferred surfactant may be any one or combination of anionic, cationic, nonionic and amphoteric surfactants.
The liquid solvent used in the present application is mainly for dispersing the particle-forming compound and the curing agent mixture (oil phase) and performing a curing reaction to form particles, and therefore any liquid solvent capable of performing the above-mentioned functions may be considered to be applied to the present application, and preferably, the above-mentioned liquid solvent is selected from water, seawater, a brine solution, an alcohol solvent selected from any one or more of ethanol, propanol and butanol, in order to reduce the cost and improve the compatibility of the system with the fracturing fluid after the composition is cured.
The curing agent functions to accelerate the curing reaction of the particle-forming compound, and therefore, one skilled in the art can select an appropriate curing agent selected from any one of isophorone diamine, boron trifluoride derivatives, imidazoline, thiol, hydrazide, polyamide, monoethanolamine, benzyl dimethylamine, lewis acid, tertiary amine, isophorone, imidazole, sulfide, amide, or derivatives thereof, depending on the composition of the particle-forming compound.
In order to further improve the mechanical strength of the particles formed from the nano-micro supported particle composition of the present application, it is preferable that the nano-micro supported particle composition has a particle forming compound and a curing agent in an amount of 10 to 75% by mass and a surfactant in an amount of 0.5 to 20% by mass, and preferably has a particle forming compound and a curing agent in an amount of 45 to 65% by mass and a surfactant in an amount of 2 to 10% by mass.
In order to further control the particle size formed, it is preferred that the aforementioned nano-micron supported particle composition further comprises an adhesion promoter, preferably the adhesion promoter is selected from calcium carbonate nanoparticles, silicate nanoparticles or a water soluble polymer comprising polyacrylamide or polyvinyl alcohol, preferably the nano-micron supported particle composition has a viscosity of 10 to 60cPs. The viscosity of the composition is adjusted by the tackifier to reduce the collision probability of oil droplet particles, thereby reducing the size of generated particles.
In another exemplary embodiment of the present application, there is provided a nano-micro supported particle formed by curing a nano-micro supported particle composition, the nano-micro supported particle composition being any one of the nano-micro supported particle compositions described above, the nano-micro supported particle having a D50 of 50nm to 100 μm.
The particle-forming compound and the curing agent in the above composition are mixed together to form an oil phase in an oil/water emulsion, and the "oil" droplets become nano-micro particles after curing. Because the nano-micron particle supporting composition contains the pH control agent, the pH value of the nano-micron particle supporting composition is over 11.5 by controlling the addition amount of the pH control agent, nano-micron supporting particles from nano level to micron level can be obtained, and the D50 is 50 nm-100 mu m, and the nano-particles in the obtained nano-micron supporting particles can play a role in reducing the fluid loss of fracturing fluid; the micron particles can enter cracks with various sizes including micro cracks or be formed in the cracks with various sizes including the micro cracks, so that the micro cracks and other cracks are fully supported, and the micro crack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
The nano-micron particle composition can be used as a fracturing fluid component to form nano-micron support particles in situ in a fracture, and the prepared nano-micron support particles can be added into the fracturing fluid to increase the conductivity of nano-sized and micro-sized fractures, be used for keeping the micro-fractures open to supplement the function of a main proppant (shown in figure 1) and be used as a fluid loss additive.
Curing as described above as understood in the art, the components of the composition are mixed, for example, for 3 to 15 minutes, to form an oil/water emulsion which is then left undisturbed in a water bath at 30 to 150 ℃ for 5 to 200 minutes to form the nano-micron support particles.
In one embodiment, they are mixed together for about 10 minutes. In one embodiment, the temperature is 60 ℃. In one embodiment, the emulsion is allowed to stand in the water bath for 60 minutes.
In order to improve the transportability of the nano-micron support particles in hydraulic fracturing application so as to reach a predetermined position and have high supporting force, the D50 of the nano-micron support particles is preferably 10 to 95 μm, and the density of the nano-micron support particles is preferably not more than 1.50g/ml. Optimization of the diameter of the nano-micron support particles reduces the resistance that may be encountered in their transport, while the low density allows the nano-micron support particles to be transported far in hydraulic fracturing at low settling rates.
In another exemplary embodiment of the present application, a hydraulic fracturing method is provided, the hydraulic fracturing method comprising injecting a hydraulic fracturing fluid into a subterranean formation for fracturing, the hydraulic fracturing fluid comprising an emulsion formed from a nano-micron support particle composition of any of the above or nano-micron support particles of any of the above.
