Graphene oxide coated membranes to increase the density of water base fluids

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation, including: removing water from an aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the aqueous based wellbore servicing fluid via passage through the porous substrate, and whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased to provide a modified aqueous based wellbore servicing fluid.

TECHNICAL FIELD

The present disclosure relates generally to systems and methods for servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation; more specifically, the present disclosure relates to systems and methods for servicing a wellbore including recovering water from an aqueous based fluid; still more specifically, this disclosure relates to systems and methods for servicing a wellbore wherein water is recovered from an aqueous based fluid via contacting of the aqueous based fluid with a coated substrate including a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the aqueous based fluid via passage through the coated substrate, and whereby a water concentration and a volume of the aqueous based fluid are reduced and a density of the aqueous based fluid is increased to provide a modified wellbore servicing fluid.

BACKGROUND

During wellbore servicing (e.g., drilling) operations, aqueous based fluids can have and/or can uptake water such that a water concentration is or becomes undesirably high and/or a density of the aqueous based fluid is or becomes undesirably low. Conventionally, the density of, for example, a drilling fluid is increased via the addition of a weighting agent, such as barite. Such addition of weighting agent typically increases the fluid volume. Over time this process may be deemed undesirable, for example, when storage apparatus for the fluid has a limited volume.

Accordingly, there exists a need for a system and method of recovering water from aqueous based fluids during wellbore servicing operations, whereby a water concentration of the water based fluid can be reduced (e.g., and a density increased and/or a volume decreased) and/or the water concentration (e.g., the density and/or volume) maintained. Desirably, the systems and methods enable recovery of potable water and/or the production of a reduced volume of waste material needing disposal.

DETAILED DESCRIPTION

The terms “water based fluids” and “water base fluids” are utilized interchangeably herein, and refer to fluids including a base fluid selected from fresh water, seawater, saturated brine, formate brine, or a combination thereof.

As utilized herein, the term “hydrophilic” indicates “water attracting”, i.e., having more thermodynamically favorable interactions with water than with oil or other hydrophobic solvents.

As utilized herein, the term “oleophobic” indicates “oil repelling”, i.e., lacking an affinity to oil.

As utilized herein, the term “drilling fluids” includes drill-in fluids, such as brines.

Herein disclosed are systems and methods for servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation. The herein disclosed systems and methods provide for removing water from an aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a coated substrate including a porous substrate coated with a hydrophilic and oleophobic coating. Via contact of the aqueous based wellbore servicing fluid with the coated porous substrate, water is removed from the aqueous based wellbore servicing fluid via passage through the porous substrate, whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased to provide a modified aqueous based wellbore servicing fluid.

In embodiments, the herein disclosed systems and methods can be utilized to improve water base wellbore servicing (e.g., drilling) fluids management. For example, in embodiments, the disclosed systems and methods can be utilized (e.g., at a rig site) to reduce waste and manage drilling fluid density. In embodiments, the herein disclosed wellbore servicing systems and methods can be utilized to manage fluid volumes in a mud plant and potential fluid density and volumes at a rig site and provide for the production of heavier water based fluids with barite additions.

As detailed hereinbelow, coated substrates (e.g., graphene oxide coated membranes) can be utilized to increase the density of water based drilling fluids. Conventionally, increasing the density of a drilling fluid employs the addition of a weighting agent (such as barite), which typically increases the fluid volume. Over time, such a process may be deemed undesirable. Using a coated substrate of this disclosure (e.g., a coated membrane) to remove water from the aqueous based fluid will lower its volume as well as increase the fluid density. In some cases, it may be desirable to remove some water from the aqueous based wellbore servicing fluid to provide a modified aqueous based wellbore servicing fluid and add weighting material to the modified wellbore servicing fluid to maintain a constant fluid volume of the wellbore servicing fluid, while increasing the density thereof.

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation according to this disclosure includes: removing water from an aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a coated substrate including a porous substrate coated with a hydrophilic and oleophobic coating. The contacting of the aqueous based wellbore servicing fluid with the coated substrate results in removal of water from the wellbore servicing fluid via passage of water through the porous substrate, whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased to provide a modified aqueous based wellbore servicing fluid.

As depicted inFIG. 1A, which is a schematic of a coated substrate40, according to embodiments of this disclosure, the coated substrate40includes a porous substrate42including pores45and coated by hydrophilic and oleophobic coating41. The porous substrate can be any suitable substrate which can be coated with the hydrophilic and oleophobic coating and allow passage of water therethrough. In embodiments, the substrate42includes a support material. Although referred to as a “porous” substrate42, a substrate of coated substrate40can be any permeable material (e.g., with or without “pores”) which can be coated with the hydrophilic and oleophobic coating41and allow passage of water therethrough. In embodiments, the porous substrate42includes a membrane, a particulate, a tube, or a combination thereof. In the embodiment ofFIG. 1A, porous substrate42includes a cylindrical tube. In embodiments, porous substrate42includes a membrane shaped into a cylindrical tube, a flat membrane, or a membrane in another configuration. In embodiments, the porous substrate includes pores45having an average diameter of greater than or equal to about 0.5 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, or 50 nm, less than or equal to about 20 μm, 10 μm, or 1 μm, or in a range of from about 0.5 nm to about 20,000 nm, from about 5 nm to about 10,000 nm, or from about 50 nm to about 1,000 nm. In embodiments, the porous substrate includes a polymer, a ceramic, a zeolite, a molecular sieve, or a combination thereof.

