# Patent

## Title
Electroconductive proppant compositions and related methods

## Abstract

Some embodiments provide methods of obtaining data from a portion of a subterranean formation comprising providing proppant particulates wherein at least a portion of the proppant particulates are coated with an electroconductive resin that comprises a resin and a conductive material; placing the proppant particulates into a portion of a fracture so as to form an electroconductive proppant pack; providing a transmitter capable of sending an electric current into the electroconductive proppant pack; sending an electric current into the electroconductive proppant pack with the transmitter; providing a receiver capable of deflecting a reflected or conducted electric signal from the electroconductive proppant pack; and, receiving a reflected electric signal with the receiver. Other embodiments provide electroconductive proppant packs comprising proppant particulates wherein a portion of the proppant particulates are coated with an electroconductive resin and wherein the electroconductive resin comprises a resin and a conductive material.

## Background
BACKGROUND
The present invention relates to electroconductive proppant compositions and methods of using electroconductive proppant compositions in subterranean formations to determine, among other things, proppant pack characteristics such as dimensions, orientation, and conductivity.
Hydraulic fracturing is a widely-used process for improving well productivity by placing or enhancing cracks or channels from a well bore a surrounding reservoir. This operation essentially is performed by injecting a fracturing fluid into a well bore penetrating a subterranean formation at a pressure sufficient to create a fracture in the formation or to enhance a natural fracture in the formation. Proppant particulates may be placed in the fracture to prevent the fracture from closing once the pressure is released. Upon placement, the proppant particulates usually form proppant packs in or near desired fractures. These proppant packs, thus, may maintain the integrity of those fractures to create conductive paths to the well bore for desirable fluids to flow. Placing an appropriate amount of proppant particulates to form a suitable proppant pack is thus important to the success of a hydraulic fracture treatment.
The geometry of a hydraulic fracture affects the efficiency of the process and the success of a fracturing operation. FIG. 1 illustrates basic fracture geometry. A fracture's geometry may be mapped from direct measurement of the fracture growth. This has been done, for instance, by placing tiltmeters in either the active well or in an observation well and monitoring rock deformation caused by the growing fracture. However, although tiltmeters and other direct methods (e.g., microseismic measurements) have been used to determine fracture geometry, historically, fracture geometry is more commonly estimated by interpreting measured data and applying mathematical models of fracture growth. This analysis has been generally limited to data from indirect measurements (e.g., flow rate, pressure, temperature, etc.) taken from the well bores during the fracture treatments. These measurements, however, are heavily influenced by well bore effects, such as fluid rheology, fluid density, and fluid friction in the well bore, and generally are not a reliable means of determining some fracture parameters. Fracture conditions, such as the integrity of the proppant pack over time and flow rates through various portions of the fracture pack, cannot be effectively monitored using these well bore measurements
SUMMARY OF THE INVENTION
The present invention relates to electroconductive proppant compositions and methods of using electroconductive proppant compositions in subterranean formations to determine, among other things, proppant pack characteristics such as dimensions, orientation, and conductivity.
Some embodiments of the present invention provide methods of obtaining data from a portion of a subterranean formation comprising providing proppant particulates wherein at least a portion of the proppant particulates are coated with an electroconductive resin that comprises a resin and a conductive material; placing the proppant particulates into a portion of a fracture so as to form an electroconductive proppant pack; providing a transmitter capable of sending an electric current into the electroconductive proppant pack; sending an electric current into the electroconductive proppant pack with the transmitter; providing a receiver capable of deflecting a reflected or conducted electric signal from the electroconductive proppant pack; and, receiving a reflected electric signal with the receiver.
Other embodiments of the present invention provide electroconductive proppant packs comprising proppant particulates wherein a portion of the proppant particulates are coated with an electroconductive resin and wherein the electroconductive resin comprises a resin and a conductive material.
Other and further features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an example of a basic fracture geometry.
FIG. 2 illustrates an exemplary stylized fracture wherein multiple regions of proppant particulates with distinct conductivity have been placed.
FIG. 3 illustrates two possible example configurations of embodiments wherein multiple receivers are placed in the well bore in the region of the subterranean fracture to determine the spatial distribution of electroconductive proppant particulates.
FIG. 4 illustrates four possible example configurations of a transmitter and an array of receivers in an active well and in an offset observation well.



DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to electroconductive proppant compositions and methods of using electroconductive proppant compositions in subterranean formations to determine, among other things, proppant pack characteristics such as dimensions, orientation, and conductivity. The present invention provides novel methods relating to obtaining information on the characteristics of a fracture and proppant pack using both direct and indirect measurements of the fracture growth, final fracture or proppant pack placement, proppant conductivity, and the level of clean up of the fracturing fluid. The methods of the present invention generally related to the use of proppant particulates coated with an electroconductive resin.
In certain embodiments, the improved methods and compositions of the present invention comprise using electroconductive proppant compositions to obtain data from a fracture within a subterranean formation penetrated by a well bore comprising the steps of: forming an electroconductive proppant pack in a subterranean fracture; placing one or more receivers capable of receiving an electric signal into the well bore proximate to the electroconductive proppant pack; contacting the electroconductive proppant pack with an electric charge; and, measuring the resistance of the conductive proppant pack via a receiver. The resistance measurements may be interpreted to provide information regarding, among other things, the proppant pack conductivity and the dimensions and geometry of the subterranean fracture and/or the proppant pack. The receiver also may be designed to sense one or more formation parameters, including, but not limited to, pressure, temperature, dielectric constant, rock strain, porosity, and flow rate. In certain preferred embodiments, data corresponding to the subterranean formation may be obtained during fracture treatment to monitor fracture growth during a treatment operation (e.g., data monitored in “real time”).
The electroconductive proppant compositions of the present invention comprise proppant particulates coated with a curable electroconductive resin. In some embodiments of the present invention, only chosen portions of the proppant particulates making up the proppant pack are coated with electroconductive resins. In other embodiments, substantially all of the proppant particulates making up the proppant pack are coated with electroconductive resin. In some embodiments from about 20% to about 100% of the proppant particulates are coated with a curable electroconductive resin. In other embodiments from about 30% to about 90% of the proppant particulates are coated with a curable electroconductive resin. In other embodiments from about 50% to about 850% of the proppant particulates are coated with a curable electroconductive resin.
In certain preferred embodiments, the electroconductive proppant particulates may be placed in specific desired regions of the subterranean fracture. For example, electroconductive proppant particulates may be used during fracture treatment as only the first portion of proppant placed. Non-conductive proppant particulates or proppant particulates with a distinct conductivity as compared with the earlier placed proppant particulates may then be used during fracture treatment of a second or further portion of the subterranean formation. This method may be repeated to obtain multiple regions of distinctly conductive and/or non-conductive proppant particulates within the subterranean fracture. FIG. 2 illustrates a stylized fracture wherein multiple regions of proppant with distinct conductivity have been placed. By so placing the electroconductive proppant in specific regions of the subterranean fracture and using the methods and compositions according to the present invention detailed information about, inter alia, the proppant conductivity and the dimensions and geometry of the subterranean fracture and proppant pack may be obtained.
Suitable proppant particulates for use in the present invention include those materials often used as proppant particulates, such as nut shells, sand, ceramics, natural sand, quartz sand, particulate garnet, metal particulates, glass, nylon pellets, bauxite and other ores, polymeric materials, combinations, and the like. Suitable sizes range from 4 to 100 U.S. mesh; in certain preferred embodiments the sizes range from 10 to 70 U.S. mesh. In preferred embodiments, the particles themselves may be at least somewhat conductive (as in the case of bauxite-based particles) or very conductive (as in the case of copper-based particles).
In order, among other things, to encourage consolidation of the proppant pack and to tailor the electroconductivity of the proppant, the selected proppant particulates should be at least partially coated with a curable, electroconductive resin. Curable resins that are suitable for use in the present invention include, but are not limited to, two component epoxy-based resins, novolak resins, polyepoxide resins, phenol-aldehyde resins, urea-aldehyde resins, urethane resins, phenolic resins, furan resins, furan/furfuryl alcohol resins, phenolic/latex resins, phenol formaldehyde resins, polyester resins and hybrids and copolymers thereof, polyurethane resins and hybrids and copolymers thereof, acrylate resins, and mixtures thereof. Some suitable resins, such as epoxy resins, may be cured with an internal catalyst or activator so that when pumped down hole, they may be cured using only time and temperature. Other suitable resins, such as furan resins generally require a time-delayed catalyst or an external catalyst to help activate the polymerization of the resins if the cure temperature is low (i.e., less than 250° F.), but will cure under the effect of time and temperature if the formation temperature is above about 250° F., preferably above about 300° F. It is within the ability of one skilled in the art, with the benefit of this disclosure, to select a suitable resin for use in embodiments of the present invention and to determine whether a catalyst is required for the desired curing characteristics.
