Separation Method and System

Abstract

The present invention relates to various systems and processes for the separation of organic compounds using semipermeable materials, such as nanoporous materials. In various implementations, the nanoporous material includes a membrane, a substrate, or a combination of a membrane and a substrate. In some implementations, the nanoporous material is a liquid-impregnated material that includes a wetting fluid inserted into the pores of the material. The nanoporous material can be wetted with one or more first organic compounds, such that the nanoporous material is preferentially permeable to one or more second organic compounds and completely or substantially impermeable to other compounds. In some implementations, the nanoporous material is wetted with alcohol, such that the nanoporous material is preferentially permeable to ethanol and completely or substantially impermeable to other compounds, such as water or other compounds or mixtures. In some implementations, the selective ethanol permeation of the nanoporous material can occur even if the other compounds have smaller molecules than ethanol.

Description

[Technical Field]

[0001] The present disclosure relates to semi-permeable materials and the removal of organic compounds. [Background technology]

[0002] Separation techniques that use selective barriers to remove organic compounds can be useful in a variety of fields, such as food and beverage processing, chemical and pharmaceutical manufacturing, water treatment, fuel (e.g., oil and gas) production, and medical applications (e.g., blood treatments such as dialysis). The selective barrier can be a semipermeable membrane that allows some molecules to pass while preventing others from passing through. The properties of the semipermeable membrane can be selected based on the molecules to be removed from the starting material. The semipermeable membrane can be fabricated from biological or synthetic materials and can have pore sizes selected based on the size of the molecules to be removed. In some applications, it may be desirable to remove alcohol from various fluids, including beverages, blood, and fuel.

[0003] For example, there is growing interest worldwide in low-alcohol and non-alcohol adult beverages. Although low-alcohol and non-alcohol adult beverages have been available for many years, available low-alcohol and non-alcohol adult beverages have not yet provided satisfactory flavor profiles that can mimic or substitute for traditional alcoholic beverages.

[0004] For example, some methods for producing low-alcohol or non-alcoholic beverages involve inhibiting alcoholic fermentation during the production process, thereby reducing the alcohol content produced by fermentation. Other methods involve heating alcoholic beverages to 175°F for 15-20 minutes, thereby evaporating the ethanol in the beverage. However, the low-alcohol or non-alcoholic beverages obtained by these methods generally do not have the flavor of their alcoholic counterparts. In many cases, the resulting low-alcohol or non-alcoholic beverages either have minimal flavor or are so bad that they are undrinkable. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a need to produce low-alcohol or non-alcohol adult beverages that taste like their alcoholic counterparts and that mimic or serve as a substitute for traditional alcoholic beverages. [Means for solving the problem]

[0006] The present disclosure is directed to systems and processes for separating organic compounds using semipermeable materials. In various implementations, the semipermeable material includes a membrane, a substrate, or a combination of a membrane and a substrate. In some implementations, the semipermeable material can include one or more membranes and / or substrates. In various implementations, the semipermeable material can be wetted with one or more first organic compounds, such that the semipermeable material preferentially allows one or more second organic compounds to permeate the semipermeable material and is completely or substantially impermeable to one or more other compounds. In some implementations, the semipermeable material is a liquid-impregnated material.

[0007] In various implementations, the semipermeable material comprises a nanoporous material. In some implementations, the nanoporous material comprises a membrane, a substrate, or a combination of a membrane and a substrate. In some implementations, the nanoporous material can comprise one or more membranes and / or substrates. In various implementations, the nanoporous material can be wetted with one or more first organic compounds, such that the nanoporous material preferentially allows one or more second organic compounds to permeate the nanoporous material and is completely or substantially impermeable to one or more other compounds. In some implementations, the nanoporous material is a liquid-impregnated material. While nanoporous materials are used in describing various aspects of the methods and systems, it will be understood that the semipermeable materials described herein can be used as compatible with the separation methods and systems.

[0008] In some implementations, the nanoporous material is wetted with a first organic compound comprising an alcohol, such that the nanoporous material preferentially allows ethanol to permeate through the nanopores and is completely or substantially impermeable to other compounds, such as water or other compounds or mixtures. In some implementations, the nanoporous material is wetted with an alcohol, such that the nanoporous material preferentially allows ethanol to permeate through the nanopores and is completely or substantially impermeable to other compounds, such as water or other compounds or mixtures. In some embodiments, the selective ethanol permeation through the nanoporous material can occur even if other compounds (such as compounds that may impart flavor characteristics to a beverage) may have smaller sizes than ethanol and would pass through the nanoporous material more easily than ethanol molecules.

[0009] Various implementations of the systems and methods may include separating organic compounds from a fluid, the method including one or more of: wetting a nanoporous material with a wetting fluid containing a first compound; moving a second fluid across a first side of the nanoporous material at a first predetermined speed for a predetermined time, wherein the second fluid is in contact with the first side of the nanoporous material and wherein the second fluid contains at least one second compound; moving a third fluid across a second side of the nanoporous material at a second predetermined speed for a predetermined time; transferring at least one second compound from the second fluid to the third fluid through the nanoporous material; and recovering the second fluid from which at least a portion of the at least one second compound has been removed.

[0010] In some implementations, the method can include recovering the third fluid. In various implementations, the recovered third fluid can be used as a wetting fluid to wet the nanoporous material to separate the organic compounds from the fluid.

[0011] In various implementations, the semipermeable material includes a membrane, a substrate, or a combination of a membrane and a substrate. In some implementations, the semipermeable material includes a carbon-based membrane, a molybdenum-based membrane, or a carbon-based foam. In some implementations, the carbon-based membrane includes a graphene-based membrane. In some implementations, the molybdenum-based membrane includes molybdenum disulfide. In various implementations, the semipermeable material includes a substrate, such as a substrate composed of a polymeric, inorganic, and / or metallic material. In various implementations, the semipermeable substrate can be wetted with one or more first organic compounds, such that the substrate preferentially allows one or more second organic compounds to permeate the substrate and is completely or substantially impermeable to one or more other compounds.

[0012] In some implementations, the wetting fluid substantially comprises an alcohol. In various implementations, the wetting fluid comprises 20% or more by volume of alcohol. In some implementations, the wetting fluid is selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol (isopentyl alcohol), 2,2-dimethyl-1-propanol (neopentyl alcohol), cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenylmethanol, diphenylmethanol (diphenylcarbinol), and triphenylmethanol (triphenylmethanol), or a combination of any two or more thereof. In some implementations, the wetting fluid comprises an alcohol having a kinematic viscosity in the range of 0.55 to 15 cP at standard conditions. In some implementations, the wetting fluid comprises heptanol, butanol, ethanol, or a combination of any two or more thereof. In some implementations, the first organic compound comprises substantially heptanol.

[0013] In some implementations, the at least one second organic compound comprises ethanol. In various embodiments, when the at least one second organic compound comprises ethanol, transferring ethanol through the membrane from the second fluid to the third fluid preferentially allows ethanol to transfer to the third fluid while substantially preventing water from transferring through the membrane to the third fluid.

[0014] In some implementations, wetting a semipermeable material includes exposing a semipermeable membrane and / or substrate to a wetting fluid under conditions that allow the wetting fluid to enter the pores of the membrane or substrate. While various wetting methods and systems are discussed with respect to wetting a membrane, it will be understood that the methods can also be applied to wetting a substrate. In some implementations, a semipermeable material can be exposed to a wetting fluid one or more times (e.g., in one or more exposure steps).

[0015] In some implementations, wetting the membrane includes exposing the membrane to a wetting fluid under conditions that allow the wetting fluid to saturate the membrane. In some implementations, wetting the membrane can include one or more of the following: immersing or immersing the membrane in the wetting fluid, exposing the membrane to the wetting fluid under gravity and / or pressure, applying droplets of the wetting fluid to the membrane (e.g., spraying or spraying the wetting fluid onto the membrane), and vapor deposition of the wetting fluid onto the membrane, etc. Optionally, wetting the membrane can include agitating the membrane while applying the wetting fluid. In some embodiments, agitation can help the wetting fluid penetrate into the pores of the membrane. In some implementations, the membrane can be agitated using methods such as sonication or mechanical vibration.

[0016] In some implementations, wetting the film includes depositing a wetting fluid onto the film. In some implementations, deposition can involve maintaining the film in the presence of a wetting fluid in a closed system, so that the wetting fluid, present in a gas phase, can interact with the film and modify its state. In some implementations, deposition of the wetting fluid can involve heating the wetting fluid in the presence of the film in a vacuum. In some implementations, the wetting fluid can be heated to a temperature at which it transitions from a liquid phase to a gas phase (evaporates). Because the film and wetting fluid are contained in a vacuum, the wetting fluid will transition to a gas phase below its boiling point, and vapor particles can migrate to the film and be present at the film surface in a high enough concentration to modify its characteristics. The heated wetting fluid and film are maintained in the vacuum for a suitable period of time, e.g., one hour. This completes one deposition cycle.

