Patent Application
20190187040
The present disclosure is directed to methods and systems for monitoring and testing underground fluid reservoirs; and more particularly to methods and systems for monitoring and testing underground wells and tanks using imageable nanowires.
An underground reservoir is an underground cavity, formation or tank that contains a fluid medium. A common example of such a reservoir is a well, which is a boring into the Earth that is designed to bring up a substance, such as water or petroleum oil hydrocarbons to the surface. In fields of such underground reservoirs, it can be important to know whether two reservoirs are fluidly interconnected and to what extent the connectivity exists. In other words, it may be important to understand the contents of each of the reservoirs and whether or not contaminants have been introduced in one or more of the reservoirs. In other circumstances it is important to know if a container is leaking into its surroundings. Such connectivity can be difficult to determine, and so a need exists to develop systems and methods that enable the determination of the connectivity between any of a plurality of wells and enable the determination of the content distribution in wells.
The present disclosure provides embodiments directed to systems and methods for detecting underground connections between or leakage from reservoirs and for detecting the content of underground reservoirs that may be interconnected via distinctly patterned functionalized nanowires or microwires that are stable under the conditions often encountered in underground reservoirs such as oil and gas wells, using imaging methods and algorithms to automate the determination of statistically significant numbers of differently encoded imaging patterns.
In some embodiments, a nanowire probe system includes at least one probe population formed of a plurality of nanowires, the population of nanowires having a distinct imageable pattern associated therewith, the distinct imageable pattern associated with the population being formed on each of the plurality of nanowires of said population; and wherein the nanowires are comprised of a plurality of segments disposed adjacent each other along the longitudinal axis of the nanowire, the plurality of segments being formed from different materials having an imageable contrast therebetween, the imageable contrast between the different segments forming the imageable pattern.
In a further embodiment, the nanowire probe system includes at least two probe populations each formed of a plurality of nanowires, each population of nanowires having a distinct imageable pattern associated therewith, the distinct imageable pattern associated with the population being formed on each of the plurality of nanowires of the population.
In another embodiment, the plurality of nanowires in each population are formed of at least two sizes.
In a still further embodiment, the outer surface of each of the nanowires is functionalized with a plurality of functional groups configured to prevent agglomeration of the nanowires.
In still another embodiment, the plurality of functional groups does not obscure the imageable pattern.
In a yet further embodiment, an encapsulation layer is disposed on the outer surface of each of the nanowires, and the encapsulation layer is functionalized with a plurality of functional groups configured to prevent agglomeration of the nanowires.
In yet another embodiment, the plurality of functional groups and the encapsulation layer do not obscure the imageable pattern.
In a further embodiment again, the outer surface of each of the nanowires is functionalized with molecular groups to collect content data of a desired chemical species.
In another embodiment again, the imageable pattern is identifiable using a video imagery technique selected from the group consisting of computer vision and wavelet-based image processing.
In a further additional embodiment, at least one of the plurality of segments comprises nanoscale structures to reflect desired color patterns.
In another additional embodiment, a method of determining reservoir content includes introducing at least one probe population formed of a plurality of nanowires into a fluid medium in at least one fluid reservoir such that a mixture of nanowires and fluid medium is formed within the at least one fluid reservoir, the probe population having a distinct imageable pattern and a functionalized molecular group associated therewith, where the distinct imageable pattern associated with the population being formed on each of the plurality of nanowires of said population, and where the functionalized molecular group associated with the population function to collect content data of a desired chemical species in the at least one fluid reservoir; obtaining a sample of the mixture from at least one of the at least one fluid reservoir; imaging the sample; processing the imaged sample using a signal processor to quantitatively determine the concentration of the at least one probe population disposed within the sample, wherein the concentration of the at least one probe population indicates a flow from the at least one fluid reservoir, and wherein the signal processor is programmed with an automated algorithm and capable of differentiating the distinct imageable patterns associated with each population of nanowires; and detecting the desired chemical species from the functionalized molecular group associated with the nanowires in the sample.