As depicted in the embodiment ofFIG. 1A, the hydrophilic and oleophobic coating of coated substrate40can have a thickness T1in a range of from about 1 to about 100 nm, from about 1 to about 50 nm, or from about 1 to about 50 nm, from about 1 to about 10 nm, less than or equal to about 100, 50, 40, 30, 20, or 10 nm, and/or greater than or equal to about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm. Also as depicted in the embodiment ofFIG. 1A, the porous substrate42of coated substrate40can have a thickness T2in a range of from about 0.2 mm to about 100 mm, from about 1 mm to about 50 mm, or from about 10 mm to about 25 mm, less than or equal to about 100 mm, 50 mm, or 25 mm, and/or greater than or equal to about 0.2 mm, 1 mm, or 10 mm.

With reference toFIG. 1B, which is a cross section of the coated substrate40ofFIG. 1A, in embodiments, coated substrate40(e.g., a cylindrical or spherical porous substrate42) has an inner diameter in a range of from about 1 mm to about 50 mm, from about 1 mm to about 25 mm, from about 5 mm to about 35 mm, or from about 10 mm to about 50 mm, less than or equal to about 50 mm, 40 mm, 35 mm, 30 mm, 20 mm, or 10 mm, and/or greater than or equal to about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm.

Water passes from one side of coated substrate40to another, generally from the coated side to the (e.g., porous) substrate side. For example, as depicted inFIG. 1AandFIG. 1B, coated substrate40is configured for passage of water from an outside44to an inside43thereof, as illustrated by arrow A1. Alternatively, a substrate having a cylindrical tube shape is coated on an inside thereof with the hydrophilic and oleophobic coating41, and water is introduced into the inside43of coated substrate40and passes from inside43to outside44(e.g., in a direction opposite that indicated by arrow A1).

As noted hereinabove, the coating41of this disclosure is hydrophilic and oleophobic. In embodiments, the hydrophilic and oleophobic coating41includes graphene oxide. The natural tendency is for water to migrate through the hydrophilic and oleophobic coated substrate40(e.g., a graphene oxide coated membrane) with little or no differential pressure applied to the coated substrate40itself. Without limitation, such a graphene coated membrane technology is offered by G2O Water Technologies, Ltd., of Manchester UK. In embodiments, the contacting of the aqueous based fluid with the coated substrate40is effected at a differential pressure across the coated substrate40of less than or equal to about 10, 9, 8, 7, 6, or 5 psi.

According to this disclosure, the aqueous based wellbore servicing fluid from which water is removed by contact with the coated substrate40can include a drilling fluid, a produced water, a drill-in fluid, a packer fluid, a spacer fluid, a cleaner fluid, an acidizing fluid, a filter cake breaking fluid, a fracturing fluid, a lost circulation pill, a recovered brine, or a combination thereof. In embodiments, the aqueous based wellbore servicing fluid is an aqueous based wellbore servicing fluid that has been recovered from a wellbore60and/or a formation64(described hereinbelow with reference to the embodiment ofFIG. 2). Such an aqueous based fluid will be referred to herein as a “spent” aqueous based wellbore servicing fluid. As utilized herein a “spent” aqueous based fluid includes a produced water recovered from a formation64and a wellbore servicing (e.g., drilling) fluid that has been recovered from the wellbore60(e.g., circulated downward through a drill string61extending from the surface65into the wellbore60, out an end66of the drill string61(e.g., out a drill bit63connected to end66of the drill string61), and upward through an annular space62formed between the drill string61and the wellbore60). Although shown as pumped via end66of drill string61and through a drill bit63in the embodiment ofFIG. 2, in embodiments the wellbore servicing fluid is pumped through a bottom hole assembly (BHA) located at end66of drill string61, and the BHA can include, for example, a by-pass sub, a MWD tool, a mud motor, a logging tool, etc. In such embodiments, component63can include such a BHA.

As depicted inFIG. 2, which is a schematic of a system I for recovering water from a water base drilling fluid, according to embodiments of this disclosure, aqueous based wellbore servicing fluid can be introduced into a water removal or recovery apparatus30via a line25(which can be a pump outlet line, in embodiments) containing therein the coated substrate40(e.g., graphene oxide coated membrane(s)). Pump20can be utilized to pump aqueous based wellbore servicing fluid from an aqueous based fluid source, which can be, for example, an aqueous based fluid storage unit10into water removal apparatus30. Pump20can be fluidly connected with aqueous based fluid storage unit10via pump inlet line15and fluidly connected with water removal apparatus30via pump outlet line25. Water removed via passage through the coated substrate40can be removed from water removal apparatus30via one or more water outlet line(s)35, and modified aqueous based fluid (e.g., aqueous based fluid from which water has been removed) can be removed from water removal apparatus30via one or more modified aqueous based fluid outlet (or “return”) line(s)36.

