WO2015066347A1

WO2015066347A1 - Separation of organic compounds from liquid

Info

Publication number: WO2015066347A1
Application number: PCT/US2014/063198
Authority: WO
Inventors: Felipe LEMBCKE; Eduardo GOMEZ MAQUEO ARECHIGA
Original assignee: Lembcke Felipe; Gomez Maqueo Arechiga Eduardo
Priority date: 2013-10-30
Filing date: 2014-10-30
Publication date: 2015-05-07
Also published as: CN105960273A

Abstract

A functionalized porous ceramic membrane is disclosed for separating non-polar organic compounds from a liquid feed. The membrane may include an elongated porous ceramic body having a first end, a second end, and an outer peripheral edge surface extending between the first and second ends. The porous ceramic body, moreover, defines one or more longitudinal flow channels, each of which is defined by an inner surface, that extend between the first and second ends. And to render the membrane organophobic, hydrophilic organic acid molecules are chemically bound to and within the porous ceramic body from the inner surfaces of the flow channels to the outer peripheral edge surface. Methods and systems that utilize the functionalized porous ceramic membrane are also disclosed.

Description

SEPARATION OF ORGANIC COMPOUNDS FROM LIQUID

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application Number 61/897,593, filed on October 30, 2013, and U.S. Patent Application No. 13/087,706 (published as U.S. 2012/0261343), filed on April 15, 2011. The entire contents of each of the above-identified applications are incorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to an apparatus, a method, and a system for treating liquids, more specifically, for separating organic compounds from a liquid feed.

BACKGROUND

Removing organic compounds from liquids is important in many industries, including the oil and gas industry. However, current methods of doing so suffer from various limitations, including low liquid flow rates, blockage of the filtration element, and the need for performing multiple steps to sufficiently complete the separation process.

SUMMARY

In some embodiments, a functionalized porous ceramic membrane is used to separate non-polar organic compounds from a liquid feed that includes a mixture or emulsion of non-polar organic compounds, such as hydrocarbons, and polar compounds, such as water. The functionalized porous ceramic membrane comprises a ceramic body functionalized with hydrophilic organic acid molecules such that the membrane is rendered organophobic. Additional aspects of the present invention pertain to methods for separating non-polar organic compounds from a liquid feed. Such methods generally comprise: (1) providing the above-described functionalized porous ceramic membrane; and (2) flowing the liquid feed through the membrane. Other embodiments of the present invention pertain to systems for separation of non-polar organic compounds from a liquid feed. Such systems generally comprise: (1) a plurality of the above-described functionalized porous ceramic membranes; and (2) a flowing unit that enables the liquid feed to flow through the plurality of the functionalized porous ceramic membranes. In some embodiments, the flowing unit houses the functionalized porous ceramic membranes operating in cross-flow filtration. Additional embodiments of the present invention pertain to methods of making the above-described porous membranes.

As set forth in more detail below, the functionalized porous ceramic membranes, methods, and systems of the present invention provide numerous improvements in separating various non-polar organic compounds from liquid feeds such as industrial wastewater feeds. In addition, it is envisioned that the membranes, methods, and systems of the present invention can provide various improved applications, including the treatment of oil-contaminated sea water and the purification of frac water.

BRIEF DESCRIPTION OF THE DRAWINGS

One or more preferred exemplary embodiments of the invention will hereinafter be described in conjunction with the appended drawings, wherein like designations denote like elements, and wherein: FIG. 1 illustrates several functionalized porous ceramic membranes in accordance with one or more embodiments of the present disclosure;

FIG. 2 illustrates end portions of several functionalized porous ceramic membranes in accordance with one or more other embodiments of the present disclosure; FIG. 3 is a schematic illustration of a method for reacting alumina and a carboxylic acid to functionalize the alumina with hydrophilic carboxylate groups (R- COO-); FIG. 4 is a schematic illustration of a ceramic that has been functionalized with cysteic acid (H03SCH(NH₂)COO-), showing the neutral and Zwitterionic forms of cysteic acid;

FIG. 5 is a graphical representation of the molecular structure of various hydrophilic organic acid molecules that contain carboxylic acid functional groups;