In a still yet further embodiment, the method further includes introducing at least two probe populations each formed of a plurality of nanowires into a plurality of fluid reservoirs, where each of the at least two probe populations is introduced into a separate fluid reservoir in the plurality of fluid reservoirs such that a mixture of nanowires and fluid medium is formed within each fluid reservoir in the plurality of fluid reservoirs, where each population of nanowires having a distinct imageable pattern associated therewith, the distinct imageable pattern associated with the population being formed on each of the plurality of nanowires of said population; obtaining a sample of the mixture within each of the plurality of fluid reservoirs; imaging the samples from each of the plurality of fluid reservoirs; and processing the imaged samples using a signal processor to quantitatively determine the concentration of each of the at least two probe populations disposed within the samples, wherein the concentration of each of the at least two probe populations indicates a flow from the fluid reservoir in which each of the at least two probe populations was introduced, and wherein the signal processor is programmed with an automated algorithm and capable of differentiating the distinct imageable patterns associated with each population of nanowires.
In still yet another embodiment, the plurality of nanowires in each population are formed of at least two sizes.
In a still further embodiment again, the nanowires are comprised of a plurality of segments disposed adjacent each other along the longitudinal axis of the nanowire.
In still another embodiment again, at least two of the segments are formed from different materials having an imageable contrast therebetween, the imageable contrast between the different segments forming the imageable pattern.
In a still further additional embodiment, the outer surface of each of the nanowires is functionalized with a plurality of functional groups configured to prevent agglomeration of the nanowires.
In still another additional embodiment, the plurality of functional groups do not obscure the imageable pattern.
In a yet further embodiment again, an encapsulation layer is disposed on the outer surface of each of the nanowires.
In yet another embodiment again, the encapsulation layer is functionalized with a plurality of functional groups configured to prevent agglomeration of the nanowires.
In a yet further additional embodiment, the encapsulation layer and the plurality of functional groups do not obscure the imageable pattern.
In yet another additional embodiment, the imageable pattern is optically imageable and wherein the imaging comprises a video imagery technique selected from the group consisting of computer vision and wavelet-based image processing.
In a further additional embodiment again, the processing comprises automatically sorting the images from the sample by a processing technique selected from the group consisting of wavelet Gizburg-Landau regularization, spectral analysis of large Hermitian matrices, and modularity optimization.
In another additional embodiment again, the method further includes deconstructing and or reconstructing the imaged mixture sample using an image processing technique selected from the group consisting of total variation restoration, cartoon texture decomposition, and nonlocal TV reconstruction.
In a still yet further embodiment again, the sampling and imaging occurs within the flow from the at least one fluid reservoir.
Additional embodiments and features are set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the specification or may be learned by the practice of the invention. A further understanding of the nature and advantages of the present invention may be realized by reference to the remaining portions of the specification and the drawings, which forms a part of this disclosure.
The description will be more fully understood with reference to the following figures and data graphs, which are presented as various embodiments of the disclosure and should not be construed as a complete recitation of the scope of the disclosure, wherein:
The present disclosure may be understood by reference to the following detailed description, taken in conjunction with the drawings as described below. It is noted that, for purposes of illustrative clarity, certain elements in various drawings may not be drawn to scale.
In accordance with the provided disclosure and drawings, systems and methods of fabricating and functionalizing patterned nanowires that are stable under underground reservoir conditions, having unique wavelength imageable contrast, including some embodiments having surface functionality imparted thereon so that uniform or serial functionalization can be used are provided. Along with these nanowires, optical imaging methods and systems are provided, which are capable of determining the distribution of nanowires having different patterns to determine the mixing between or leakage from fluid reservoirs.