In embodiments, the water removed from the aqueous based wellbore servicing fluid by the contacting thereof with the coated substrate40and passage through the porous substrate42coated with the hydrophilic and oleophobic coating41is potable water. In embodiments, the water removed from the aqueous based wellbore servicing fluid and from water removal apparatus30via water outlet line(s)35is potable water having a total dissolved solids (TDS) content of less than or equal to about 5000, 4000, 3000, 2000, 1000, 750, or 500 ppm, a hydrocarbon content of less than or equal to about 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 mg/L, and/or a salt content of less than or equal to about 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400, 300, 200, or 100 ppm. In embodiments, the TDS is determined by water evaporation using a precision analytical balance. In embodiments, the TDS is estimated via a TDS meter that estimates the TDS from the electrical conductivity. In embodiments, the hydrocarbon content of the water removed via water outlet line(s)35is determined by 40 CFR Part 136 Method 608.3, 624.1, and/or 625.1. In embodiments, the conductivity is determined by measuring the electrical conductivity.

The ability of the herein disclosed system and method to remove potable water from aqueous based wellbore servicing fluids can provide advantages over conventional water removal techniques. For example, the conventional method of filtering to remove water generally allows salts, some degree of hydrocarbons, dissolved solids and the like to pass through the filter along with the removed water. Such filtered water is generally not potable, and can be hazardous, thus presenting challenges for disposal thereof. Via the herein disclosed systems and methods, an amount of hazardous waste material (e.g., hazardous water and/or solid or semi-solid waste) can be reduced relative to conventional systems and methods of removing water from (and thus increasing the density of) aqueous based wellbore servicing fluids. Additionally, conventional filtration generally utilizes higher pressures than the herein disclosed systems and methods to separate water from an aqueous based fluid.

As depicted in the embodiment ofFIG. 2, the aqueous based wellbore servicing fluid introduced into water removal apparatus30via line25can be introduced from an aqueous based fluid storage unit10(also referred to as a “water storage unit10”). In embodiments, water storage unit10can include, for example, a mud pit. As noted hereinabove, in embodiment, the aqueous based wellbore servicing fluid from which water is to be removed in water removal apparatus30can be an aqueous based wellbore servicing fluid that has been recovered from the wellbore60and/or the formation64prior to contact with the coated substrate40including porous substrate42coated with the hydrophilic and oleophobic coating41. For example, with reference to the embodiment ofFIG. 2, in embodiments, an aqueous based wellbore servicing fluid is introduced into aqueous based fluid storage unit10via a pathway70fluidly connected with wellbore60extending from a surface of the earth65and penetrating subterranean formation64. Alternatively, in embodiments, an aqueous based wellbore servicing fluid is introduced directly into water removal apparatus30(e.g., without a water storage unit10). In embodiments, the modified aqueous based wellbore servicing fluid from which water has been removed in water removal apparatus30is returned into the wellbore60, for example via pathway75from aqueous based fluid storage apparatus10or directly from water removal apparatus30.

In embodiments, the aqueous based wellbore servicing fluid includes a drilling fluid and the drilling fluid is circulated downward through a drill string61extending from the surface of the earth65into the wellbore60in formation64, out a drill bit63connected to an end66of the drill string61, and upward through an annular space62formed between the drill string61and the wellbore60.

In embodiments, after the removing of the water therefrom, the aqueous based wellbore servicing fluid (e.g., the modified aqueous based wellbore servicing fluid in modified aqueous based fluid outlet line(s)36) has a target density. Aqueous based wellbore servicing fluids, such as drilling fluids, generally have target rheologies (e.g., densities) that are needed for providing a desired function. For example, without limitation, aqueous based drilling fluids may have a target density needed to lift drill cuttings away from a drill bit63during drilling operations. In embodiments, a method of this disclosure can further include adding a weighting material and/or water to the aqueous based wellbore servicing fluid, after the removing of the water therefrom, to attain the target density. For example, in the embodiment ofFIG. 2, one or more water and or weighting agent inlet lines55can be fluidly attached to aqueous based fluid storage unit10and/or directly into water removal apparatus30, whereby water and/or weighting agent(s) can be introduced thereto. Any weighting material known to those of skill in the art can be added to the aqueous based wellbore servicing fluid or the modified aqueous based wellbore servicing fluid to increase the density thereof to reach the desired target density. Such a weighting agent includes, without limitation, barite.

In embodiments, an amount of water removed in water removal apparatus30and an amount of weighting agent (e.g., barite) added to the aqueous based fluid (e.g., the modified aqueous based fluid from which water has been removed in water removal apparatus30) added are accurately controlled. In embodiments, the method is utilized as a constant volume method, whereby an amount of water removed from water removal apparatus30via water outlet line(s)35and an amount of weighting agent (e.g., barite) added to the aqueous based fluid (e.g., the modified aqueous based fluid from which water has been removed in water removal apparatus30) are controlled such that an amount of water to be removed is calculated and the process run until a constant volume of aqueous based fluid in aqueous based fluid storage unit10is achieved. After removing the water from the aqueous based wellbore servicing fluid in water removal apparatus30, a predetermined amount of weighting agent (e.g., barite) can be added to the system (e.g., to water removal apparatus30, modified aqueous based fluid outlet line36, and/or aqueous based fluid storage unit10) to complete the density increase to the target density.

FIG. 3is a schematic of another system II for recovering water from a water base drilling fluid, according to embodiments of this disclosure. The embodiment ofFIG. 3is the same as that ofFIG. 2, except a water or weighting material inlet line55is not utilized for introducing a weighting material (e.g., barite) into aqueous based fluid storage unit10. Via the system II, a fluid volume in the system can decrease as water is removed from the aqueous based wellbore servicing fluid via water removal apparatus30.