[0017] If additional wetting fluid is desired, the deposition cycle can be performed two or more times until the desired wetting effect of the film is achieved. Optionally, the film can be maintained at a temperature below room temperature, such as below 25° C., or below 22° C., or below 20° C., or below 15° C., or below 10° C., or below 5° C., or below 0° C., or in the range of about 5° C. to about 25° C. In some implementations, wetting the film further comprises spraying at least one layer of wetting fluid onto the film.

[0018] In some implementations, pressure is applied to the second fluid on the first side of the membrane. In some implementations, pressure is applied to the second fluid on the first side of the membrane using a gas. In some implementations, the gas is a substantially inert gas. In some implementations, the pressure is 30 bar or less, or 20 bar or less, or 10 bar or less, or 5 bar or less. In some implementations, the third fluid includes water.

[0019] In some implementations, moving the second fluid across the first side of the membrane at a first predetermined velocity for a predetermined time further includes moving the second fluid tangentially across the first side of the membrane. In some implementations, moving the third fluid across the second side of the membrane at a second predetermined velocity for a predetermined time further includes moving the third fluid tangentially across the second side of the membrane. In some implementations, the second fluid is moved in a first direction across the first side of the membrane and the third fluid is moved in a second direction across the second side of the membrane, where the first direction and the second direction are the same. In some implementations, the second fluid is moved in a first direction across the first side of the membrane and the third fluid is moved in a second direction across the second side of the membrane, where the first direction and the second direction are different. In some implementations, the first direction and the second direction are opposite directions. In some implementations, the third fluid is water, and the water is moved across the second side of the membrane for a predetermined time. In some implementations, the second predetermined speed is faster than the first predetermined speed, e.g., the second predetermined speed may be in a range of 1 to 5 times faster than the first predetermined speed. In some implementations, the first predetermined speed is faster than the second predetermined speed, e.g., the first predetermined speed may be in a range of 1 to 5 times faster than the second predetermined speed. The relative difference in the speeds of fluid movement can be determined based on various factors, such as the relative volumes of the first and second fluids, the desired separation rate, and the size of the organic compounds to be separated from the fluids.

[0020] In some implementations, the film comprises a carbon-based film, a molybdenum-based film, or a carbon-based foam. In some implementations, the film further comprises a substrate. In various implementations, the nanoporous material comprises only a substrate (i.e., no film).

[0021] In some implementations, transferring the second organic compound through the membrane from the second fluid to the third fluid is achieved without adding an external substance (such as glucose) to the third fluid. In some implementations, transferring the second organic compound through the membrane from the second fluid to the third fluid is achieved without applying pressure to the second fluid, the third fluid, or both the second and third fluids. In some implementations, the second organic compound is transferred through the membrane from the second fluid to the third fluid using osmosis.

[0022] When a substrate is utilized, the second organic compound can be transferred through the substrate from the second fluid to the third fluid without the addition of an external substance (such as glucose) to the third fluid. In some implementations, the second compound can be transferred through the substrate from the second fluid to the third fluid without applying pressure to the second fluid, the third fluid, or both the second and third fluids. In some implementations, the second organic compound is transferred through the substrate from the second fluid to the third fluid using osmosis.

[0023] In various implementations, a pre-wetted nanoporous material is provided sealed in a package, the pre-wetted nanoporous material including graphene oxide, one or more substrates, or a combination of graphene oxide and one or more substrates, and a wetting fluid, wherein the wetting fluid is contained within the graphene oxide film, within the one or more substrates, or within the graphene oxide and the one or more substrates.

[0024] In some implementations, the pre-wetted nanoporous material can include a graphene oxide film.

[0025] In various implementations, a pre-wetted nanoporous material is provided sealed in a package, the pre-wetted nanoporous material including molybdenum disulfide, one or more substrates, or a combination of molybdenum disulfide and one or more substrates, and a wetting fluid, wherein the wetting fluid is contained within the molybdenum disulfide film, within the one or more substrates, or within the molybdenum disulfide and the one or more substrates.

[0026] In some implementations, the pre-wetted nanoporous material can include a molybdenum disulfide film.

[0027] In various implementations, a pre-wetted nanoporous material is provided that is sealed in a package, the pre-wetted nanoporous material including a carbon-based foam, one or more substrates, or a combination of a carbon-based foam and one or more substrates, and a wetting fluid, wherein the wetting fluid is contained within the carbon-based foam, within the one or more substrates, or within the carbon-based foam and the one or more substrates.

[0028] In some implementations, the pre-wetted nanoporous material includes a substrate. In various implementations, a wetting fluid is contained within the substrate. In some implementations, the one or more substrates include one or more polymer layers or polymer sheets. In some implementations, the one or more polymer layers or polymer sheets are independently selected from polyamide, polytetrafluoroethylene, polyethersulfone, polycarbonate, polyvinylidene fluoride, polysulfone, polyvinyl chloride, cellulose acetate, nitrocellulose, polyimide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, poly(4-methyl-1-pentene), poly(dimethylsiloxane), poly(arylene ether ketone), poly(etherimide), polyethersulfonamide, or a combination or mixture of any two or more thereof. In various implementations, the one or more polymer layers or polymer sheets can include a surface structure. In some implementations, the one or more substrates can include a metal mesh, aluminum, alumina, copper, activated carbon, or a combination of any two or more thereof.

[0029] In some implementations, the wetting fluid can include 20% or more by volume of alcohol. In various implementations, the wetting fluid is selected from methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol (isopentyl alcohol), 2,2-dimethyl-1-propanol (neopentyl alcohol), cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenylmethanol, diphenylmethanol (diphenylcarbinol), and triphenylmethanol (triphenylmethanol), or a combination of any two or more thereof. In some implementations, the wetting fluid can include an alcohol having a kinematic viscosity in the range of 0.55 to 15 cP at standard conditions. In some implementations, the wetting fluid includes heptanol in an amount of 20% or more by volume.

[0030] In various implementations, the pre-wetted nanoporous material can be sealed in a gas- and water vapor-proof package. In various implementations, the pre-wetted nanoporous material can be sealed in an opaque material, for example, if the nanoporous material is susceptible to light-induced modifications. In some implementations, the package can include aluminum foil. In various implementations, the package can include multiple layers of foil and plastic. In various implementations, the package can include ethylene / vinyl alcohol, polyamide, polyvinyl alcohol, polyvinylidene chloride, evaporated aluminum, silicon oxide, aluminum oxide, or a combination of any two or more thereof. In various implementations, the package for the pre-wetted nanoporous material can include a pouch, vacuum bag, or tray.

[0031] In various implementations, the pre-wetted nanoporous material sealed in a package can further include a quantity of free wetting fluid within the package.

[0032] In some implementations, the pre-wetted nanoporous material sealed in the packaging may include a substrate / membrane / substrate structure. For example, the pre-wetted nanoporous material may be provided in a multilayer format, where multiple layers of substrate and membrane are provided. In some implementations, each membrane may be independently selected from a graphene-based membrane, a molybdenum-based membrane, or a carbon-based foam. In some implementations, each substrate may be independently selected from polyamide, polytetrafluoroethylene, polyethersulfone, polycarbonate, polyvinylidene fluoride, polysulfone, polyvinyl chloride, cellulose acetate, nitrocellulose, polyimide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, poly(4-methyl-1-pentene), poly(dimethylsiloxane), poly(arylene ether ketone), poly(etherimide), polyethersulfonamide, or a combination or mixture of any two or more thereof. In some implementations, the pre-wetted nanoporous material may include a nylon / graphene oxide / nylon multilayer structure.

[0033] In some implementations, a protective layer can be provided on the sealed pre-wetted nanoporous material in the package. Suitable protective layers can include polymeric films, such as any of the polymers described herein. In some embodiments, the protective polymeric film can include nylon or polycarbonate.