The problem of tracing flowing reservoirs, and particularly in underground reservoirs where access is limited has long been a problem and a number of solutions have been proposed. (See, e.g., U.S. Pat. No. 4,755,469 or WO2011084656A1, the disclosures of which are incorporated herein by reference.) Most conventional systems for studying flow into and out of underground formations require the use of radioisotopes. (See, e.g., USPN 507771) While these systems can be successfully implemented, they typically require the use of very sophisticated detection schemes such as laser spectroscopy, mass spectrometry or electrochemical cells. (See, e.g., WO2007/102023 or U.S. Pat. No. 8,596,354) Many such solutions even propose systems in which samples would be sent to a laboratory for analysis. (See, e.g., Alaskar et al., GRC Transactions, vol. 34 (2010)) So far no system for reservoir flow monitoring has been proposed that would allow for the automated determination of the statistical populations of various probes in real time.
Additionally, problems exist in detecting particular content of reservoirs, especially in underground reservoirs where access is limited, detecting the content requires various types of sampling methods to determine the content and/or level of contamination within a given reservoir. Current methods involve taking full samples of the medium within the well and performing chemical analysis that is known in the art. The current problems associated with taking actual fluid samples may result in inaccurate tests or false negative tests results. It can be difficult to obtain a sample large enough to fully detect the contaminants in mediums which contain highly diluted contaminants against larger backgrounds of other chemical species. Current methods may include injecting a Fluoro luminescence dyes that would be able to react to light and potentially indicate a level of contamination. These methods however involve the introduction of dyes and other potentially harmful elements into the reservoir.
In many embodiments, methods are provided for the real-time monitoring of the flow, content and/or contamination level between two or more reservoirs that may also be interconnected. A schematic according to embodiments of such a system is provided in
Although the example schematic provided in
Exemplary embodiments of suitable fluid reservoir types include, for example, oil wells, water tables, underground or above ground storage tanks, etc. The requirements for use of the present system include a fluid medium into which the probes may be introduced (e.g., oil, water, etc.), a fluid pathway to introduce the probes into the reservoirs (e.g., a well head, pumping station, etc.), and a fluid pathway for sampling the fluid medium in the reservoirs (e.g., a pumping station, fluid sampling path, etc.). It should be understood that the same fluid pathway may be used for introducing and sampling the fluid medium. In many embodiments the sampling and/or introduction fluid path may also comprise the fluid path utilized for extraction of the fluid medium of the reservoir being monitored. In addition, although in some embodiments the probes are sampled external to the well or reservoir, in other embodiments, detectors could be permanently positioned in various locations within the reservoir or introduced within the reservoir to image the fluid medium in-situ.
The probes according to embodiments comprise nanowires or microwires, formed with imageable patterns disposed thereon. In many embodiments, as shown schematically in
The nanowires may be formed of any material suitable for use under the particular fluid reservoir conditions to be monitored. In many embodiments the materials for the nanowire probes are chosen with the following requirements in mind: 1) that the materials be relatively stable, i.e., not subject to material degradation, under the conditions found in the fluid reservoir; and 2) that the materials allow for the formation of features having an optical contrast suitable for monitoring via optical imaging sampling techniques. Exemplary materials may include two or more semiconductors, metals, oxides, ceramics, polymers, mixtures thereof, etc. In some such embodiments the probes are comprised of nanowires formed of alternating segments of two of more different metals that create an imageable contrast, such as, for example, Au, Cu, Ag, Pt, etc. The imageable contrast may be between any two imageable wavelengths, for example, between two visible wavelengths or between UV, IR or a combination of visible, IR and UV wavelengths. In many embodiments, the contrasting wavelengths of the segments are all in the visible spectrum such that optical scanning systems such as those similar to conventional barcode scanning systems may be used. In some embodiments, the nanowire probes are made of materials that do not react or interact with the environment where they are to be placed. For example, an environment exhibiting magnetic characteristics, some ferrous or other magnetizable materials may aggregate and/or be removed from the internal volume of a reservoir. As such, various embodiments will use non-ferrous materials that do not exhibit magnetic or magnetizable properties.