Water removal apparatus30can have a variety of configurations, so long as water can removed therein via contacting of the aqueous based fluid introduced thereto with a coated substrate40, as described herein, and water (e.g., that passes through the coated substrate(s)40) and the water-reduced modified aqueous based fluid (e.g., the aqueous based fluid from which the water has been removed) can be removed therefrom. For example, in embodiments, system I ofFIG. 2or system II ofFIG. 3includes a water removal apparatus30as depicted inFIG. 4, which is a schematic of a water removal apparatus30according to embodiments of this disclosure. Water removal apparatus30ofFIG. 4includes a coated substrate40having a cylindrical or tube shaped porous substrate42coated with hydrophilic and oleophobic coating41. In the embodiment ofFIG. 4, porous cylindrical substrate42is coated on an outside thereof with the coating41. In this embodiment, coated cylindrical substrate40defines an inside43or “removed water flow section”43inside cylindrical porous substrate42, and an outside44or “aqueous based fluid flow section”44between coating41and wall (e.g., outer wall)37. The outer wall37and the coated substrate40can, in such embodiments, include concentric tubes or cylinders defining outside44of coated substrate tube40and inside43of coated substrate tube40. In this embodiment, hydrophilic and oleophobic coating41of coated substrate tube40attracts water from aqueous based fluid introduced into the aqueous based fluid flow section or outside44(e.g., via an inlet line connected therewith, which can, in embodiments, be a pump outlet line(s)25), which water passes through cylindrical coated substrate40to the inside43of cylindrical coated substrate40which serves, in this arrangement, as a removed water flow section43. Accordingly, in the embodiment of FIG.4, water flows from outside44to inside43of cylindrical coated substrate40in the direction indicated by arrow A1. In such embodiments, an aqueous based fluid inlet line(s) (e.g., a pump outlet line(s)25) can be fluidly connected with and introduce aqueous based fluid into outside44of coated substrate40, while a removed water outlet line(s)35can be fluidly connected with and remove water from inside44of coated substrate40.

In alternative embodiments, the hydrophilic and oleophobic coating41of a cylindrical coated substrate40is coated on the inside surface of porous substrate42, in which embodiments, inside43of cylindrical coated substrate40can provide the aqueous based fluid flow section, and outside44of cylindrical coated substrate40can provide the removed water flow section. In such embodiments, water from the aqueous based fluid introduced into inside43(e.g., via an inlet line connected therewith, which can, in embodiments, be a pump outlet line(s)25) can flow from inside43to outside44, in a direction opposite to that indicated by arrow A1inFIG. 4. In such embodiments, an aqueous based fluid inlet line (e.g., a pump outlet line(s)25) can be fluidly connected with and introduce aqueous based fluid into inside43of coated substrate40, while a removed water outlet line(s) can be fluidly connected with and remove water from outside44of coated substrate40. In embodiments, a water removal apparatus30of this disclosure includes a plurality of cylindrical coated substrates40, with associated water inlet lines (e.g., pump outlet lines25), removed water outlet lines35, and insides43and outsides44(which can provide aqueous based fluid flow sections and/or removed water flow sections).

FIG. 5Ais a schematic of another system III for recovering water from a water base fluid, according to embodiments of this disclosure. Water removal apparatus30(shown in side view cross section inFIG. 5A) can have one or more layers or “beds” of coated substrate, with two layers of coated substrate40, first coated substrate layer40A and second coated substrate layer40B, depicted in the embodiment ofFIG. 5A. In such embodiments, aqueous based fluid can be introduced (e.g., from aqueous based fluid source10, pump inlet line15, pump20, and pump outlet line25) into one or more aqueous based fluid flow sections26of water removal apparatus30and water that passes from the aqueous based fluid, through the coated substrate layers40A,40B can be removed via one or more removed water flow sections27. The aqueous based fluid flow sections26provide contact of the aqueous based fluid introduced into water removal apparatus30with the coating41of first coated substrate layer40A and second coated substrate layer40B. The removed water sections27provide a flow path for water that passes through first coated substrate layer40A and second coated substrate layer40B, on a side of substrate42opposite the coating41. One aqueous based fluid flow section26and two removed water flow sections, including first water flow section27A and second water flow section27B, are depicted in the embodiment ofFIG. 5A.FIG. 5Bshows a front view cross section of the water removal apparatus30ofFIG. 5A. A water removal apparatus30can include any number of coated substrates40(e.g., coated substrate layers, such as first coated substrate layer40A and second coated substrate layer40B of the embodiment ofFIGS. 5A and 5B), aqueous based fluid flow sections26, and removed water flow sections27(e.g., the single aqueous based fluid flow section26and two water flow sections including first water flow section27A and second water flow section27B shown in the embodiment ofFIG. 5AandFIG. 5B).