[0034] It should be understood that in some implementations, the various methods and devices discussed herein, when applied to alcoholic beverages, enable dealcoholization of the beverage while minimizing changes to the beverage's physicochemical attributes. As used herein, "dealcoholization" involves removing ethanol from an alcoholic beverage having an initial alcohol content to provide a beverage having a final alcohol content lower than the initial alcohol content. For example, alcoholic beverages produced by fermentation (such as beer, cider, wine, and mead) typically have an initial alcohol content of less than 15% (v / v), while alcoholic beverages produced by distillation (such as vodka, gin, tequila, whiskey, mezcal, brandy, and similar spirits) typically have an initial alcohol content of at least 20% (v / v), or between about 20% and about 40% (v / v). In some implementations, the methods and devices discussed herein may enable the removal of ethanol from alcoholic beverages to provide beverages having reduced alcohol levels (compared to their initial alcohol content) while maintaining the sensory and nutritional values ​​of the original beverages. In other words, in some implementations, the novel methods and apparatus discussed herein can produce reduced-alcohol beverages that taste the same as or very similar to the corresponding original full-alcohol-containing beverages, and that can closely resemble or substitute for traditional alcoholic beverages. In some implementations, dealcoholization can remove a desired amount of ethanol from the alcoholic beverage, for example, a relatively small amount (such as about 0.5 to about 5%), a moderate amount, or substantially all of the ethanol in the alcoholic beverage.

[0035] In some implementations, the methods and apparatus discussed herein allow for the substantial removal of ethanol, i.e., ethyl alcohol, from an alcoholic beverage while substantially preventing the removal of other compounds from the alcoholic beverage. The resulting beverage can either contain low alcohol or be substantially alcohol-free, while retaining many or most of the compounds that give the original alcoholic beverage its characteristic taste. For example, when the methods and apparatus discussed herein are applied to a brewed alcoholic beverage (e.g., stout beer) to produce a modified stout beer, the modified stout beer continues to maintain the taste characteristics of unmodified stout beer, while the modified stout beer has low alcohol or is substantially alcohol-free. As another example, when the methods and apparatus discussed herein are applied to a distilled spirit such as gin, the modified gin continues to maintain the taste and aroma characteristics of unmodified gin, while the modified gin has low alcohol or is substantially alcohol-free. In other words, in some implementations, the novel methods and apparatus discussed herein can produce low-alcohol or non-alcoholic beverages that can mimic or substitute for traditional alcoholic beverages and taste the same or very similar to the corresponding alcoholic beverages. As used herein, a low-alcohol beverage may contain 2.5% alcohol by volume (ABV) or less, or 2% ABV or less, or 1% ABV or less, or 0.5% ABV or less. [Brief explanation of the drawings]

[0036] [Figure 1A] 1 shows a close-up schematic view of several layers of graphene oxide according to some implementations. [Figure 1B] 1 shows X-ray diffraction patterns of graphene oxide films according to several implementations. [Figure 2A] 1 shows a process diagram illustrating a method for separating one or more compounds from a fluid according to some implementations. [Figure 2B]1 shows a process diagram illustrating a method for separating one or more compounds from a fluid according to some implementations. [Figure 3] 1 shows X-ray diffraction patterns and profile recordings of films formed by slot die coating according to some implementations. [Figure 4A] 1 shows a schematic diagram of alternating layers of graphene oxide and substrate according to some implementations. [Figure 4B] 1 shows a schematic diagram of alternating layers of graphene oxide and substrate according to some implementations. [Figure 4C] 1 shows a schematic diagram of alternating layers of graphene oxide and substrate according to some implementations. [Figure 5A] 1 shows a cutaway schematic of a membrane separating fluid reservoirs for filtering one or more compounds from a fluid, according to some implementations. [Figure 5B] 1 shows a cutaway schematic of a membrane separating fluid reservoirs for filtering one or more compounds from a fluid, according to some implementations. [Figure 6] 1A-1C show cutaway schematic views of fluid reservoir configurations for separating one or more compounds from a fluid, according to some implementations. [Figure 7] 1 shows ethanol concentration as a function of time when graphene oxide films were prepared by vapor wetting and spray wetting according to some implementations. [Figure 8] 1 shows ethanol concentration as a function of time when an ethanol-containing fluid is processed by one method of separating ethanol according to some implementations. [Figure 9] 1 shows ethanol concentration as a function of time when an ethanol-containing fluid is processed by one method of separating ethanol using a membrane including a substrate prepared according to some implementations. [Figure 10] 1 shows the dealcoholization performance of semipermeable membranes according to some implementations. [Figure 11] 1 shows the dealcoholization performance of semipermeable membranes according to some implementations. [Figure 12A]1 shows the dealcoholization performance of semipermeable membranes according to some implementations. [Figure 12B] 1 shows the dealcoholization performance of semipermeable membranes according to some implementations. [Figure 12C] 1 shows the dealcoholization performance of semipermeable membranes according to some implementations. [Figure 13] 1 shows the dealcoholization performance of various semipermeable membranes according to several implementations. [Figure 14] 1 illustrates the dealcoholization performance of various microporous substrates according to several implementations. DETAILED DESCRIPTION OF THE INVENTION

[0037] Various implementations of the concepts disclosed herein relate to processes and systems for removing or separating compounds from a fluid. In the context of this application, "separating" may be understood to mean reducing the amount of a compound from a fluid such that the final product or final fluid has a lower amount of the compound compared to the initial starting fluid. In some implementations, the compound separated from the fluid may be partially, substantially, or even completely removed from the fluid.

[0038] In some implementations, processes and systems for separating organic compounds from a fluid are described. In some embodiments, removing or separating organic compounds from a fluid includes removing or separating ethanol from a fluid, such as an alcoholic beverage (e.g., an alcoholic beverage produced by fermentation, brewing, distillation, etc.). In some implementations, the alcoholic beverage may include beer, wine, or liquor. In some implementations, the ethanol may be substantially or even completely removed from the alcoholic beverage. In some implementations, the ethanol may be partially removed from the alcoholic beverage. In some implementations, when ethanol is separated from a fluid, only ethanol is separated. In some implementations, when ethanol is separated from a fluid, one or more additional compounds or products are also separated along with the ethanol. In some implementations, the additional compound or product can be any chemical species. In some implementations, the additional compound or product can be any inorganic or organic molecule.

[0039] The dealcoholization of alcoholic beverages is utilized to describe certain concepts because these applications are useful for highlighting properties and advantages. However, it will be readily apparent that the methods and apparatus described herein can be used to remove other organic compounds from liquids in areas such as food and beverage processing, chemical and pharmaceutical manufacturing, water treatment, fuel (e.g., oil and gas) production, and medical applications (e.g., blood treatments such as dialysis). In some implementations, certain methods and apparatus can be used in the clarification of liquids (such as juices) or in the purification of liquids (such as fuels).

[0040] In some implementations, the performance of separation systems and methods can be assessed by observing selectivity (selectivity refers to the ability of a semipermeable material to allow ethanol transport while substantially or completely preventing the transport of other compounds, such as water) and dealcoholization rate.

[0041] In some embodiments, the selectivity of the membrane is evaluated by measuring R and R * This may involve the use of two selectivity and performance indices, denoted as R. The selectivity index may indicate the ratio of the change in alcohol content (expressed as %) to the change in volume (expressed as %) for a given separation process.

[0042]

number

[0043] The R selectivity index can be a valuable tool to probe the potential mechanisms responsible for changes in alcohol content and volume fluctuations. This value can help determine whether these changes are truly due to dealcoholization, dilution of the feed solution by the waste compartment, or whether the membrane allows the passage of both water and alcohol.

[0044] If R>1, this may indicate a minimal volume adjustment but a significant change in alcohol content, corresponding to dilution of the feed solution with waste solution (water). Conversely, a situation where there is a significant change in the volume of the feed solution but a small change in alcohol content would result in R<1, characterizing a non-selective membrane. The target value of R=1 indicates an ethanol-selective membrane.

[0045] To facilitate a comparison of the performance of membranes that exhibit slight dilution with membranes that exhibit slight competitive passage of both water and ethanol, another performance comparison factor, R * was developed.

[0046]

number

[0047] R *The performance scale approaches a value of 1 for a highly ethanol-selective membrane. In various embodiments, desirable membrane performance is one in which R is close to 1 and R * This is accompanied by a high dealcoholization rate, close to 1.

[0048] In some implementations, the separation process favors organic compounds over inorganic compounds, even though one organic compound contains larger molecules than one inorganic compound, ie, the organic compound includes ethanol and the inorganic compound is essentially water.

[0049] In some implementations, the separation or removal of organic compounds from a fluid involves using a semi-permeable material. In the context of this application, "semi-permeable" may be understood to mean a material that allows some compounds to pass (permeate) while substantially preventing the passage of other compounds.