FIG. 6 A is a schematic cross-sectional illustration of a porous ceramic body prior to being functionalized with hydrophilic organic acid molecules in accordance with one embodiment of the present disclosure;

FIG. 6B is a schematic illustration of a functionalized porous ceramic membrane in accordance with one embodiment of the present disclosure;

FIG. 7 is a scanning electron microscope (SEM) image of a surface of a functionalized porous ceramic membrane, in accordance with one embodiment of the present disclosure, wherein the surface of the membrane has been functionalized with L-cysteic acid; FIG. 8 is an SEM image of a surface of a functionalized porous ceramic membrane, in accordance with another embodiment of the present disclosure, wherein the surface of the membrane has been functionalized with L-cysteic acid;

FIG. 9 A is an SEM image of a surface of a functionalized porous ceramic membrane, in accordance with yet another embodiment of the present disclosure, wherein the surface of the membrane has been functionalized with a hydrophilic organic acid molecule;

FIG. 9B is an SEM image of a surface of a conventional ceramic membrane;

FIG. 9C is an SEM image of the surface of the ceramic membrane of FIG. 9A at a higher magnification rate; FIG. 10 is a partial perspective view of one end a flowing unit that houses a plurality of functionalized porous ceramic membranes in accordance with one embodiment of the present disclosure; and

FIG. 11 is perspective view of a flowing unit that houses a plurality of functionalized porous ceramic membranes in accordance with one embodiment of the present disclosure.

DETAILED DESCRIPTION

Oily wastewaters are an inconvenient byproduct of many industrial processes. Ratios of hydrocarbon water emulsions vary greatly from industry to industry. Nonetheless, oily wastewater represents a significant environmental hazard that cannot be easily assuaged. Furthermore, oily wastewater results in a significant economic drain, especially since the water must be cleaned up prior to use. Many techniques exist for the separation of these emulsions, although all have significant drawbacks to consider.

For instance, in recent years, membrane filtration has been shown to be one of the best methods for commercial separation of oily wastewaters. This is due to processing factors, such as recyclability of throughput material in cross flow membrane assemblies, ease of cleaning, as well as highly pure permeate with no chemical tainting. A significant drawback of membrane purification is membrane fouling, which can be due to a number of factors, such as adsorption inside the membrane, deposition on the membrane surface to form a cake layer, and blocking of the membrane pores. Hydrophilic membranes have been shown to achieve anti- fouling properties. In fact, in many ways, hydrophilic membranes are preferable over hydrophobic membranes. Without being bound by theory, it is envisioned that such properties are due to hydrophilic membranes being less sensitive to adsorption.

Accordingly, several methods, such as surface segregation, surface coating, and surface graft polymerization, have been utilized to enhance surface hydrophilicity in order to control the antifouling properties of membrane materials. However, many of these methods suffer from various limitations. For instance, ceramic membranes offer good commercialization methods for separation. However, traditionally, ceramic membranes require very small pores (<10 nm) for oil-water separation. Such small pore sizes may decrease fluid flow rate and cause clogging.

To overcome problems with decreased flow rate and clogging, the use of large membranes or high pressure may be required. Another method to overcome these problems is through permeate back-flush in order to declog the membrane. However, such methods are only partially effective and present many technical burdens. The smaller the pore size, the easier it is to become clogged.

To address the aforementioned problems, one aspect of the present disclosure provides methods of separating non-polar organic compounds (e.g., hydrocarbons) from a liquid feed (e.g., frac water, saltwater, etc.). Such methods generally comprise: (1) providing a functionalized porous ceramic membrane that has been functionalized with hydrophilic organic acid molecules (e.g., cysteic acid); and (2) flowing the liquid feed through the functionalized porous ceramic membrane to achieve cross-flow filtration. Other embodiments of the present invention pertain to systems for separation of non-polar organic compounds from a liquid feed. Such systems generally comprise a plurality of functionalized porous ceramic membranes, as described, and a flowing unit that houses the plurality of the functionalized porous ceramic membranes and enables a liquid feed to flow through the membranes. Additional embodiments of the present invention pertain to the above-described functionalized porous ceramic membranes and methods of making them.