The particle-forming compound and the curing agent in the above composition are mixed together to form an oil phase in an oil/water emulsion, and the "oil" droplets become nano-micro particles with deformability that effectively prevents the nano-micro particles from being crushed when the cracks attempt to close after the injection is stopped. Because the nano-micron particle supporting composition contains the pH control agent, the pH value of the nano-micron particle supporting composition is enabled to be more than 11.5 by controlling the adding amount of the pH control agent, nano-micron supporting particles from a nano level to a micron level can be obtained, the D50 of the nano-micron particle supporting composition is 50 nm-100 microns, and the nano-particles in the obtained nano-micron supporting particles can play a role in reducing the fluid loss of fracturing fluid; the micron particles can enter cracks with various sizes including micro cracks or be formed in the cracks with various sizes including the micro cracks, so that the micro cracks and other cracks are fully supported, and the micro crack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
The nano-micron particle composition forms emulsion which is added into fracturing fluid and/or filler, so that nano-micron support particles are formed in situ in the fracture, or the nano-micron support particles are added into the filler and/or the fracturing fluid, so that the conductivity of nano and micron fractures is increased, the micro fractures are kept open to supplement the function of a main proppant, and the nano support particles can also play the role of a fluid loss reducer. Thus, the above-described nanoparticle composition or nanoparticle may be used as at least part of a fluid loss additive and at least part of a proppant.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The composition of the composition used to prepare the oil/water emulsion to form the particles is shown in table 1. The components were mixed for 10 minutes to form an emulsion, the pH thereof was measured, and then allowed to stand in a water bath at 60 ℃ for 1 hour to react to form spherical particles (i.e., nano-micron support particles), the density (absolute density) of which was 1.09g/ml.
TABLE 1
Wherein the Tween is TM Is a registered trademark of Croda International plc, tween TM 20 contains an alkoxy ester and is used as a surfactant.
Hostafrac SF14413 is a product of Clariant Corporation, and includes proprietary composition 6615 in an amount of 10 to 20% by weight, ethoxylated isotridecanol in an amount of 10 to 20% by weight, proprietary composition 6715 in an amount of 1 to 10% by weight, solvent naphtha in an amount of 1 to 5% by weight, and naphthalene in an amount of 0.1 to 1% by weight, and is used as a surfactant.
Max CLR TM Is a trademark of Polymer Composites Corporation. Max CLR TM A is a modified bisphenol A epoxy resin formulation comprising 90 to 100 weight percent phenol, 4- (1-methylethylidene) bis, a polymer and (chloromethane) ethylene oxide, 1 to 5 weight percent epoxidized diluent, 0 to 10 weight percent epoxidized modified methyl glycerol ether, and 0.1 to 0.5 weight percent non-silicone additive.
Max CLR TM B is an amine modified curing agent comprising about 5 to 15 weight percent benzyl alcohol, 15 to 35 weight percent isophorone associative adduct and 50 to 60 weight percent aliphatic amine adduct.
The nano-micron support particles formed in example 1 are shown in fig. 2, and the nano-micron support particles formed in example 2 are shown in fig. 4. The particle size distribution was measured by a Mastersizer 3000 laser particle size analyzer and the results are shown in figure 3. The diameter of the nano-micron support particles formed in example 1 is mainly distributed between 0.5 μm and 250 μm, and the D50 is 80 μm, as shown in Table 2.
Comparative example 1 resulted in a particle size distribution as shown in fig. 5 (pH = 9.78), with a particle diameter distribution of predominantly between 40 mesh and 7 mesh (particle size of 0.400mm to 2.83 mm) and a D50 of about 1.7mm.
The particle size distribution obtained in comparative example 2 is shown in fig. 5 (pH = 7.84), the particle diameter distribution is between 40 mesh and 8 mesh (particle size is 0.400mm to 2.38 mm), and the D50 is about 1.2mm.
The resulting particle size distributions of comparative examples 3 and 4 are also recorded in fig. 5.
The diameter distributions, D50 and density data are shown in table 2.