[0050] In some implementations, the separation of organic compounds from a fluid involves using a nanoporous material. Generally, nanoporous materials can include materials having an average pore size of about 1000 nm or less, or about 900 nm or less, or about 800 nm or less, or about 700 nm or less, or about 600 nm or less, or about 500 nm or less, or about 400 nm or less, or about 300 nm or less, or about 200 nm or less, or about 100 nm or less. Nanoporous materials are used to describe certain concepts because these applications are useful for highlighting properties and advantages. However, it will be readily apparent that the pore size of a material can be selected to provide a molecular weight cutoff that enables selective removal of desired organic materials from a starting fluid. Thus, in some implementations, materials with pore sizes that are not nanoporous can be utilized. In some implementations, the separation or removal of organic compounds from a fluid involves using a microporous material.

[0051] According to some implementations, the separation method does not include adding an external substance, such as an osmotic agent including sugars (e.g., glucose) and / or salts (e.g., sodium chloride), to the third fluid. In various implementations, the separation method does not include applying pressure to the system, such as applying pressure to the second fluid, applying pressure to the third fluid, or applying pressure to the second and third fluids. In some implementations, the separation method may also include applying some external pressure to the system, for example, 30 bar or less, or 25 bar or less, or 20 bar or less, or 15 bar or less, or 10 bar or less, or 5 bar or less.

[0052] According to various implementations, the nanoporous material is initially wetted with a wetting fluid in such a way that the nanoporous material becomes saturated with the wetting fluid. In some implementations, this saturation can continue over time as one or more compounds pass through the nanoporous material. In some implementations, at least a portion of the wetting fluid is retained in the nanoporous material as the wetting fluid condenses between the pores (or nanopores) of the nanoporous material.

[0053] As discussed herein, a nanoporous material may include one or more membranes (such as a carbon-based membrane, a molybdenum-based membrane, and / or a carbon-based foam), one or more substrates (such as a polymeric or metallic substrate), or a combination thereof. The specific number and arrangement of membrane and substrate layers may be selected based on factors such as the organic compounds to be removed, the starting material, the desired amount of organic compound removal, the volume of the starting material, the volume of the fluid to be treated, and the rate of organic compound removal.

[0054] In some implementations, the nanoporous material includes a membrane. In some implementations, the nanoporous material includes a membrane combined with one or more other materials. In some implementations, the membrane can include one or more layers of graphene having a nanoporous structure. In some implementations, the membrane can include one or more layers of graphene oxide having a nanoporous structure. In some implementations, the nanoporous material can include one or more layers of molybdenum disulfide. In some implementations, the one or more other materials can include one or more layers of a substrate. In some implementations, the substrate can include a polymer (organic or inorganic) or a metallic material. In some implementations, the one or more other materials can include one or more layers of aerogel with a porous structure, which can provide structural support and / or create mixing action near the membrane surface during fluid flow across the membrane surface. In various implementations, the nanoporous material includes a substrate without a membrane. The substrate can include a polymer (organic or inorganic) or a metallic material.

[0055] In some implementations, the separation / removal process may be based on the selective permeability of a graphene oxide membrane, a molybdenum disulfide membrane, or a carbon foam, which allows ethanol to preferentially permeate the membrane over water and / or other compounds, enabling ethanol removal / separation from the fluid. In some implementations, the separation / removal process is based on the selective permeability of a wetting fluid-pretreated polymeric or metal substrate, which allows ethanol to preferentially permeate the substrate over water and / or other compounds, enabling ethanol removal / separation from the fluid.

[0056] Some suitable methods of fabricating semipermeable materials, including membranes, are disclosed below, although it should be understood that other methods of fabricating membranes may also be used.

[0057] In some implementations, the semipermeable material can include a nanoporous membrane. In some implementations, the nanoporous membrane can include a multilayer membrane. In some implementations, the multilayer membrane can include a carbon-based layer, a molybdenum-based layer, or the like. In various implementations, the carbon-based multilayer membrane can include a graphene oxide (GO) membrane. In various implementations, the molybdenum-based multilayer membrane can include a molybdenum disulfide (MoS2) membrane. In some implementations, the semipermeable membrane can include a carbon-based foam.

[0058] In some implementations, an aqueous monolayer suspension of GO or MoS2 can be prepared. In various implementations, the aqueous monolayer suspension can be assembled into a nanoporous membrane.

[0059] GO films can be produced from commercial GO suspensions purchased from GOgraphen (William Blythe Limited, UK) or Graphenea, Inc. (Cambridge, Massachusetts). In various implementations, a GO dispersion (e.g., GO flake water) can be prepared for application to a substrate. In some implementations, the GO dispersion can be subjected to centrifugation at a low speed (e.g., about 2000 rpm or some other suitable speed). In some implementations, the precipitated solids from the centrifugation process can be collected when the density of the dispersion (e.g., the remaining GO suspension) is approximately 1.003 mg L-1. -1The GO suspension is discarded until adjusted to a density of 10,000 nm. In some implementations, GO flakes larger than 10,000 nm can be discarded from the GO suspension. In some implementations, this density can be reached in about four cycles of the centrifugation process (e.g., one cycle can include centrifuging the GO-dispersed water and discarding the sediment). In some implementations, 1 mL of the GO-dispersed water remaining from one or more cycles of the centrifugation process can be diluted with water, for example, up to a volume of 10 mL. In some implementations, the water is substantially pure water. In some implementations, the water is ultrapure water, such as that obtainable from a Mili-Q® purification system. It should be understood that in some implementations, the water can be combined with one or more other compounds or products.

[0060] In some implementations, the GO solution can be diluted (e.g., 20 ml obtained from one of the sources above can be diluted in 200 ml of water). The resulting diluted solution can be sonicated for a suitable time (e.g., about 10 minutes) to enhance the separation of monolayers within the aggregates. The solution can then be centrifuged (e.g., at about 3000 g for about 30 minutes) to separate the heavier aggregates from the lighter GO monolayers. These sonication and centrifugation cycles can be repeated a desired number of times (e.g., three times) until the resulting solution contains primarily exfoliated GO monolayers. The exfoliated GO monolayers can be stored at refrigerated temperatures to minimize reduction prior to film formation.

[0061] In some implementations, the GO-in-water suspension can be sonicated in a sonicator bath for a predetermined period of time immediately prior to use. In some implementations, the predetermined period of sonication can be 5-10 minutes, or some other suitable period of time. Other methods of resuspending the GO suspension can also be used.

[0062] In some implementations, molybdenum-based films can be prepared according to a method previously reported by Eda et al. (Eda, G., Yamaguchi, H., Voiry, D., Fujita, T., Chen, M. and Chhowalla, M. (2011) Photoluminescence from Chemically Exfoliated MoS2. Nano Letters, 11, 5111-5116. https: / / doi.org / 10.1021 / nl201874w). Generally, lithium intercalation can be achieved by soaking 3 g of natural MoS2 crystals (Sigma-Aldrich) in 3 ml of 1.6 M butyllithium solution in hexane (Sigma-Aldrich) in an argon-filled flask for about 2 days. In some implementations, Li x The MoS2 can be recovered by vacuum filtration and washed with hexane (e.g., four times with 50 ml of hexane) to remove excess lithium and organic residues. Immediately thereafter (e.g., within about 30 minutes to minimize deintercalation), the Li x Exfoliation can be achieved by sonicating MoS2 in water for 1 hour. The mixture can be centrifuged several times to remove excess lithium in the form of LiOH and unexfoliated material. The product can be called an "aqueous monolayer suspension" of MoS2.

[0063] In some implementations, an aqueous monolayer suspension of GO or MoS2 can be deposited onto a porous substrate. In various embodiments, deposition onto a porous substrate can enhance the mechanical stability of the resulting nanoporous membrane. In some implementations, deposition of the aqueous monolayer suspension of GO or MoS2 can be achieved by processes such as vacuum filtration, pressure-induced filtration, or slot die coating.

[0064] In some implementations, when the semipermeable material includes one or more graphene oxide layers and a substrate, the membrane is prepared by vacuum filtration of a graphene oxide dispersion onto the substrate. In some implementations, the process for preparing the membrane includes starting with a graphene oxide dispersion. For example, the graphene oxide dispersion may include 0.4 wt% graphene oxide (GO) flakes in water. The graphene oxide dispersion is applied to the substrate in one or more steps by various methods described herein.

[0065] In some implementations, the semipermeable membrane can include a carbon-based foam. In some embodiments, the carbon-based foam can include carbon fibers stacked together in a hierarchical structure, with micrometer-scale confinement (interfiber porosity) combined with nanoscale confinement (individual fiber porosity). In some implementations, the carbon-based foam can include GO foam or carbon foam (e.g., commercially available from Kynol Europa GmbH), which are typically used as electrodes for capacitor applications. In some embodiments, the GO foam can be produced by freeze-drying a commercial GO aqueous suspension, such as those discussed elsewhere herein.