FIGS. 1-2 illustrate several embodiments of functionalized porous ceramic membranes 10 for separating non-polar organic compounds from a liquid that includes a mixture or emulsion of non-polar organic compounds (e.g., hydrocarbons) and polar compounds (e.g., water. The functionalized porous ceramic membrane 10 comprises an elongated porous ceramic body 12 having a first end 14, a second end 16, and an outer peripheral edge surface 18 extending longitudinally between perimeters of the first and second ends 14, 16. The porous ceramic body 12 defines one or more longitudinal flow channels 20, each of which extends between the first end 14 and the second end 16, and the ceramic structure surrounding the flow channels 20 exhibits an average pore size ranging from about 0.01 μιη to about 5 μιη and, more narrowly, from about 0.01 μιη to about 1.4 μιη. These longitudinal flow channels 20 may vary in size, cross-sectional profile, and number, as represented in FIGS. 1-2, with a typical body defining anywhere from 1 to 100 flow channels 20 that have diameters ranging from 2 mm to 8 mm. The porous ceramic body 12 is preferably cylindrical in shape, although it is not necessarily required to be.

The porous ceramic body 12 may be composed of any of a wide variety of ceramic materials. For instance, in some embodiments, the porous ceramic body 12 can be composed of a crystalline ceramic oxide such as, for example, alumina (A1₂0₃,), titania (Ti0₂,), silica (Si0₂), magnesia (MgO), and/or zirconia (Zr0₂). Other ceramic materials known to those skilled in the art may of course be used as well. The porous ceramic body 12 can be fabricated along with its flow channels 20 by any suitable ceramic preparation technique. Several ceramic preparation techniques that are applicable here include ceramic shell casting, powder ceramic processing, injection molding, or hot wax molding.

The longitudinal flow channels 20 include inner surfaces 22 that are preferably provided by one or more porous ceramic coatings 24, as shown best in FIGS. 6A-6B, that are often prepared and deposited by the manufacturer of the porous ceramic body 12. These ceramic coatings 24 may have the same average pore size as the ceramic body 12, or a reduced average pore size, and may function to enhance the surface area within the flow channels 20 to improve filtration and separation mechanics as well as reduce fouling. Referring now specifically to FIG. 6A, which depicts a general and exaggerated cross-sectional illustration of part of a flow channel 20, a first porous ceramic coating 24a may applied over and along the length of the ceramic body 12 within the flow channel 20. The first porous ceramic coating 24a may be applied by a two-step application and sintering process, which will be explained in more detail below, and may have a porosity that exhibits an average pore size that ranges from of about 0.01 μιη to about 1.4 μιη, and may have a thickness in the range of about 0.5 mm to about 1 mm. The composition of the first porous ceramic coating 24a may be the same or different from that of the porous ceramic body 12, and is preferably composed of a crystalline ceramic oxide such as alumina (A1203,), titania (Ti02,), silica (Si02), Magnesia (MgO), and/or zirconia (Zr02). The first porous ceramic coating 24a may be formed in place by, first, extruding a viscous ceramic paste through the longitudinal flow channels 20. The viscous ceramic paste includes particles of the ceramic that is intended to be formed. When extruded through the flow channels 20 of the porous ceramic body 12, the viscous ceramic paste deposits ceramic particles at and along the flow channels 20 within the open pores of the porous ceramic body 12. After the viscous ceramic paste has been extruded through the flow channels 20, a "green" ceramic particle layer is present on the porous ceramic body 12 within the flow channels 20, which is then sintered in a furnace at a temperature ranging from about 1800°C to about 3000°C to arrive at the first porous ceramic coating 24a. Additionally, if desired, the first porous ceramic coating 24a may be slip-coated with a ceramic solution that includes ceramic particles of preferably the same composition as the viscous ceramic paste. The ceramic solution deposits more particles, which, like before, may be sintered in a furnace at a temperature ranging from about 1800°C to about 3000°C, to thereby increase the thickness of the first porous ceramic coating 24a. The slip-coating procedure may be repeated, although it does not necessarily have to be, in order to obtain the desired thickness of the first porous ceramic coating 24a, which preferably ranges from about 0.5 mm to about 1.0 mm.