FIG. 6Ais a schematic of another system IV for recovering water from a water base fluid, according to embodiments of this disclosure.FIG. 6Bis a front cross section view of water removal apparatus30of the embodiment ofFIG. 6A. Water removal apparatus30(shown in side view cross section inFIG. 6A) can include one or more cylindrical tubes (e.g., cylinders) of coated substrate (e.g., cylindrical coated membranes), with two, first cylindrical coated substrate40A and second cylindrical coated substrate40B) depicted in the embodiment ofFIG. 6Aand eight (first through eighth cylindrical coated substrates40A-40H) depicted in the embodiment ofFIG. 6B. In this embodiment, aqueous based fluid can be introduced from aqueous based fluid source10, pump inlet line15, pump20, and pump outlet line25into one or more aqueous based fluid flow sections26of water removal apparatus30and water that passes from the aqueous based fluid, through the coating41of first cylindrical coated substrate40A and water that passes from the aqueous based fluid through the coating41of the second cylindrical coated substrate40B, and so on, can be removed via one or more removed water flow sections27. Two removed water flow sections, first removed water flow section27A and second removed water flow section27B, are depicted in the embodiment ofFIG. 6A. In this embodiment, outsides44of the coated substrates40(e.g., outsides44of first cylindrical coated substrate40A and second cylindrical coated substrate40B, and so on) provide the aqueous based fluid flow sections26, while insides43of the coated substrates40(e.g., insides43of first cylindrical coated substrate40A and second cylindrical coated substrate40B) provide the removed water flow sections27(e.g., first removed water flow section27A inside first cylindrical coated substrate40A and second removed water flow section27B inside second cylindrical coated substrate40B, and so on).FIG. 6Bshows a front cross section view of the water removal apparatus30ofFIG. 6Aincluding eight coated substrates40A-40H with associated insides43providing water flow sections27A-27H and outsides44providing water flow section26. A water removal apparatus30can include any number of coated substrates40. For example, a water removal apparatus can include one or a plurality of coated substrates40. In embodiments, a water removal apparatus30of this disclosure includes from 1 to 50, from 1 to 20, from 10 to 50, from 2 to 100, or more coated substrates40.

A water removal apparatus30can include any number of coated substrates40(e.g., cylindrical coated substrates or coated tubes, such as first cylindrical coated substrate40A and second cylindrical coated substrate40B, and so on, of the embodiment ofFIGS. 6A and 6B), aqueous based fluid flow sections26, and removed water flow sections27. An aqueous based fluid inlet line, such as pump outlet line25, can be utilized to introduce the aqueous based fluid into aqueous based fluid flow section(s)26, a removed water outlet line35can be utilized to remove water from each of the removed water flow sections27, and a modified aqueous based fluid outlet line36can be utilized to remove modified (e.g., water-reduced) aqueous based fluid from the aqueous based fluid flow section(s)26(e.g., at an end thereof). For example, in the embodiment ofFIG. 5AandFIG. 5B, pump outlet line25can be utilized to introduce aqueous based fluid into aqueous based fluid flow section26, modified aqueous based fluid outlet line36can be utilized to remove modified aqueous based fluid from aqueous based fluid flow section26(e.g., at an opposite end thereof from the aqueous based fluid inlet at pump outlet25), and first removed water outlet line35A and second removed water outlet line35B can be utilized to remove water from first removed water flow section26A and second removed water flow section26B, respectively. First removed water outlet line35A and second removed water outlet line35B can be manifolded into removed water outlet line35, in embodiments. In the embodiment ofFIG. 6AandFIG. 6B, pump outlet line25and one or more aqueous based fluid inlet lines (e.g., first aqueous based fluid inlet line25A, second aqueous based fluid inlet line25B, and third aqueous based fluid inlet line25C depicted inFIG. 6A) can be utilized to introduce aqueous based fluid into aqueous based fluid flow section(s)26, first modified aqueous based fluid outlet line36A, second modified aqueous based fluid outlet line36B, and third aqueous based fluid outlet line36C, and so on, can be utilized to remove modified aqueous based fluid from aqueous based fluid flow section(s)26(e.g., at an opposite end thereof from the aqueous based fluid inlet at aqueous based fluid inlets25), and first removed water outlet line35A and second removed water outlet line35B, and so on, can be utilized to remove water from first removed water flow section27A and second removed water flow section27B, and so on, respectively. The one or more modified aqueous based fluid outlet lines36(e.g., first modified aqueous based fluid outlet line36A, second modified aqueous based fluid outlet line36B, third modified aqueous based fluid outlet line36C, and so on) can be manifolded into modified aqueous based fluid outlet line36, in embodiments. Similarly, the one or more removed water outlet lines35(e.g., first removed water outlet line35A and second removed water outlet line35B, and so on) can be manifolded into removed water outlet line35, in embodiments.

One or more contaminated aqueous stream lines25can be utilized to introduce contaminated aqueous based fluid into each contaminated aqueous based fluid flow section26. One or more modified aqueous based fluid outlet lines36can be utilized to remove modified aqueous based fluid from each contaminated aqueous based fluid flow section26. One or more removed water outlet lines35can be utilized to removed treated water from each removed water flow section27.

Although aqueous based fluid flow section26of the embodiment ofFIG. 6AandFIG. 6Bis shown as a continuous section inFIG. 6B(i.e., because coated substrates40are depicted as not touching), in embodiments, coated substrate tubes (e.g., first cylindrical coated substrate40A, second cylindrical coated substrate40B, etc.) can be in contact with neighboring coated substrate tubes, and a plurality of aqueous based fluid inlet flow lines, e.g., aqueous based inlet flow lines25A,25B,25C, and so on) can be utilized to introduce the aqueous based fluid into disparate aqueous based fluid flow sections26of a water removal apparatus30, in embodiments.

In the embodiment ofFIG. 6AandFIG. 6B, water removal apparatus30is designed in a similar manner as a heat exchanger, wherein the coated substrate tubes40of the water removal apparatus30separate the flow of aqueous based fluid and the removed water that passes through the coating41(e.g., coated walls) and substrates42of the coated substrate tubes40the way the heat exchange tubes of a heat exchanger separate a heat exchanger fluid from a process fluid and heat passes through the walls of the heat exchanger tubes. The inside and the outside of the tubes act as the aqueous based fluid flow sections26and the removed water flow sections27, respectively, or vice versa.