TABLE 2
From the comparison of the above data, it can be found that the emulsion of the composition forms particles having a larger particle size under acidic conditions, and the particle size decreases as the pH increases, but the particle size increases again after entering the alkaline range; and the D50 increases with the increase of pH at pH values less than 11.5, but the D50 does not increase but decreases to 1mm or less and less than 0.1mm at pH values exceeding 11.5.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the particle-forming compound and the curing agent in the above composition are mixed together to form an oil phase in an oil/water emulsion, and the "oil" droplets become nano-micro particles with deformability that is effective to prevent the nano-micro particles from being crushed when the cracks attempt to close after the injection has ceased. Because the nano-micron particle supporting composition contains the pH control agent, the pH value of the nano-micron particle supporting composition is enabled to be more than 11.5 by controlling the adding amount of the pH control agent, nano-micron supporting particles from a nano level to a micron level can be obtained, the D50 of the nano-micron particle supporting composition is 50 nm-100 microns, and the nano-particles in the obtained nano-micron supporting particles can play a role in reducing the fluid loss of fracturing fluid; the micron particles can enter or form fractures with various sizes including microcracks, so that the microcracks such as microcracks are fully supported, and the microcrack flow conductivity is remarkably improved under the combined action of the two particles, so that the crude oil yield is improved.
All of the compositions and methods claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this disclosure have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps without departing from the concept, spirit and scope of the disclosure. More specifically, it will be apparent that certain agents which are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and spirit of the invention as defined by the appended claims.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nano-micron support particle formed by curing a nano-micron support particle composition, wherein the nano-micron support particle composition comprises a liquid solvent, at least one surfactant, a particle forming compound, at least one curing agent, and a pH control agent;
in the nano-micron supporting particle composition, the mass content of the particle forming compound and the curing agent is 10-75%, and the mass content of the surfactant is 0.5-20%;
the nano-micron supported particle composition also comprises a tackifier, wherein the tackifier is selected from calcium carbonate nanoparticles, silicate nanoparticles or a water-soluble polymer containing polyacrylamide or polyvinyl alcohol, and the viscosity of the nano-micron supported particle composition is 10 to 60 cPs;
the pH value of the nano-micron support particle composition is controlled to be more than 11.5 by controlling the addition amount of the pH control agent, so that nano-micron support particles from a nano level to a micron level can be obtained, and the D50 of the nano-micron support particles is 50nm to 100 mu m; the nano-particles in the nano-micro support particles can play a role in reducing the fluid loss of the fracturing fluid, the micro-particles can enter the fracture and further play a role in fully supporting the fracture, and the fracture flow conductivity is remarkably improved under the combined action of the nano-particles and the micro-particles.
2. The nano-micron supported particle of claim 1, wherein the pH control agent is sodium hydroxide and/or potassium hydroxide.
3. The nano-micron supported particle of claim 1, wherein the particle forming compound is selected from the group consisting of a resin entity selected from any one of the group consisting of aliphatic epoxies, epoxy functional resins, polyurethane resins, acrylic resins, phenolic resins, and ether-aldehyde resins, and a diluent selected from any one or more of the group consisting of glycidyl amine epoxies, cycloaliphatic epoxies, anhydrides, bisphenol a diglycidyl ethers, polyglycidyl ethers, glycidyl ethers, bisphenol F diglycidyl ethers.
4. The nano-micron supported particle of claim 1, wherein the surfactant is any one or combination of anionic, cationic, nonionic and amphoteric surfactants.
5. The nano-micron support particle of claim 1, wherein the liquid solvent is selected from the group consisting of water, seawater, brine solutions, alcohol solvents selected from any one or more of ethanol, propanol, and butanol.
6. The nano-micron supported particle of claim 1, wherein the curing agent is selected from any one of isophorone diamine, boron trifluoride derivatives, imidazolines, thiols, hydrazides, polyamides, monoethanolamine, benzyldimethylamine, lewis acids, tertiary amines, isophorone, imidazole, sulfides, amides, or derivatives thereof.
7. The nano-micron supporting particle as claimed in claim 1, wherein the mass content of the particle forming compound and the curing agent is 45 to 65%, and the mass content of the surfactant is 2 to 10%.
8. The nano-micron support particle of claim 1, wherein the nano-micron support particle has a D50 of 10 to 95 μ ι η.
9. The nano-micron supported particle of claim 1, having a density of 1.50g/ml or less.
10. A hydraulic fracturing method comprising injecting a hydraulic fracturing fluid into a subterranean formation for fracturing, wherein the hydraulic fracturing fluid comprises the nano-micron support particle of any one of claims 1 to 9.
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