Additional porous ceramic coatings of yet smaller average pore size may be formed over the first porous ceramic coating 24a, as shown in FIG. 6A, although such additional coatings are not necessarily required. For example, a second porous ceramic coating 24b, which is defined by an average pore size that ranges from about 5 nm to about 100 nm, may be formed over the first porous ceramic coating 24a. Further, a third porous ceramic coating 24c, defined by an average pore size that ranges from about 1 nm to about 5 nm, may be formed over the second porous ceramic coating 24b. These additional porous ceramic coatings 24b, 24c may be formed using some or all of the same techniques previously-described with respect to the first porous ceramic coating 24a albeit with ceramic particles of smaller grain sizes. And although the thicknesses of the additional ceramic coatings 24b, 24c may vary depending on a variety of factors, in some instances the second porous ceramic coating 24b and the third porous ceramic coating 24c may have thicknesses that range from about 0.3 mm to 1.0 mm, if they are even applied in the first place. The functionalized porous ceramic membrane 10 is derived by functionalizing the porous ceramic body 12, including its porous ceramic coatings 24 within the longitudinal flow channels 20, with hydrophilic organic acid molecules to render the entire structure organophobic. This may involve exposing the porous ceramic body 12 and its porous ceramic coatings 24 to hydrophilic organic acid molecules that contain a functional group capable of reacting with the available ceramic materials to form an organo-metal bond. Non-limiting examples of such molecules include carboxylic acids, acidic molecules, basic molecules, zwiterrionic molecules, phenyl amines, phenyl amidines (e.g., 1,3- diphenylamidine), amino pyridines (e.g., methylaminopyridine), and combinations thereof. The term organophobic, as used herein, refers to the fact that the porous membrane 10 is predisposed to repel non-polar organic compounds, such as hydrocarbons, and to segregate such organic compounds from water.

The hydrophilic organic acid molecules may include a carboxylic acid functional group, which can react with the metal component of the ceramic materials to form an organo-metal bond, as is graphically depicted in FIG. 3. These molecules may also be difunctional, meaning that the molecules include other functional groups, such as sulfonic acid or hydroxyl functional groups, in addition to the carboxylic acid group, or they may simply include hydrocarbon tails that are attached to the carboxylic acid group. In preferred embodiments, the hydrophilic organic acid molecules may be carboxylic acids, which have the general formula RC0₂H. Exemplary carboxylic acids that may be used to functionalize the porous ceramic body 12 and any porous ceramic coatings 24 include cysteic acid, 3,5-diiodotyrosine, trans-fumaric acid, malonic acid, octanoic acid, stearic acid, 3,5-dihydroxybenzoic acid, parahydroxy benzoic acid, as shown in FIG. 5, and combinations thereof. FIG. 4 graphically illustrates an exemplary functionalized porous ceramic membrane 10 in which the porous ceramic body 12 and its porous ceramic coatings 24 are functionalized with cysteic acid in zwitterionic (right) and neutral (left) forms. FIGS. 7 and 8 are scanning electron microscope images of a porous ceramic surface functionalized with L-cysteic acid.