While the chosen resin may itself be somewhat conductive, in certain embodiments, the resin may be mixed with a conductive material in an amount sufficient to obtain a desired degree of conductivity. Suitable conductive materials include, but are not limited to, powders that comprise conductive particulates, e.g., graphite, copper, iron, zinc, brass, tin, conductive plastics, conductive graphite materials, or combinations thereof. In one exemplary embodiment, the conductive resin may comprise an epoxy resin containing fine graphite powder. In another exemplary embodiment, the conductive resin may comprise a furan resin containing fine particulate copper. In certain exemplary embodiments, the conductive material has a particle distribution size of from about 0.1 μm to about 100 μm. In other exemplary embodiments, the conductive material has a particle distribution size of from about 15 μm to about 50 μm.
In certain preferred embodiments, the curable electroconductive resin bonds to adjoining particulates to form an aggregate of particulates that may form a proppant pack. The resin may be present in an amount sufficient to consolidate the proppant particulates but should not fill the pore spaces or openings between the particulates. The conductive resin may be coated on the proppant particulates in an amount from about 0.1% to about 6% by weight of the proppant particulates, preferably an amount from about 1% to about 3% by weight of the proppant particulates. In a preferred embodiment, the resin may bond the proppant particulates in a coarse aggregate to fix the particulates in the fracture and provide a flow path for produced fluids through the subterranean fracture.
Some methods of the present invention use transmitters to send an electrical signal into an electroconductive proppant pack and receivers to collect information from the electroconductive proppant pack. In a preferred embodiment, the signal comprises an electric current or an electromagnetic field. In certain preferred embodiments, the electric or electromagnetic signal from the transmitter is conducted along, and reflected back from the electroconductive proppant to the receiver and may be used to determine, inter alia, the dimensions and geometry of the subterranean fracture. For example, the strength, offset, and phase of the reflected signal may be used to determine, inter alia, height, width, length, and orientation of the subterranean fracture. In other preferred embodiments, an electric current can be used to determine the electric impedance within the electroconductive proppant. The measured impedance within the subterranean fracture may be used to quantitatively measure the proppant conductivity or the distribution of proppant conductivity through the subterranean fracture after placement of proppant.
In a preferred embodiment, at least one receiver is placed in the well bore of the subterranean formation. For example, a single receiver may be placed in the well bore at the fracture initiation point. In another example, multiple receivers may be placed in the well bore in the region of the subterranean fracture to determine the spatial distribution of electroconductive proppant in the subterranean fracture (e.g., to determine the fracture height and width). FIG. 3 illustrates two possible configurations. In a further example, a single receiver or multiple receivers may be placed in one or more observation wells to obtain data from a point of view outside of the active, or producing well bore. In addition, placing receivers in multiple observation wells may allow determination of the dimensions and orientation of the subterranean fracture, including but not limited to, the fracture length, height, and azimuth, by triangulation of the received data. FIG. 4 is an exemplary embodiment showing four possible configurations of a transmitter and an array of receivers in the active well and in an offset observation well, to determine, inter alia, the length, height and width of a hydraulic fracture, preferably in real-time.
Some embodiments of the present invention further include self-contained sensors placed in the proppant pack capable of collecting additional data about the proppant and providing the data to the receivers. In certain preferred embodiments, the sensors may be placed within the subterranean fracture during the fracturing treatment. Any sensors known to one skilled in the art may be used with the methods and compositions of the present invention. Examples of suitable sensors that may be used with the methods and compositions of the present invention have been described in U.S. Pat. No. 6,538,576, the relevant disclosure of which is incorporated herein by reference. The sensors may be used to obtain, inter alia, temperature, pressure, porosity, resistivity, magnetic field, and flow rate data. In certain exemplary embodiments, the electric current or electromagnetic field provided by the transmitter into the subterranean fracture may be used to provide power to one or more sensors. Various methods suitable for powering such devices are described, for example, in U.S. Pat. No. 6,408,943, the relevant disclosure of which is incorporated herein by reference.
While the invention has been depicted and described by reference to exemplary embodiments of the invention, such a reference does not imply a limitation on the invention, and no such limitation is to be inferred. The invention is capable of considerable modification, alteration, and equivalents in form and function, as will occur to those ordinarily skilled in the pertinent arts having the benefit of this disclosure. The depicted and described embodiments of the invention are exemplary only, and are not exhaustive of the scope of the invention. Consequently, the invention is intended to be limited only by the spirit and scope of the appended claims, giving full cognizance to equivalence in all respects.