In addition to the imageable contrasting segments that many of the nanowires may comprise, other functional characteristics may be desired beyond chemical content and flow connectivity, such as for example, determining location and placement of a certain quantity or disbursement of the nanowire probes. In accordance with many embodiments the alternating segments of metals will comprise nanoscale structures on the order of wavelengths that may be specifically selected to reflect desired colored patterns. In some embodiments the alternating segments may comprise plasmonic materials arranged to have one or more plasmonic resonances thereof, thus resonating at a desired color wavelength. The plasmonic resonances will produce an optical response that can be modeled in accordance with present teachings of plasmonic materials.
Utilizing nanowires with such alternate detection features may allow the optical imaging device to detect the desired number of plasmonic type nanowires within any given reservoir and may also be useful in determining flow rates etc. In many embodiments the nanowires containing such color reflection methods may further incorporate functional molecular concentrator groups such that multiple sampling operations can be achieved on the same level.
Although nanowire probes having identical diameters and lengths are shown in
In order to disperse the nanowire probes within the reservoir and particularly to prevent agglomeration of the probes after production, the outer surfaces of the nanowire probes may be further functionalized. In some embodiments, as shown in
In many embodiments the functional molecular groups will function to collect content data in the form of a concentrator thereby combining small amounts of data into a measureable quantity for detection. The concentrator function allows for the ability for the nanowires to capture and subsequently be tested for at least one desired chemical species, even if the desired chemical species are highly diluted against large backgrounds of other chemical species; thus requiring smaller amounts of detection wires within the fluid reservoirs. In certain embodiments, these concentrators will be capable of longevity within the reservoir such that the collected samples may be tested in a post extraction environment. Longevity of the molecular concentrators is critical to ensure the most effective sampling once the nanowire probes have been retrieved from the reservoir. In accordance with many embodiments the detected desired chemical species on the concentrators may be tested using any variety of chemical testing methods known in the art.
In other embodiments, where more robust functionalization is desired, as shown in
Regardless of the functional groups or encapsulation layers chosen to functionalize the probe nanowires, in many embodiments the materials are selected such that they are largely transparent, i.e., such that neither the functional nor encapsulation layers will interfere with the measurements of the imageable patterns formed on the probes.
Regardless of the functional groups or encapsulation layers chosen to functionalize the probe nanowires, in many embodiments the materials are selected such that they are largely transparent, i.e., such that neither the functional nor encapsulation layers will interfere with the measurements of the imageable patterns formed on the probes. In many embodiments the functional groups or encapsulation layers can be sufficiently thin to be effectively transparent.
Embodiments are also directed to methods of forming nanowire probes. In many embodiments, as shown schematically in
During fabrication, one side of the membrane is covered with a conductive layer (36), such as, for example a metallic paint such Ag, Au or Pt. The nanowires (38) are then grown within the pores (37) by use of electrochemical deposition. In particular, the nanowire probes grown in accordance with embodiments of the methods are formed with stripes of controlled length by reductive desorption from a solution containing a salt of the material, such as a metal, to be deposited. (See, e.g., CR Martin, Science 266, 1961 (1994); D Routkevitch et al., Journal of Physical Chemistry 100, 14037 (1996); and SR Nicewarner-Pena et al., Science 294, 5540 (2001).) In embodiments, the solutions and thus metals may be changed in order to grow segments (39 to 39′″ of
In many embodiments, these systems and methods may be used to fabricate large numbers of nanowires. In particular, in some embodiments techniques for making membranes from large-area aluminum foil may be used to scale up production of the metal nanowires, as needed, and increased throughput may be tested by using flowing samples. (See, e.g., MH Lee, et al., Nano Letters 11, 3425 (2011); and WS Liao, et al., Journal of Physical Chemistry C 117, 22362 (2013).) These nanowires may be produced in populations of identical nanowires, where different batches may employ different imageable patterns to differentially “label” each of the reservoirs into which each population of nanowire probes are introduced.