[0066] In various embodiments, a substrate can be provided on a semipermeable material (e.g., a membrane or foam). In various embodiments, the substrate can be included on one or both sides of the semipermeable material. For example, in some implementations, a carbon-based foam can be encapsulated between two substrates, thereby forming a substrate / foam / substrate structure. In some implementations, encapsulating the foam between two substrates can provide additional stability to the foam, which can be beneficial during use. In some implementations, the foam can be encapsulated between two nylon substrates or two polycarbonate substrates.

[0067] In some implementations, the substrate may include a polymer film or sheet. In some implementations, the polymer film or sheet may include a polymer selected from polytetrafluoroethylene (PTFE, commonly referred to as Teflon®), polyethersulfone (PES), polycarbonate (PC), polyvinylidene fluoride (PVDF), polysulfone (PSF), polyvinyl chloride (PVC), and polyamide (nylon), or a combination or mixture of any two or more thereof. Other suitable polymers may include, for example, cellulose acetate (CA), nitrocellulose (NC), polyimide (PI), polyacrylonitrile (PAN), polypropylene (PP), polyethylene (PE), polyvinyl alcohol (PVA), poly(4-methyl-1-pentene), poly(dimethylsiloxane) (PDMS), poly(arylene ether ketone) (PAEK), poly(etherimide) (PEI), and polyethersulfonamide (PESA), or a combination or mixture of any two or more thereof.

[0068] In some implementations, a polymer layer (such as PTFE) may or may not be laminated onto a net or nonwoven support (e.g., a polypropylene net or nonwoven polypropylene support). In some implementations, the substrate polymer may be hydrophobic. In some embodiments, "hydrophobic" refers to a polymer that is essentially nonpolar and therefore not soluble in water or other polar solvents. In some implementations, the polymer layer or polymer sheet may include a surface architecture. One suitable polymer layer that includes a surface architecture includes a polycarbonate track etch (PCTE) layer. In some implementations, the polymer sheet or polymer layer may include a polyamide, such as nylon.

[0069] In some implementations, the substrate can include metal mesh, aluminum, alumina (aluminum oxide, including anodized aluminum oxide (AAO)), copper, or activated carbon, for example, the substrate has a pore size ranging from about 10 nm to about 500 nm or from about 20 nm to about 450 nm.

[0070] In some implementations, the substrate can include a carbon substrate. In various implementations, the carbon substrate can include a nanocarbon material. In some implementations, the nanocarbon material can include one-dimensional carbon nanotubes (CNTs). Suitable CNTs can be prepared as hollow fibers. Such CNT hollow fibers can be prepared by a wet spinning method combined with pyrolysis, as discussed by Fan, X. et al., “A novel reduced graphene oxide / carbon nanotube hollow fiber membrane with high forward osmosis performance,” Desalination 451 (2019) 117-124. Graphene oxide can be fabricated using a modified Hummers method and then exfoliated in distilled water (approximately 1.0 mg / ml) under ultrasonic treatment for 4 hours. After centrifugation at 8000 rpm for 5 minutes, a homogeneous GO suspension is obtained. In some implementations, GO can then be coated onto the CNT hollow fiber membrane through a titanium tube sealed at one end with Teflon®. A DC voltage of 3.5 V is applied between the titanium cathode and the CNT hollow fiber anode. After a 30-second deposition period, the sample is chemically reduced by introducing hydrogen iodide vapor into the lumen side for 5 minutes.

[0071] In some implementations, the film may include more than one substrate. Similar all-nanocarbon-based films may be utilized in accordance with the concepts described herein.

[0072] In some implementations, the GO suspension can be applied to two or more surfaces of a substrate.

[0073] In some implementations, the GO suspension can be applied to the substrate by vacuum filtration. In these embodiments, the GO suspension can be fed into a pressure filtration device containing the substrate. In some implementations, the pressure filtration device includes a feed side and a draw side. In some implementations, the feed side and the draw side of the pressure filtration device can be separated by a substrate, such as a polymer layer discussed herein. In some implementations, the draw side can include an outlet tube and / or a draw reservoir. In some implementations, the feed side can include an inlet tube and / or a feed reservoir. For example, the GO suspension can be fed into a pressure filtration device containing a polycarbonate sheet or layer that allows water molecules to pass through but captures or retains GO in aqueous suspension. In some implementations, the substrate can cover any suitable area and can range from about 20 μm to about 30 μm in thickness, or from about 22 μm to about 28 μm in thickness. In some implementations, the substrate can be approximately 24 μm in thickness. It should be understood that the thickness of the substrate can be other suitable thicknesses depending on the application. For example, in applications where pressures are relatively high, the substrate thickness may be increased to add strength so that the resulting structure can withstand the added pressure.

[0074] In some implementations, the substrate may be characterized by a porosity of about 4.7% and an average pore size ranging from about 10 nm to about 12,000 nm. In some implementations, the average pore size may range from about 10 nm to about 12,000 nm, or from about 20 nm to about 10,000 nm, or from about 20 nm to about 1,000 nm, or from about 20 nm to about 500 nm, or from about 20 nm to about 450 nm. It should be understood that other substrates with other suitable porosities may also be used. In some implementations, the substrate is tested in a pressure filtration device to ensure that water does not leak from unintended locations in the pressure filtration device. In some implementations, the substrate in the pressure filtration device should be substantially leak-free.

[0075] In some implementations, a GO suspension is added to a pressure filtration device, and pressure is applied to force the GO suspension in the pressure filtration device against the substrate. In some implementations, pressure is applied to the GO suspension using a gas, such as an inert gas like argon. It should be understood that other suitable gases can be used, and other suitable mechanisms can be used to apply pressure to the GO suspension. In some implementations, an inert gas, such as argon, can be applied at a substantially constant pressure. For example, in some implementations, the gas can be applied at a pressure of 1 bar. In some implementations, once a flow of water (e.g., from the GO suspension) is detected at the outlet pipe of the pressure filtration device, the pressure can be increased. In some implementations, the pressure can be increased to 2.5 bar or some other suitable amount of pressure. In some implementations, the pressure can be higher or lower. In some implementations, a level of pressure is applied to the GO suspension in the pressure filtration device until the water is removed in the pressure filtration device and one or more layers of GO are applied to the substrate. In some implementations, the process is complete when substantially all of the water from the GO suspension has flowed into the draw side of the pressure filtration device. In some implementations, when fabrication of the GO layer on the substrate is proceeding properly (e.g., no tears or cracks form in the GO layer), a clear aqueous solution is collected from the draw side of the pressure filtration device. It should be understood that in some implementations, a GO layer comprises one or more GO flakes. In some implementations, multiple GO layers comprise multiple layers of GO flakes. In some implementations, the remaining GO layer is placed under pressure for a predetermined period of time. In some implementations, the predetermined period under pressure is 2 hours (or some other suitable period of time) after the last detectable water molecule is released from the pressure filtration device. In some implementations, the one or more GO layers combine with the substrate to form a GO membrane (GOM).

[0076] In some implementations, an aerogel layer can be added over the GO side of the GOM. In some implementations, the aerogel layer creates a vertical structure on the surface of the GOM such that when a fluid is flowed tangentially over the aerogel layer of the GOM, the vertical structure of the aerogel layer creates a mixing action in the fluid flowing over the GOM, breaking up any concentration polarization (or gel polarization) layers that may build up in the fluid flow near the surface of the GOM.

[0077] It should be understood that in some implementations, the GOM can be formed without additional non-graphene-based layers (e.g., without a substrate), i.e., in some implementations, the GOM can be formed with one or more layers of GO flakes.

[0078] In alternative implementations, the GO layer (layer of GO flakes) can be made by alternative methods. For example, the GO layer can be prepared using the Hummers method (e.g., by processing natural graphite flakes and treating these flakes with potassium permanganate and sodium nitrate in concentrated sulfuric acid). Another alternative method for preparing the GO layer includes the Brodie method (adding potassium chlorate to a slurry of graphite in fuming nitric acid). The resulting GO can be applied to a porous substrate layer using alternative techniques, such as spray coating, impregnation, and hot-dip plating.

[0079] In some implementations, in which the semipermeable material includes a membrane (e.g., graphene oxide) and a substrate, the membrane is prepared by printing a graphene oxide dispersion onto the substrate. In some implementations, the graphene oxide dispersion is printed onto the substrate using methods such as slot-die coating or roll-to-roll processing (e.g., roll-to-roll lithography). Typically, such coating methods produce thin films through solution processing. According to these embodiments, the GO dispersion can be delivered to the surface of the substrate through a precision coating head (e.g., a slot die or other print head). In some implementations, the process for preparing graphene oxide includes starting with an aqueous dispersion of graphene oxide. For example, the graphene oxide dispersion can include 0.4 wt % graphene oxide (GO) flakes in water.