## Claims

1. A method of obtaining data from a portion of a subterranean formation comprising:
providing proppant particulates wherein at least a portion of the proppant particulates are coated with an electroconductive resin that comprises a resin and a conductive material;
placing the proppant particulates into a portion of a fracture so as to form an electroconductive proppant pack;
providing a transmitter capable of sending an electric current into the electroconductive proppant pack;
sending an electric current into the electroconductive proppant pack with the transmitter;
providing a receiver capable of deflecting a reflected or conducted electric signal from the electroconductive proppant pack; and,
receiving a reflected electric signal with the receiver.

2. The method of claim 1 wherein the portion of the proppant particulates are coated with an electroconductive resin is from about 20% to about 100% of the total proppant particulates used.

3. The method of claim 1 wherein the proppant particulates are coated with an electroconductive resin comprises a first portion of particulates coated with a first electroconductive resin and a second portion of particulates coated with a second electroconductive resin and wherein the first electroconductive resin exhibits a distinct conductivity as compared to the second electroconductive resin.

4. The method of claim 1 wherein the proppant particulates comprise nut shells, sand, ceramics, natural sand, quartz sand, particulate garnet, metal particulates, glass, nylon pellets, bauxite and other ores, polymeric materials, and combinations thereof.

5. The method of claim 1 wherein the proppant particulates range in size from about 4 U.S. Mesh to about 100 U.S. Mesh.

6. The method of claim 1 wherein the proppant particulates are at least partially conductive.

7. The method of claim 1 wherein the resin in the electroconductive resin comprises an epoxy based resin, a novolak resin, a polyepoxide resin, a phenol-aldehyde resin, a urea-aldehyde resin, a urethane resin, a phenolic resin, a furan resin, a furan/furfuryl alcohol resin, a phenolic/latex resin, a phenol formaldehyde resin, a polyester resin, a hybrid polyester resin, a copolymer polyester resin, a polyurethane resin, hybrid polyurethane resin, a copolymer polyurethane resin, an acrylate resin, or a combination thereof.

8. The method of claim 1 wherein the conductive material in the electroconductive resin comprises a conductive metal material or a conductive plastic material.

9. The method of claim 8 wherein the metal powder comprises graphite powder, copper powder, iron powder, zinc powder, brass powder, tin powder, or combinations thereof.

10. The method of claim 8 wherein the conductive metal powder has a particle distribution size of from about 0.1 μm to about 100 μm.

11. The method of claim 8 wherein the conductive metal powder has a particle distribution size of from about 15 μm to about 50 μm.

12. The method of claim 1 wherein the proppant particulates coated with electroconductive resin comprise from about 0.1% to about 6% electroconductive resin by weight of the proppant particle.

13. The method of claim 1 wherein, while placing the proppant particulates into a portion of a fracture so as to form an electroconductive proppant pack, sensors are simultaneously placed so as to create an electroconductive proppant pack further comprising sensors.

14. An electroconductive proppant pack comprising proppant particulates wherein a portion of the proppant particulates are coated with an electroconductive resin and wherein the electroconductive resin comprises a resin and a conductive material.

15. The electroconductive proppant pack of claim 14 wherein the portion of the proppant particulates are coated with an electroconductive resin is from about 20% to about 100% of the total proppant particulates.

16. The electroconductive proppant pack of claim 14 wherein the proppant particulates coated with an electroconductive resin comprise a first portion of particulates coated with a first electroconductive resin and a second portion of particulates coated with a second electroconductive resin and wherein the first electroconductive resin exhibits a distinct conductivity as compared to the second electroconductive resin.

17. The electroconductive proppant pack of claim 14 wherein the proppant particulates comprise nut shells, sand, ceramics, natural sand, quartz sand, particulate garnet, metal particulates, glass, nylon pellets, bauxite and other ores, polymeric materials, and combinations thereof.

18. The electroconductive proppant pack of claim 14 wherein the proppant particulates range in size from about 4 U.S. Mesh to about 100 U.S. Mesh.

19. The electroconductive proppant pack of claim 14 wherein the proppant particulates are at least partially conductive.

20. The electroconductive proppant pack of claim 14 wherein the resin in the electroconductive resin comprises an epoxy based resin, a novolak resin, a polyepoxide resin, a phenol-aldehyde resin, a urea-aldehyde resin, a urethane resin, a phenolic resin, a furan resin, a furan/furfuryl alcohol resin, a phenolic/latex resin, a phenol formaldehyde resin, a polyester resin, a hybrid polyester resin, a copolymer polyester resin, a polyurethane resin, hybrid polyurethane resin, a copolymer polyurethane resin, an acrylate resin, or a combination thereof.

21. The electroconductive proppant pack of claim 14 wherein the conductive material in the electroconductive resin comprises a conductive metal material or a conductive plastic material.

22. The electroconductive proppant pack of claim 21 wherein the metal powder comprises graphite powder, copper powder, iron powder, zinc powder, brass powder, tin powder, or combinations thereof.

23. The electroconductive proppant pack of claim 21 wherein the conductive metal powder has a particle distribution size of from about 0.1 μm to about 100 μm.

24. The electroconductive proppant pack of claim 21 wherein the conductive metal powder has a particle distribution size of from about 15 μm to about 50 μm.

25. The electroconductive proppant pack of claim 14 wherein the proppant particulates coated with electroconductive resin comprise from about 0.1% to about 6% electroconductive resin by weight of the proppant particle.