The hydrophilic organic acid molecules are chemically bound to and throughout the entire pore structure of the porous ceramic body 12, as well as the entire pore structure of the porous ceramic coating(s) 24. In other words, the hydrophilic organic acid molecules are not confined solely to the surfaces of the ceramic coating(s) 24 or to the surfaces of the porous ceramic body 12, but are in fact dispersed into and throughout the pores of the porous ceramic coatings(s) 24 and the porous ceramic body 12 from the inner surfaces 22 of the longitudinal flow channels 20 to the outer peripheral edge surface 18. Dispersing the hydrophilic organic acid molecules throughout the porous ceramic body 12 and the porous ceramic coatings 24 provides the membrane 10 with its capacity to selectively separate non-polar organic compounds from polar compounds such as water. In particular, as a liquid feed containing a mixture or emulsion non-polar organic compounds and polar compounds is passed through the functionalized porous ceramic membrane 10, the hydrophilic organic acid molecules repel non-polar organic compounds and reject them from the pores of the porous ceramic coating(s) 24 and the underlying porous ceramic body 12 as a liquid feed flows along the longitudinal flow channels 20. The hydrophilic organic acid molecules can be exposed to, and reacted with, the ceramic materials of the porous ceramic body 12 and the porous ceramic coating(s) 24 by directing a reaction solution that contains the hydrophilic organic acid molecules through the longitudinal flow channels 20. For example, a reaction solution containing 2-5 wt.% of the hydrophilic organic acid molecules (as powder added to deionized water) can be pumped from a feed tank to a heater, where the solution is heated up to about 80°C-95°C, and then through the longitudinal flow channels 20 of the porous ceramic body 12. As the reaction solution flows through the flow channels 20, some of it permeates from the inner surfaces 22 of the flow channels 20 and across the outer peripheral edge surface 18 of porous ceramic body 12. The solution that permeates through the porous ceramic body 12 and the solution that exits the flow channels 20 is recirculated back to the feed tank and eventually pumped back through the longitudinal flow channels 20 as part of a continuous process that may last for 12 hours to 24 hours or until the desired level of functionalization has been achieved. In operation, a liquid feed containing an upstream concentration of organic compounds flows through the longitudinal flow channels 20 of the functionalized porous ceramic membrane 10 from an inlet at the first end 14 of the ceramic body 12 to an outlet at the second end 16 of the ceramic body 12. The path or paths that the liquid feed takes through the flow channels 20 brings the liquid feed into intimate contact with the porous ceramic coating(s) 24 such as the first porous ceramic coating 24a and possibly, if present, the second and third porous ceramic coatings 24b, 24c described above. As the liquid feed flows along the flowing channels 20, non-polar organic compounds in the liquid are rejected from the functionalized surface of the porous ceramic coating(s) 24 and the porous ceramic body 12 and, therefore, remain in the liquid feed passing through the flowing channels 20. The liquid feed, upon exiting the membrane 10 at the outlet or concentrate side of the membrane 10, thus contains a downstream concentration of organic compounds that is greater than the initial concentration of organic compounds. At the same time, the organophobic membrane 10 allows water along with polar components of the liquid (as long as their molecular size does not exceed the pore size of the membrane 10) to flow through the porous ceramic coating(s) 24 and the porous ceramic body 12 transverse to the flow direction of the liquid feed through the flow channels 20, and eventually across the outer peripheral edge surface 18 or permeate side of the porous membrane 10.

The systems of the present invention are designed for the separation of non-polar organic compounds from various liquid feeds. Such systems generally comprise: (1) a plurality of functionalized porous ceramic membranes 10; and (2) a flowing unit 30 that enables the liquid feed to flow through the plurality of functionalized porous ceramic membranes 10. The flowing unit 30 houses the plurality of the functionalized porous ceramic membranes 10 and accommodates the separation mechanism of the membranes 10— that is, the separation of water through the membranes 10 transverse to the flow of liquid feed through the flow channels 20. While a wide variety of flowing unit constructions may be employed to house the functionalized porous ceramic membranes 10, direct a liquid feed through the membranes 10, and keep the permeate separate from the liquid feed entering and exiting the membranes 10, one particularly effective example is shown in FIGS. 10- 11. The flowing unit 30 may include a canister 32, an inlet diffuser 34, an outlet diffuser 36, and a support and sealing assembly 38 situated on opposite ends of the canister 32. The canister 32 is a hollow and elongated structure that defines an interior space 40. A plurality of the functionalized porous ceramic membranes 10, such as anywhere from 10 to 200 of them, extend through the interior space 40 from an inlet end 42 of the canister 32 to an outlet end 44.