[0080] In some implementations, the substrate can include one or more polymer layers or sheets, as described above. In some implementations, the substrate can include metal mesh, aluminum, alumina (aluminum oxide), copper, or activated carbon, as described above. In some implementations, the membrane can include two or more substrates.

[0081] In some implementations, a structural material can be included in the semipermeable material. The structural material can comprise one or more layers within the semipermeable material. The structural material can be added anywhere within the semipermeable material, for example, at a fluid-contacting surface of a membrane (e.g., a feed-contacting surface or a draw-contacting surface) or at an interior location (such as between two other membrane and / or substrate layers).

[0082] In some implementations, the structural material can include a material that provides additional strength or structure to the membrane, for example, the structural material can include silicone, graphene, or the like.

[0083] In some implementations, the structural material may be provided as a patterned layer so as not to interfere with the permeability of the semipermeable (e.g., nanoporous) material. For example, in some implementations, the structural material may be provided in a honeycomb or other open pattern so that the material can provide additional structure and strength to all materials without adversely affecting the selective permeability of the membrane and / or substrate. In some implementations, the structural material may be provided over the entire or less than the entire surface area of ​​the membrane and / or substrate. In some implementations, the structural material may be provided as strips along the perimeter of the membrane and / or substrate to provide surrounding handling support. In some implementations, the structural material may be provided as an open pattern (e.g., honeycomb) over the entire surface area in the plane of the membrane and / or substrate.

[0084] In some implementations, the GO-dispersed water (e.g., GO flake water) can be centrifuged at a low speed (e.g., 2000 rpm or some other suitable speed). In some implementations, precipitated solids from the centrifugation process are discarded until the density of the dispersion (e.g., the remaining GO suspension) is adjusted to approximately 12 mg / ml. In some implementations, GO flakes larger than 10,000 nm can be discarded from the GO suspension. In some implementations, this density can be reached in about four cycles of the centrifugation process (e.g., one cycle can include centrifuging the GO-dispersed water and discarding the precipitate). In some implementations, 1 mL of the GO-dispersed water remaining from one or more cycles of the centrifugation process can be diluted with a suitable diluent to provide a desired final concentration. For example, in some implementations, 1 mL of the GO-dispersed water can be diluted with a suitable diluent, for example, up to a volume of 100 mL. In some implementations, the diluent includes water or an alcohol. In some implementations, the water is substantially pure water. In some implementations, the water is ultrapure water, such as that obtainable from a Mili-Q® purification system. It should be understood that in some implementations, the water may be combined with one or more other compounds or products. In some implementations, the alcohol may be selected from alcohols described elsewhere herein as suitable wetting fluids. In some implementations, the alcohol may include ethanol.

[0085] In some implementations, the GO suspension in water is conditioned by sonication and / or blending to redistribute any agglomerated GO flakes prior to coating. In some implementations, the GO suspension in water is conditioned by sonication for a predetermined period of time in a sonication bath. In some implementations, the predetermined period of sonication can be 10 minutes or some other suitable period of time. The GO suspension can then be diluted as desired. In some implementations, 10 ml of GO suspension is diluted in 90 ml of distilled water to provide a relatively thin coating.

[0086] In some implementations, slot die coating can be achieved using a nano roll coater, such as a Nano Roll Coater slot die coater manufactured by FOM Technologies (Denmark).

[0087] For slot die coating, the selected substrate is loaded onto the support drum of a roll coater, and the drum temperature is raised to a desired setpoint. In some implementations, the desired setpoint may be a high temperature that increases the drying rate of the GO suspension on the substrate. In some implementations, the support drum is heated to a desired temperature (setpoint) of 60°C. The slot die head is lowered to a position directly above the substrate (e.g., 5 mm). The drum with the substrate is rotated until a short length (e.g., 0.5 cm) of the substrate protrudes beyond the slot die head toward the user. The direction of coating is toward the user, meaning that the majority of the substrate length is wrapped around the drum toward the rear of the machine.

[0088] Next, the GO suspension is loaded into the sample syringe of the slot die machine, and the syringe pump is independently operated to feed the GO suspension into the tubing line until a small droplet of coating fluid is visible protruding from the slot die coating lip. The coating process is initiated by selecting the flow rate and coating speed on the slot die user interface. The slot die head is then lowered the remaining distance to the substrate, and a film of the GO suspension is observed forming on the substrate. The distance between the slot die head and the substrate may be referred to as the working distance. This working distance may affect the width of the coating strip applied to the substrate and is not the primary parameter for controlling the wet film thickness of the coating layer. In some implementations, the working distance may be approximately 40 μm, although other working distances may also be used. The slot die head may also be manually adjusted to include the edge of the coating strip according to the manufacturer's instructions.

[0089] In some embodiments, the thickness of the GO coating layer can be primarily affected by factors such as the fluid delivery rate via the syringe pump, the substrate speed below the slot die head, and / or the width of the coating strip. In some implementations, decreasing the pump speed, increasing the substrate speed, and / or increasing the coating width can decrease the thickness of the wet-coated GO layer, and vice versa. In some implementations, the GO suspension is applied via a slot die coater at a flow rate of about 2 ml / min to about 6.5 ml / min, or about 4.5 ml / min to about 6.5 ml / min, although other flow rates can be used. In some implementations, the coating width can be about 100 mm and the coating speed can be about 70 cm / min, although other coating widths and speeds can be used as desired. In some implementations, for example, when a relatively thick coating is desired, the coating speed can be 10 cm / min and the flow rate can be about 4 ml / min.

[0090] In some implementations, the coating process continues until the desired coating thickness is achieved. In some implementations, when coating a GO suspension onto a porous polycarbonate substrate using the FOM Nano Roller Coater as described, the target thickness and width of the final film can be about 0.5 μm to about 1 μm and about 40 nm to about 90 nm, respectively. The final dimensions of the film coating can be adjusted depending on the application, and therefore the thickness and width can vary. In some implementations, multiple coatings of the GO suspension can be applied to achieve the target thickness. In some implementations, thin films can be produced by diluting the GO suspension prior to application to the substrate. In some implementations, thicker films can be produced by coating at a faster speed, such as 10 cm / min, and / or at a faster discharge rate (such as about 4 ml / min). In some implementations, the film thickness can be characterized by profile recording or cross-sectional scanning electron microscopy (SEM). In some implementations, the stacking state of the GO flakes and the integrity of the film can be characterized by SEM and / or X-ray diffraction (XRD) analysis. Figure 3 illustrates images of films produced by slot die coating compared to coating by vacuum filtration.

[0091] In some implementations, the substrate is maintained on the support drum for a suitable amount of time to allow the substrate to dry before an additional layer of GO is applied and / or removed from the coater.

[0092] In some implementations, larger scale film production can utilize the concept of slot die coating. In some implementations, films can be fabricated using roll-to-roll processing.

[0093] In some implementations, the GOM may include one or more layers of GO flakes. In some implementations, the GOM may include 10,000 layers of GO flakes. According to some principles, the thickness of the GO flake layers in the GOM has an impact on compound selectivity. While it may appear that thinner GO flake layers result in more and more easily filtered compounds from a liquid, a certain thickness of the GO flake layers may be required to optimize compound filtration selectivity (e.g., selectively filtering ethanol from an alcoholic beverage). That is, according to some embodiments, a certain range of GO flake layer thicknesses can provide better compound filtration selectivity than thinner GO flake layers. For example, if the GO layer is too thin, it will not possess enough wetting compounds to induce filtration selectivity (e.g., if a GOM is wetted to selectively filter ethanol, if the layer of GO flakes in the GOM is not thick enough, the layer of GO flakes will not possess enough wetting compounds to selectively filter ethanol from an alcoholic beverage added to one side of the GOM after the wetting period). In some implementations, the thickness of the GO layer in the GOM ranges from 100 nm to 5000 nm. In some implementations, the thickness of the GO layer in the GOM ranges from 200 nm to 4000 nm. In some implementations, the thickness of the GO layer in the GOM ranges from 300 nm to 3000 nm. In some implementations, the thickness of the GO layer in the GOM ranges from 400 nm to 2500 nm. In some implementations, the thickness of the GO layer in the GOM ranges from 500 nm to 2000 nm. In some implementations, the selection of the GO layer thickness range can depend on one or more factors, such as the temperature, the type of liquid, the type of compound being filtered from the liquid, and the altitude at which the process is performed. In some implementations, the GOM can include multiple GO layers that combine to provide an overall GO layer thickness ranging from about 10 μm to about 30 μm. In some implementations, as the surface area of ​​the GOM is increased, the layers of GO flakes are added, and the thickness is also increased. It should be understood that the GOM can have more or fewer layers of GO flakes.