In embodiments, these systems may be used to produce nanowire probes formed, for example, with metal (such as, for example Au, Ag, Cu and Pt) semiconductor, polymer, or oxide striped nanowires that: 1) are stable under well conditions; 2) have a pattern with an imageable contrast; and 3) optionally either have sufficiently similar surface chemistry so that uniform or serial functionalization can be used or have an encapsulation layer that allows for such uniform or serial functionalization. An optical micrograph of a selection of different striped metal nanowires formed in accordance with such embodiments is provided as an example in
Some embodiments are also directed to optical imaging of populations of nanowires having different imageable patterns, including contrasting patterns and wavelength color patterns. A schematic of such a system (40) is shown in
Using such imaging methods, and utilizing sampling methods, embodiments will be directed to systems adapted to determine the flow or mixing between or leakage from sampled reservoirs. In many embodiments, a signal processor (50) programmed with automated algorithms and methods may also be provided to automatically determine the statistical distribution of the nanowire probes of different imageable patterns within the sampling population. As discussed, embodiments may incorporate static distributions or flow distributions (as shown in
In many embodiments, automated tracking and identification systems and methods may be used to identify the different imageable patterns (e.g., contrast and/or color patterns) from the sample of nanowire probes at a desired wavelength. Embodiments of such systems and methods may be adapted from systems designed to automatically track and identify barcodes using video imagery. In some embodiments such systems may utilize Intel's or others' computer vision software (contour searching function that is capable of identifying rectangles that bound features in the image and an iterative algorithm that identifies symbols such as bar codes). In other embodiments, a wavelet-based image processing metric with several applications including one- and two-dimensional bar code deblurring may also be used. (See, e.g., JA Dobrosotskaya and A L Bertozzi, IEEE Transactions on Image Processing 17, 657 (2008).) Such embodiments may also include automatic sorting algorithms that take images as input and sort them into like categories.
In addition to systems and methods of imaging the patterned nanowires, other embodiments are directed to the tracking, sorting, and identification of these cylindrical striped particles. In some such embodiments the nanowire images are reconstructed and important features extracted. In particular, state-of-the-art reconstruction as well as image decompositions may be incorporated into some embodiments to enhance the images of the striped metal nanorods. In many embodiments one or more of the following methodologies may be used: total variation restoration (LI Rudin, et al., Physica D 60, 259 (1992)); cartoon texture decomposition (L Vese and S Osher, Journal of Scientific Computation 19, 553 (2003); and JE Gilles and S Osher, UCLA CAM Report 11-73, (2011)); and nonlocal TV reconstruction (G Gilboa and S Osher, Multiscale Modeling and Simulation 7, 1005 (2008)). In particular, nonlocal TV reconstruction works well for supervised segmentation determination. In addition, a new cartoon texture decomposition has been developed that may be incorporated into embodiments.
Having described several embodiments, it will be recognized by those skilled in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the invention. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.
Those skilled in the art will appreciate that the presently disclosed embodiments teach by way of example and not by limitation. Therefore, the matter contained in the above description or shown in the accompanying drawings should be interpreted as illustrative and not in a limiting sense. The following claims are intended to cover all generic and specific features described herein, as well as all statements of the scope of the present method and system, which, as a matter of language, might be said to fall therebetween
This application claims priority to U.S. Provisional Application No. 62/634,755, entitled “Determining Fluid Reservoir Contents and Flow Configuration Using Functionalized Nanowire Probes” to Weiss et al., filed Feb. 23, 2018, the disclosure of which is incorporated herein by reference in its entirety. This application claims priority as a continuation-in-part of U.S. application Ser. No. 15/308,049, entitled “Determining Fluid Reservoir Connectivity Using Nanowire Probes” to Weiss et al., filed Oct. 31, 2016, which is a national stage entry of Application No. PCT/US2015/029173, filed May 15, 2015, which claims priority to U.S. Provisional Application No. 61/988,808, filed May 15, 2014, the disclosures of which are incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62634755 | Feb 2018 | US | |
| 61988808 | May 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15308049 | Oct 2016 | US |
| Child | 16284861 | US |