The plurality of functionalized porous ceramic membranes 10 are held in place generally parallel to one another by support and sealing assemblies 38. To be more specific, as shown, each support and sealing assembly 38 may include a sealing plate 46 and a guide plate 48. The sealing plate 46 (shown only at the inlet end 32) includes a series of interconnected sealing rings 50 that include two coaxially-aligned and axially-spaced metal washers. Each sealing structure ring receives an end— either the first end 14 or the second end 16— of a porous membrane 10 and fluidly seals the entrance and the exit of the flow channels 20 from the interior space 40 of the canister 32. The guide plate 48 is disposed over the sealing plate 46 and includes a plurality of apertures 52 for guiding liquid into (inlet end 42) or out of (outlet end 44) the porous membranes 10. When used to separate non-polar organic compounds from a liquid feed— e.g., an industrial wastewater feed such as, for example, a frac water feed— the flowing unit 30 is typically used in conjunction with multiple similar flowing units arranged in series or in parallel, although at times the operation of only one such flowing unit 30 is described below. In practice, a flow of liquid feed having an upstream concentration of non-polar organic compounds is supplied by the inlet diffuser 34 against the guide plate 48 at the inlet end 32 of the canister 32. The liquid feed then enters the plurality of flow channels 20 of the many functionalized porous ceramic membranes 10 through their accessible first or inlet ends 14. As the liquid feed flows along the flow channels 20, the organophobic nature of the functionalized porous ceramic membranes 10 repels non-polar organic materials and keeps them from infiltrating the pores of the porous ceramic coatings 24 and the ceramic body 12, while water and other polar compounds are allowed to flow transversely in that direction until they eventually cross the outer peripheral edge surface 18 or permeate side of the porous membranes 10 and into the interior space 40 of the canister 32. An aqueous film may also form along the longitudinal flow channels 20 as a result of the transverse flow of water into and across the membrane 10, which functions to further inhibit the passage of non-polar organic compounds and help prevent fouling. The liquid feed that exits the longitudinal flow channels 20 and is directed away from the canister 32 by the outlet diffuser 36 has a downstream concentration of non-polar organic compounds that is greater than the upstream concentration. This is due to the fact that water and other polar compounds have been extracted from the liquid feed and introduced into the interior space 40 of the canister 32 as the liquid feed passed through the functionalized porous ceramic membranes 10. Within the interior space 40, therefore, is a permeate comprised of water having a very low concentration of non-polar organic compounds or in some cases being free of such compounds within acceptable tolerance ranges as understood by those skilled in the art. The permeate that accumulates in the interior space 40 of the canister 32 is eventually forced or drawn out of the canister 32 through a permeate outlet 54 as a result of the flow pressure supplied by the liquid feed passing through the functionalized porous ceramic membranes 10 or by some other mechanism such as, for example, a pump. The liquid feed may be re-circulated through the flowing unit 30 multiple times to derive more and more permeate with each pass.

The functionalized porous ceramic membranes, methods, and systems of the present invention can be used to separate various types of non-polar organic compounds from various liquid feeds. For instance, in some embodiments, the non-polar organic compounds to be separated are hydrocarbons, such as crude oil, and the liquid feed may be water, such as saltwater that has been contaminated with crude oil from an oil spill.

Another application of the functionalized porous ceramic membranes, methods, and systems of the present invention is the pretreatment in the purification of sea water. By way of background, reverse osmosis has been a general method for the desalination of sea water. Unfortunately, the desalination resins are very susceptible to organic and biological fouling that rapidly destroy the usefulness of the system. Using the present invention as a pre-treatment step, sea water can be easily and cheaply purified of organic and biological material in order to make the desalination process more economically viable. In other embodiments, the functionalized porous ceramic membranes, methods, and systems of the present invention may be used to purify frac water, such as frac water resulting from the hydraulic fracturing of gas containing shale reservoirs. Such applications of the present invention can be beneficial, especially in view of declining well production per acre surface density (number of wells per acre) and increases in frac water usage (as much as 1,000,000 gallons per well). In particular, the membranes, methods, and systems of the present invention can be used to purify post-production frac water to remove organic contaminants. Such purified water can be re-introduced into the environment or re-used for additional fracking.

It has thus been demonstrated from the above results that a functionalized porous ceramic membrane is capable of screening non-polar hydrocarbons from hydrocarbon- water emulsions. Without being bound by theory, it is envisioned envision that the above results are due to attraction of polar molecules like water to the surface of the membrane, while non-polar molecules are rejected away from it. This interaction allows formation of an aqueous layer on the surface of the filter, which helps prevent fouling and more importantly provides an entropic barrier for which the oil droplets contained within the emulsions studied cannot cross.