A plethora of configurations of the coated substrate40(e.g., layers or sheets, as depicted in the embodiments ofFIGS. 5A and 5B, tubes or cylinders, as depicted in the embodiments ofFIGS. 6A and 6B) are possible, and within the scope of this disclosure. For example, by way of further nonlimiting example, in alternative embodiments, the porous substrate42includes hollow particulates, and the particulate substrate is coated with the hydrophilic and oleophobic coating41to provide a coated substrate40including coated particulates. In such embodiments, water removal apparatus30can include a bed, layer, or containment of such coated particulates. In such embodiments, aqueous based fluid introduced into water removal apparatus30, for example via an aqueous based fluid inlet line such as pump outlet line25contacts the particulates of coated substrate40, water passes through the hydrophilic and oleophobic coating41of the coated particulates, and enters a hollow core, center, or region of the particulates. In such embodiments, the coated particulates having removed water sequestered therein can be regenerated (i.e., water removed therefrom), and be reused in water removal apparatus30. Regeneration can include heating, pressing, or the like to remove the water from the spent coated substrate particulates prior to re-use.

In embodiments, a method of this disclosure further includes cycling the coated porous substrate40/40A-40H through a backwash to clean an upstream surface thereof. Such cycling can be effected continuously, in embodiments.

Via the system and method of this disclosure, the aqueous based fluids (e.g., aqueous based drilling fluids in a mud plant) can be recycled several times through various density ranges. The density of the aqueous based wellbore servicing fluid in aqueous based wellbore servicing storage tank10can be alternately increased and decreased, as needed. The density of the aqueous based wellbore servicing fluid in aqueous based wellbore servicing fluid storage unit10can be increased by increasing an amount of water removed from the aqueous based wellbore servicing fluid in water removal apparatus30by increasing an amount of the aqueous based fluid introduced into water removal apparatus30via pump outlet line(s)25, and/or an amount of modified aqueous based wellbore servicing fluid removed from water removal apparatus30(and returned to aqueous based fluid storage unit10) via water reduced aqueous based fluid outlet line(s)36), and/or by increasing an amount of weighting agent and/or decreasing an amount of water introduced into aqueous based wellbore servicing fluid storage unit10(and/or directly into water reduced aqueous based fluid outlet line(s)36and/or into water removal apparatus30).

The density of the aqueous based wellbore servicing fluid in aqueous based wellbore servicing fluid storage unit10can be reduced by decreasing an amount of water removed from the aqueous based wellbore servicing fluid in water removal apparatus30by decreasing an amount of the aqueous based fluid introduced into water removal apparatus30via pump inlet line(s)15, pump(s)20, and pump outlet line25(s), and/or an amount of modified aqueous based wellbore servicing fluid removed from water removal apparatus30(and returned to aqueous based fluid storage unit20) via modified aqueous based fluid outlet line(s)36), and/or reducing an amount of weighting agent and/or increasing an amount of water introduced into aqueous based fluid storage unit10(and/or directly into modified aqueous based fluid outlet line36and/or into water removal apparatus30).

In embodiments, the aqueous based wellbore servicing fluid includes an aqueous based drilling fluid, and a method of servicing a wellbore60extending from a surface of the earth65and penetrating a subterranean formation64, includes: removing water (e.g., via water outlet line(s)35) from the aqueous based drilling fluid by contacting the aqueous based drilling fluid (e.g., in water removal apparatus30after introduction thereto via pump inlet line15, pump20, and/or pump outlet line25) with a coated substrate40including a porous substrate42coated with a hydrophilic and oleophobic coating41, whereby water is removed (e.g., via removed water outlet line(s)35) from the aqueous based drilling fluid via passage through the coated substrate40having the porous substrate42coated with the hydrophilic and oleophobic coating41, whereby a water concentration and a volume of the aqueous based drilling fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased; and optionally adding a weighting material and/or water (e.g., via one or more water and/or weighting agent inlet lines55) to the aqueous based drilling fluid after the removing of the water therefrom (e.g., added directly to water removal apparatus30, water reduced, modified aqueous based wellbore servicing fluid outlet line(s)36, and/or aqueous based wellbore servicing fluid storage unit10, or a combination thereof).

In embodiments, the method further includes maintaining a substantially constant volume of the aqueous based drilling fluid in a mud pit (utilized as aqueous based fluid storage unit10) containing same by controlling an amount of the water removed by the contacting of the aqueous based drilling fluid with the coated substrate40and an amount of the weighting material and/or the water optionally added to the aqueous based drilling fluid after the removing of the water therefrom.

As noted hereinabove, in embodiments aqueous based source10includes an aqueous based storage unit10. For example, in embodiments, the aqueous based fluid is an aqueous based drilling fluid, and the aqueous based drilling fluid is stored, prior to and/or after the removing of the water therefrom, in a mud pit10. In such embodiments, a weighting material can be added (e.g., via water and/or weighting agent inlet line(s)55) to the mud pit10containing the aqueous based drilling fluid to increase the fluid density, as described hereinabove with reference to the embodiment ofFIG. 2. Alternatively, the source of the aqueous based fluid includes the wellbore60(e.g., aqueous based fluid is introduced directly from wellbore60into water removal apparatus30). As noted hereinabove, in embodiments, the aqueous based drilling fluid is recovered from the wellbore60prior to contact with the coated substrate40and the aqueous based wellbore drilling fluid is returned into the wellbore60after contact with the coated substrate40.