[0094] In some implementations, the process for making a GOM includes using GO flakes with a desired average width range. For example, in some implementations, GO flakes with an average width ranging from about 100 nm to about 10,000 nm, or from about 200 nm to about 800 nm, or from about 300 nm to about 600 nm, or from about 400 nm to about 500 nm may be useful according to some principles. In some implementations, GO flakes with a particular average width may be selected based on factors such as the temperature, the type of liquid, the type of compound being filtered from the liquid, and the altitude at which the method is performed. In some implementations, the in-plane and inter-plane spacing of the GO flakes in the GOM may be important to the process of filtering organic compounds. Number 1 in FIG. 1A shows a close-up cross-sectional view of several GO layers in a GOM in some implementations. The GO flakes 5 overlap each other and generally have in-plane and inter-plane spacing relative to each other. In some implementations, the GO flakes include an in-plane spacing 15 of approximately 2 nm. In some implementations, the GO flakes comprise an interplanar spacing of approximately 1 nm. In some implementations, a useful range of interplanar spacing between GO flakes is from about 0.7 nm to about 1.5 nm. When the interplanar spacing between GO flakes is less than about 0.7 nm, organic molecules such as ethanol will not be able to pass through the GOM. When the interplanar spacing between GO flakes is greater than about 1.5 nm, preferential passage of certain organic molecules (e.g., ethanol) may be lost, allowing unwanted molecules (e.g., water and / or other compounds) to pass through the GOM along with the organic molecules desired to be filtered through the GOM. In some implementations, the GO membrane may have a pore size distribution of about 1.5 nm to about 7 nm, or about 1.8 nm to about 6 nm. It should be understood that the methods of forming a GOM discussed herein are suitable methods for achieving appropriate interplanar and interplanar spacing between GO flakes and GO layers to allow selective permeability.

[0095] In some implementations, the GO flakes are formed by cooking a carbon-based material. In some implementations, the carbon-based material can be caramel. In some implementations, the GO flakes can be purified by at least partially removing oxygen from the carbon-based material used to form the GO flakes. In some implementations, oxygen can be removed from the GO during the process using ascorbic acid.

[0096] In some implementations, GO membrane production can be scaled up using a relatively large amount of GO suspension. In some implementations, scaled-up GO production can include 9 mL of highly diluted GO flake dispersion diluted with water (e.g., purified water or other suitable water) to a total volume of up to 90 mL. The GO flake suspension in water is further sonicated in a sonication bath for a predetermined period of time (e.g., 5 minutes) before being fed into a pressure filtration device already containing a substrate. The substrate can include a surface area, a porosity of about 4.7%, an average pore size of about 200 nm, and a thickness of approximately 24 μm. It should be understood that other suitable water-permeable substrates can have different properties.

[0097] As previously mentioned, in some implementations, properly formed GO layers in a GOM are substantially free of cracks, tears, or cracks in the GO layer of the GOM. Structural characterization of properly formed GO films reveals the absence of such cracks, tears, or cracks throughout the GOM (while still containing nanoporous regions in the GOM or GO layer). As illustrated in Figure 1B, in some implementations, an X-ray diffraction pattern of a GOM composed of graphene oxide showing the presence of GO as a broad / high peak centered at substantially 10 degrees is typically due to the GO layer of the GOM being free of problematic cracks, tears, and / or cracks. In some implementations, a low peak in the X-ray diffraction pattern of GO may also indicate possible issues with the integrity of the GO layer of the GOM.

[0098] In some implementations, the GO film can include alternating layers of GO and substrate. In some implementations, the GO film can include an alternating structure with three layers. For example, in some embodiments, the GO film can include two or more substrate layers. In some implementations, the GO film can include a GO layer located between a first substrate layer and a second substrate layer to form a GOM having a sandwich structure including a first substrate layer / GO layer / second substrate layer. For example, in some implementations, the GOM includes a substrate on each fluid-contacting surface. The first substrate layer and the second substrate layer can include the same or different materials. In some implementations, the GOM can include a nylon / GO layer / nylon structure, as illustrated in FIG. 4A. In another example, the GO film can include a substrate located between a first GO layer and a second GO layer to form a GOM having a sandwich structure including a GO layer / substrate / GO layer. In this embodiment, the GOM includes a GO layer on each fluid-contacting surface. The first GO layer and the second GO layer can each include a thickness. The thickness of the first GO layer can be the same as or different from the thickness of the second GO layer. In some implementations, the GOM can include a GO layer / nylon / GO layer structure, as illustrated in FIG. 4B.

[0099] In some implementations, the GO film can include alternating layers of GO and substrate to provide a final product having four or more layers. In some implementations, the GO film can include alternating substrate / GO layers to provide a GOM having an overall structure of substrate / GO / substrate / GO, thus including two layers of GO and two layers of substrate, where the properties of each substrate layer can be independently selected. In some implementations, the substrate layers include the same material. In some implementations, the substrate layers include different materials. Similarly, the specific properties of each GO layer can be the same or different, as desired. The total number of GO and substrate layers, as well as their specific arrangement, can be selected as desired.

[0100] In some implementations, the GO film can be assembled to include multiple layers of GO and substrate in an irregular (non-repeating) pattern. A suitable example is shown in FIG. 4C, where the GO film includes a structure of GO / substrate / substrate / GO / substrate. In the illustrated embodiment, two different substrates are utilized, and therefore the pore size of the film varies from layer to layer. In some implementations, the substrate layer can have a pore size larger than that of the GO layer. In the example of FIG. 4C, the nylon substrate has a pore size of 200 nm, while the PVC substrate has a pore size of 5000 nm. It will be understood that the specific properties of each layer of the GOM can be selected to provide a desired overall film profile.

[0101] 2A, a process diagram illustrating a method for filtering one or more compounds from a fluid using a filtration system with a semipermeable material according to some implementations is shown. For illustrative purposes, the method is discussed with respect to a membrane-based filtration system. However, it will be understood that the method for wetting and filtering one or more compounds from a fluid also includes methods using a filtration system including a semipermeable material, which may include a membrane, a substrate (without a membrane), or a combination of a membrane and a substrate.

[0102] In some implementations, as shown in block 100, the process includes wetting a semipermeable material (e.g., a membrane) with a wetting fluid including at least one first organic compound. In some implementations, the membrane can be a carbon-based membrane (e.g., a GO-based membrane such as the GOM discussed above), a molybdenum-based membrane (e.g., MoS), or a carbon-based foam. While GOM is used as an exemplary membrane in the discussion below, it should be understood that other suitable membranes and substrates with the same or similar characteristics can be used. For example, the semipermeable material can include only one or more layers of GO. In some implementations, the semipermeable material can include only one or more layers of substrate. In various implementations, the semipermeable material can include one or more GO layers in combination with one or more substrate layers. In some implementations, the membrane can include a structural material.

[0103] In some implementations, the substrate may include a polymer film or sheet. In some implementations, the polymer film or sheet may include a polymer selected from polytetrafluoroethylene (PTFE, commonly referred to as Teflon®), polyethersulfone (PES), polycarbonate (PC), polyvinylidene fluoride (PVDF), polysulfone (PSF), polyvinyl chloride (PVC), and polyamide (nylon), or a combination or mixture of any two or more thereof. Other suitable polymers may include, for example, cellulose acetate (CA), nitrocellulose (NC), polyimide (PI), polyacrylonitrile (PAN), polypropylene (PP), polyethylene (PE), polyvinyl alcohol (PVA), poly(4-methyl-1-pentene), poly(dimethylsiloxane) (PDMS), poly(arylene ether ketone) (PAEK), poly(etherimide) (PEI), and polyethersulfonamide (PESA), or a combination or mixture of any two or more thereof.

[0104] In some implementations, a polymer layer (such as PTFE) may or may not be laminated onto a net or nonwoven support (e.g., a polypropylene net or nonwoven polypropylene support). In some implementations, the substrate polymer may be hydrophobic. In some embodiments, "hydrophobic" refers to a polymer that is essentially nonpolar and therefore not soluble in water or other polar solvents. In some implementations, the polymer layer or polymer sheet may include a surface architecture. One suitable polymer layer that includes a surface architecture includes a polycarbonate track etch (PCTE) layer. In some implementations, the polymer sheet or polymer layer may include a polyamide, such as nylon.