It is to be understood that the foregoing is a description of one or more preferred exemplary embodiments of the invention. The invention is not limited to the particular embodiment(s) disclosed herein, but rather is defined solely by the claims below. Furthermore, the statements contained in the foregoing description relate to particular embodiments and are not to be construed as limitations on the scope of the invention or on the definition of terms used in the claims, except where a term or phrase is expressly defined above. Various other embodiments and various changes and modifications to the disclosed embodiment(s) will become apparent to those skilled in the art. All such other embodiments, changes, and modifications are intended to come within the scope of the appended claims.

As used in this specification and claims, the terms "for example," "for instance," "such as," and "like," and the verbs "comprising," "having," "including," and their other verb forms, when used in conjunction with a listing of one or more components or other items, are each to be construed as open-ended, meaning that the listing is not to be considered as excluding other, additional components or items. Other terms are to be construed using their broadest reasonable meaning unless they are used in a context that requires a different interpretation.

Claims

1. A functionalized porous ceramic membrane for separating non-polar organic compounds from a liquid feed, the membrane comprising:

an elongated porous ceramic body having a first end, a second end, and an outer peripheral edge surface extending between the first and second ends, the porous ceramic body defining one or more longitudinal flow channels, each of which is defined by an inner surface, that extend between the first and second ends, and wherein the porous ceramic body is functionalized with hydrophilic organic acid molecules to render the membrane organophobic, the hydrophillic organic acid molecules being chemically bound to and within the porous ceramic body from the inner surfaces of the flow channels to the outer peripheral edge surface.

2. The functionalized porous ceramic membrane set forth in claim 1, wherein the inner surfaces of the longitudinal flow channels are provided by one or more porous ceramic coatings.

3. The functionalized porous ceramic membrane set forth in claim 2, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 1.4 μιη, and wherein a first porous ceramic coating is disposed over the porous ceramic body within the longitudinal flow channels, the first porous ceramic coating in each flow channel having an average pore size ranging from about 0.01 μιη to about 1.4 μιη.

4. The functionalized porous ceramic membrane set forth in claim 3, wherein each of the porous ceramic body and the first porous ceramic coating are composed of a crystalline ceramic oxide.

5. The functionalized porous ceramic membrane set forth in claim 4, wherein each of the porous ceramic body and the first porous ceramic coating are composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

6. The functionalized porous ceramic membrane set forth in claim 1, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 5 μηι and is composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

7. The functionalized porous ceramic membrane set forth in claim 1, wherein the hydrophilic organic acid molecules include a functional group that can react with the ceramic of the porous ceramic body to form an organo-metal bond.

8. The functionalized porous ceramic membrane set forth in claim 7, wherein the hydrophilic organic acid molecules include a carboxylic acid functional group.

9. The functionalized porous ceramic membrane set forth in claim 8, wherein the hydrophilic organic acid molecules include one or more of cysteic acid, 3,5- diiodotyrosine, trans-fumaric acid, malonic acid, octanoic acid, stearic acid, 3,5- dihydroxybenzoic acid, parahydroxy benzoic acid groups, or combinations thereof.

10. The functionalized porous ceramic membrane set forth in claim 9, wherein the hydrophilic organic acid molecules include cysteic acid.

11. A method for separating non-polar organic compounds from a liquid feed, the method comprising:

providing a functionalized porous ceramic membrane that includes an elongated porous ceramic body having a first end, a second end, and an outer peripheral edge surface extending between the first and second ends, the porous ceramic body defining one or more longitudinal flow channels, each of which is defined by an inner surface, that extend between the first and second ends, and wherein the porous ceramic body is functionalized with hydrophilic organic acid molecules to render the membrane organophobic, the hydrophillic organic acid molecules being chemically bound to and within the porous ceramic body from the inner surfaces of the flow channels to the outer peripheral edge surface;

flowing a liquid feed that includes a mixture or emulsion of non-polar organic compounds and polar compounds through the longitudinal flow channels of the membrane, the membrane allowing polar compounds to flow transversely from the inner surfaces of the longitudinal flow channels across the outer peripheral edge surface of the porous ceramic body while rejecting non-polar organic compounds, the liquid feed having a greater concentration of non-polar organic compounds upon exiting the longitudinal flow channels than when entering the flow channels.