In embodiments, a method of servicing a wellbore60extending from a surface of the earth65and penetrating a subterranean formation64according to this disclosure includes: circulating an aqueous based wellbore servicing fluid from the surface65, into the wellbore60, and back to the surface65; and maintaining a desired density of the aqueous based wellbore servicing fluid by: removing water from the aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a coated substrate40having a porous substrate42coated with a hydrophilic and oleophobic coating41, whereby water is removed from the aqueous based wellbore servicing fluid via passage through the coated substrate40, and whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased; and optionally adding a weighting material and/or water (e.g., to aqueous based fluid source or storage unit10via one or more water and/or weighting agent inlet line(s))55) to the aqueous based wellbore servicing fluid after the removing of the water therefrom (e.g., via removed water outlet line(s)35). In some specific embodiments, as noted above, the hydrophilic and oleophobic coating41includes graphene oxide. In some such embodiments, the aqueous based wellbore servicing fluid is an aqueous based drilling fluid, and a water content of the aqueous based drilling fluid increases as it circulated from the surface65, into the wellbore60, and back to the surface65.

In embodiments, a method of servicing a wellbore60extending from a surface of the earth65and penetrating a subterranean formation64according to this disclosure includes: recovering a spent fluid from the wellbore60; forming a concentrated composition by removing a portion of the water from the spent fluid recovered from the wellbore60, wherein the portion of the water is removed by contacting the spent fluid with a coated substrate40including a porous substrate42coated with a hydrophilic and oleophobic coating41, as described herein, whereby water is removed (e.g., via water removal line(s)35) from the spent fluid via passage through the coated substrate40to provide the concentrated composition. In embodiments, the concentrated composition has a water concentration and a volume that are less than a water concentration and a volume of the spent fluid, respectively, and a density that is greater than a density of the spent fluid. The method can further include disposing of the concentrated composition at a location proximate the wellbore60and/or transporting the concentrated composition to a location remote from the wellbore60and disposing thereof. In some such embodiments, the spent fluid includes a spent aqueous based wellbore servicing fluid. In embodiments, the spent aqueous based wellbore servicing fluid includes a spent aqueous based drilling fluid. In embodiments, the spent fluid includes produced water.

In embodiments, the volume of the concentrated composition is at least 5, 10, 20, 30, or 40 percent less than a volume of the spent aqueous based wellbore servicing fluid recovered from the wellbore60. As described hereinabove, in embodiments, the water removed from the spent fluid via the passage through the porous substrate42(of coated substrate40) is potable water.

The method can further include utilizing the water that is removed from the spent fluid via the passage through the coated substrate40(e.g., and removed from water removal apparatus30via removed water outlet line(s)35) onsite or offsite as drinking water, wash water, irrigation water, cooling water, a component of an aqueous containing wellbore servicing fluid (e.g., an aqueous based or oil based wellbore servicing fluid), or a combination thereof. The water removal can be effected as detailed hereinabove. For example, in embodiments, the hydrophilic and oleophobic coating41utilized in this method includes graphene oxide.

Those of ordinary skill in the art will readily appreciate various benefits that may be realized by the present disclosure. For instance, in embodiments, the herein disclosed system and method enable real time adjustment of the water content of an aqueous based wellbore servicing fluid, whereby a density thereof can be adjusted to reach a target density. The herein disclosed system and method also enable the removal of water from an aqueous based wellbore servicing fluid whereby a volume of the aqueous based wellbore servicing fluid can be decreased and maintained at a desired constant volume and/or kept below a maximum desired amount (e.g., a maximum aqueous based fluid storage capacity or volume of an aqueous base fluid storage unit10, such as. for example, a mud pit). In embodiments, via the herein disclosed system and method, potable water can be produced from aqueous based wellbore servicing fluids, and the potable water utilized onsite (e.g., for drinking water, wash water, irrigation water, cooling water, a component of a new aqueous containing wellbore servicing fluid (e.g., an aqueous based or oil based wellbore servicing fluid), or a combination thereof) and/or sent off site. In embodiments, the removal of water from aqueous based wellbore servicing fluids as per this disclosure can result in a reduced amount of hazardous or un-environmentally friendly materials (liquids and/or solids or semi-solids) for which permits and/or further treatment are required for disposal.

ADDITIONAL DISCLOSURE

Embodiment A

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation, comprising: removing water from an aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the aqueous based wellbore servicing fluid via passage through the porous substrate, and whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased to provide a modified aqueous based wellbore servicing fluid.

Embodiment B

The method of Embodiment A, wherein the hydrophilic and oleophobic coating comprises graphene oxide.

Embodiment C

The method of Embodiment A or Embodiment B, wherein the aqueous based wellbore servicing fluid is a drilling fluid.

Embodiment D

The method of any of Embodiment A through Embodiment C, wherein the aqueous based wellbore servicing fluid is recovered from the wellbore prior to contact with the porous substrate and wherein the modified aqueous based wellbore servicing fluid is returned into the wellbore.

Embodiment E

The method of any of Embodiment A through Embodiment D, wherein the porous substrate comprises a membrane, a particulate, a tube, or a combination thereof.