12. The method set forth in claim 11, wherein the liquid feed includes hydrocarbons and water.

13. The method set forth in claim 12, wherein the liquid feed includes frac water.

14. The method set forth in claim 13, wherein the inner surfaces of the longitudinal flow channels are provided by one or more porous ceramic coatings.

15. The method set forth in claim 14, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 1.4 μιη, and wherein a first porous ceramic coating is disposed over the porous ceramic body within the longitudinal flow channels, the first porous ceramic coating in each flow channel having an average pore size ranging from about 0.01 μιη to about 1.4 μιη.

16. The method set forth in claim 15, wherein each of the porous ceramic body and the first porous ceramic coating are composed of a crystalline ceramic oxide.

17. The method set forth in claim 16, wherein each of the porous ceramic body and the first porous ceramic coating are composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

18. The method set forth in claim 11, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 5 μιη and is composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

19. The method set forth in claim 11, wherein the hydrophilic organic acid molecules include a functional group that can react with the ceramic of the porous ceramic body to form an organo-metal bond.

20. The method set forth in claim 19, wherein the hydrophilic organic acid molecules include a carboxylic acid functional group.

21. The method set forth in claim 20, wherein the hydrophilic organic acid molecules include one or more of cysteic acid, 3,5-diiodotyrosine, trans-fumaric acid, malonic acid, octanoic acid, stearic acid, 3,5- dihydroxybenzoic acid, parahydroxy benzoic acid groups, or combinations thereof.

22. A system for separating non-polar organic compounds from polar compounds, the system comprising:

a flowing unit that comprises a canister, the canister defining an interior space and having an inlet end and an outlet end; and

a plurality of functionalized porous ceramic membranes housed within the canister and passing through the interior space, each of the functionalized porous ceramic membranes having an elongated porous ceramic body having a first end, a second end, and an outer peripheral edge surface extending between the first and second ends, the porous ceramic body defining one or more longitudinal flow channels, each of which is defined by an inner surface, that extend between the first and second ends, and wherein the porous ceramic body is functionalized with hydrophilic organic acid molecules to render the membrane organophobic, the hydrophillic organic acid molecules being chemically bound to and within the porous ceramic body from the inner surfaces of the flow channels to the outer peripheral edge surface;

wherein, during flow of a liquid feed from the inlet end of the canister to the oulet end via the longitudinal flow channels of the functionalized porous ceramic membranes, polar compounds flow transversely through the membranes and into the interior space of the canister while non-polar organic compounds remain in the liquid feed such that an outlet concentration of non-polar organic compounds at the outlet of the canister is greater than in inlet concentration of organic compounds at the inlet of the canister.

23. The system set forth in claim 22, wherein the liquid feed includes hydrocarbons and water.

24. The system set forth in claim 23, wherein the liquid feed includes frac water.

25. The system set forth in claim 22, wherein the inner surfaces of the longitudinal flow channels are provided by one or more porous ceramic coatings.

26. The system set forth in claim 25, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 1.4 μιη, and wherein a first porous ceramic coating is disposed over the porous ceramic body within the longitudinal flow channels, the first porous ceramic coating in each flow channel having an average pore size ranging from about 0.01 μιη to about 1.4 μιη.

27. The system set forth in claim 26, wherein each of the porous ceramic body and the first porous ceramic coating are composed of a crystalline ceramic oxide.

28. The system set forth in claim 27, wherein each of the porous ceramic body and the first porous ceramic coating are composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

29. The method set forth in claim 22, wherein the porous ceramic body has an average pore size ranging from about 0.01 μιη to about 5 μιη and is composed of alumina, titania, silica, magnesia, zirconia, or a combination thereof.

30. The system set forth in claim 22, wherein the hydrophilic organic acid molecules include a functional group that can react with the ceramic of the porous ceramic body to form an organo-metal bond.

31. The system set forth in claim 30, wherein the hydrophilic organic acid molecules include a carboxylic acid functional group.

32. The system set forth in claim 31, wherein the hydrophilic organic acid molecules include one or more of cysteic acid, 3,5-diiodotyrosine, trans-fumaric acid, malonic acid, octanoic acid, stearic acid, 3,5- dihydroxybenzoic acid, parahydroxy benzoic acid groups, or combinations thereof.