Embodiment F

The method of any of Embodiment A through Embodiment E, wherein the porous substrate comprises a polymer, a ceramic, a zeolite, a molecular sieve, or a combination thereof.

Embodiment G

The method of any of Embodiment A through Embodiment F, wherein the contacting is effected at a differential pressure across the coated porous substrate of less than or equal to about 10, 9, 8, 7, 6, or 5 psi.

Embodiment H

The method of any of Embodiment A through Embodiment G, wherein the water removed via passage through the porous substrate coated with the hydrophilic and oleophobic coating is potable water.

Embodiment I

Embodiment J

The method of any of Embodiment A through Embodiment I, wherein, after the removing of the water therefrom, the aqueous based wellbore servicing fluid has a target density.

Embodiment K

The method of any of Embodiment A through Embodiment J further comprising adding a weighting material and/or water to the aqueous based wellbore servicing fluid, after the removing of the water therefrom, to attain a target density.

Embodiment L

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation, the method comprising: removing water from the aqueous based drilling fluid by contacting the aqueous based drilling fluid with a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the aqueous based drilling fluid via passage through the porous substrate, and whereby a water concentration and a volume of the aqueous based drilling fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased; and optionally adding a weighting material and/or water to the aqueous based drilling fluid after the removing of the water therefrom.

Embodiment M

The method of Embodiment L further comprising maintaining a substantially constant volume of the aqueous based drilling fluid in a mud pit containing same by controlling an amount of the water removed by the contacting of the aqueous based drilling fluid with the porous substrate and an amount of the weighting material and/or the water optionally added to the aqueous based drilling fluid after the removing of the water therefrom.

Embodiment N

The method of Embodiment M, wherein the aqueous based drilling fluid is stored, prior to and/or after the removing of the water therefrom, in a mud pit, and/or wherein the weighting material is added to a mud pit containing the aqueous based drilling fluid.

Embodiment O

The method of any of Embodiment L through Embodiment N, wherein the aqueous based drilling fluid is recovered from the wellbore prior to contact with the porous substrate and wherein the aqueous based wellbore drilling fluid is returned into the wellbore after contact with the porous substrate.

Embodiment P

The method of Embodiment O, wherein the drilling fluid is circulated downward through a drill string extending from the surface into the wellbore, out a bottom hole assembly (BHA) connected to an end of the drill string, and upward through an annular space formed between the drill string and the wellbore.

Embodiment Q

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation, the method comprising: circulating an aqueous based wellbore servicing fluid from the surface, into the wellbore, and back to the surface; and maintaining a desired density of the aqueous based wellbore servicing fluid by: removing water from the aqueous based wellbore servicing fluid by contacting the aqueous based wellbore servicing fluid with a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the aqueous based wellbore servicing fluid via passage through the porous substrate, and whereby a water concentration and a volume of the aqueous based wellbore servicing fluid are reduced and a density of the aqueous based wellbore servicing fluid is increased; and optionally adding a weighting material and/or water to the aqueous based wellbore servicing fluid after the removing of the water therefrom.

Embodiment R

The method of Embodiment Q, wherein the hydrophilic and oleophobic coating comprises graphene oxide.

Embodiment S

The method of Embodiment Q or Embodiment R, wherein the aqueous based wellbore servicing fluid is an aqueous based drilling fluid, and wherein a water content of the aqueous based drilling fluid increases as it circulated from the surface, into the wellbore, and back to the surface.

Embodiment T

A method of servicing a wellbore extending from a surface of the earth and penetrating a subterranean formation, comprising: recovering a spent fluid from the wellbore; forming a concentrated composition by removing a portion of the water from the spent fluid recovered from the wellbore, wherein the portion of the water is removed by contacting the spent fluid with a porous substrate coated with a hydrophilic and oleophobic coating, whereby water is removed from the spent fluid via passage through the porous substrate to provide the concentrated composition, wherein the concentrated composition has a water concentration and a volume that are less than a water concentration and a volume of the spent fluid, respectively, and a density that is greater than a density of the spent fluid; and disposing of the concentrated composition at a location proximate the wellbore, transporting the concentrated composition to a location remote from the wellbore and disposing thereof, or disposing of a first portion of the concentrated composition at a location proximate the wellbore and transporting a second portion of the concentrated composition to a location remote from the wellbore and disposing thereof.

Embodiment U

The method of Embodiment T, wherein the volume of the concentrated composition is at least 5, 10, 20, 30, or 40 percent less than a volume of the spent aqueous based wellbore servicing fluid recovered from the wellbore.

Embodiment V

The method of Embodiment T or Embodiment U, wherein the spent fluid comprises a spent aqueous based wellbore servicing fluid.

Embodiment W

The method of any of Embodiment T through Embodiment V, wherein the spent aqueous containing wellbore servicing fluid comprises a spent aqueous based drilling fluid.

Embodiment X

The method of any of Embodiment T through Embodiment W, wherein the spent fluid comprises produced water.

Embodiment Y

The method of any of Embodiment T through Embodiment X, wherein the water removed from the spent fluid via the passage through the porous substrate is potable water.

The method of any of Embodiment T through Embodiment Y further comprising utilizing the water that is removed from the spent fluid via the passage through the porous substrate onsite or offsite as drinking water, a component of an aqueous based wellbore servicing fluid, or a combination thereof.

The method of any of Embodiment T through Embodiment Z1, wherein the hydrophilic and oleophobic coating comprises graphene oxide.