[0105] In some implementations, the substrate can include metal mesh, aluminum, alumina (aluminum oxide, including anodized aluminum oxide (AAO)), copper, or activated carbon, for example, the substrate has a pore size ranging from about 10 nm to about 500 nm or from about 20 nm to about 450 nm. In some implementations, the substrate can include a carbon substrate. In various implementations, the carbon substrate can include a nanocarbon material. In some implementations, the nanocarbon material can include one-dimensional carbon nanotubes (CNTs). Suitable CNTs can be prepared as hollow fibers. Such CNT hollow fibers can be prepared by wet spinning in conjunction with pyrolysis, as discussed by Fan, X. et al., “A novel reduced graphene oxide / carbon nanotube hollow fiber membrane with high forward osmosis performance,” Desalination 451 (2019) 117-124. Graphene oxide can be fabricated using a modified Hummers method and then exfoliated in distilled water (approximately 1.0 mg / ml) under ultrasonic treatment for 4 hours. After centrifugation at 8000 rpm for 5 minutes, a homogeneous GO suspension is obtained. GO can then be coated onto a CNT hollow fiber membrane through a titanium tube, one end of which is sealed with Teflon®. A DC voltage of 3.5 V is applied between the titanium cathode and the CNT hollow fiber anode. After a 30-second deposition period, the sample is chemically reduced by introducing hydrogen iodide vapor into the lumen side for 5 minutes.

[0106] It has been surprisingly discovered that wetting a semipermeable material (e.g., a GOM) with a wetting fluid that includes a first organic compound can cause the GOM, when later exposed to another fluid containing a second organic compound, to preferentially allow the second organic compound to pass through the membrane more readily. In some implementations, wetting the GOM includes exposing the GOM to a wetting fluid that includes at least one first organic compound.

[0107] In some implementations, the first organic compound of the wetting fluid is a different alcohol than the second organic compound. In some implementations, the second organic compound includes ethanol, and the first organic compound of the wetting fluid includes an alcohol other than ethanol. In some implementations, the first organic compound includes heptanol or butanol. In some implementations, the first organic compound includes an alcohol having from about 2 to about 24 carbon atoms. Suitable alcohols may include primary, secondary, or tertiary alcohols, may be allyl alcohol or benzyl alcohol, may be saturated or unsaturated, and may be linear, branched, or cyclic. In some implementations, the first organic compound of the wetting fluid is the same alcohol as the second organic compound. In some implementations, the first organic compound and the second organic compound of the wetting fluid are ethanol.

[0108] In some implementations, the first organic compound comprises an alcohol selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol (isopentyl alcohol), 2,2-dimethyl-1-propanol (neopentyl alcohol), cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenylmethanol, diphenylmethanol (diphenylcarbinol), and triphenylmethanol (triphenylmethanol), or a combination of any two or more thereof.

[0109] In some implementations, the first organic compound comprises a fatty alcohol, which may be derived from natural fats and oils. In some implementations, suitable fatty alcohols are derived from vegetable oils, for example, having 6 to 24 carbon atoms. The exact chain length may vary depending on the source of the alcohol. In some implementations, suitable fatty alcohols may be obtained from coconut oil (having 12 to 14 carbon atoms), palm kernel oil (having 16 to 18 carbon atoms), or rapeseed oil or mustard seed oil (having 20 to 22 carbon atoms). For fatty alcohols containing fewer carbon atoms, the wetting fluid may comprise a colorless, oily liquid. For fatty alcohols containing a larger number of carbon atoms, the alcohol may comprise a waxy solid.

[0110] Suitable first organic compounds include, but are not limited to, one or more fatty alcohols such as tert-butyl alcohol, tert-amyl alcohol, 3-methyl-3-pentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, cis-9-hexadecen-1-ol, 1-n-heptadecanol, 1-octadecanol, 1-octadecenol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, cis-13-docosene-1-ol, and 1-tetracosanol.

[0111] Suitable first organic compounds include, but are not limited to, pentan-3-ol, 6-methylhept-5-en-2-ol, but-3-en-2-ol, 3,3-dimethylbutan-2-ol, 2,6-dimethylocta-1,5,7-trien-3-ol, dodecan-2-ol, 2-methylhexan-3-ol, 3-methylpentan-2-ol, 4-methylpentan-2-ol, non-1-en-3-ol, nonan-3-ol, octa-1,5-dien-3-ol, undeca-1,5-dien-3-ol, and (Z)-4-hepten-2-ol.

[0112] In some implementations, the first organic compound can have a viscosity that allows the wetting fluid to be retained within the pores of the semipermeable material, ie, the first organic compound can have a kinematic viscosity in the range of about 0.55 to about 15 cP at standard conditions.

[0113] In some implementations, the wetting fluid includes the first organic compound in an amount ranging from about 1% to about 99% by volume, or from about 10% to about 99% by volume, or from about 15% to about 99% by volume, or from about 20% to about 99% by volume, or from about 25% to about 99% by volume, or from about 30% to about 99% by volume. In some implementations, the first organic compound can be combined with a liquid in which it is miscible. In some implementations, the first organic compound is combined with water or ethanol. In some implementations, the wetting fluid includes the first organic compound at a concentration of about 50% (by volume) in ethanol.

[0114] In some implementations, the wetting fluid is heptanol (CH 16 In some implementations, the heptanol includes 1-heptanol or heptan-2-ol. In some implementations, the wetting fluid is substantially pure heptanol. In some implementations, the heptanol is present in ethanol or water at a concentration of up to about 99% (by volume). In some implementations, the heptanol is present in ethanol or water at a concentration ranging from about 10% to about 99%, or from about 15% to about 99%, or from about 20% to about 99%, or from about 30% to about 99% (by volume). In some implementations, the wetting fluid includes heptanol at a concentration of about 50% (by volume) in ethanol.

[0115] In some implementations, the wetting fluid is butanol (CH 10In some implementations, the butanol comprises butan-1-ol. In some implementations, the wetting fluid is substantially pure butanol. In some implementations, the butanol is present in ethanol or water at a concentration of up to about 99% (by volume). In some implementations, the butanol is present in ethanol or water at a concentration ranging from about 10% to about 99%, or from about 15% to about 99%, or from about 20% to about 99%, or from about 30% to about 99% (by volume). In some implementations, the wetting fluid comprises butanol at a concentration of about 50% (by volume) in ethanol.

[0116] In some implementations, the wetting fluid is a substantially purified form of at least one first organic compound. For example, wetting the GOM can include immersing the GOM in a wetting fluid of an alcohol having 24 or fewer carbon atoms. In some implementations, the alcohol is a substantially pure alcohol (e.g., 99% pure alcohol). It should be understood that the percentage of alcohol in the wetting fluid can be any suitable percentage. In some implementations, the percentage of alcohol in the wetting fluid ranges from 20% to 100%. In some implementations, the wetting fluid includes an alcohol combined with water or with another shorter-chain alcohol, such as ethanol. In some embodiments, for example, for longer-chain fatty alcohols, the wetting fluid can be heated and / or dissolved in the shorter-chain alcohol to achieve a desired viscosity that allows the wetting fluid to penetrate the GOM.

[0117] In various embodiments, the wetting fluid may be selected based on factors such as solubility in alcohol, insolubility in water, and viscosity, hi some embodiments, a suitable wetting fluid may exhibit a viscosity suitable to remain within the host semipermeable membrane during use.

[0118] In some implementations, wetting the semipermeable material (e.g., GOM) in the wetting fluid includes substantially infiltrating the wetting fluid into the porous region of the GOM. In various implementations, wetting the GOM in the wetting fluid can include one or more of immersing or infiltrating the nanoporous material in the wetting fluid, applying the wetting fluid under gravity feed or pressure, spraying, vapor deposition, and the like. In various implementations, the porous membrane network of the semipermeable material is saturated with the wetting fluid before performing the separation process. For illustrative purposes, implementations involving GOM as the semipermeable material are described. However, it will be understood that any of the other semipermeable materials described herein can be substituted for GOM.

[0119] In some implementations, the GOM is immersed or infiltrated in the wetting fluid for a predetermined amount of time. In some implementations, the predetermined amount of infiltration time is 5 minutes. In some implementations, the thickness of the GOM and / or the viscosity of the wetting fluid may determine how long the GOM is infiltrated in the wetting fluid. It should be understood that the predetermined amount of infiltration time may be any suitable time. In some implementations, wetting the GOM with the wetting fluid includes substantially removing or replacing air or bubbles in the nanoporous regions of the GOM with the wetting fluid. In some implementations, the properties of the GOM may include allowing the GOM to retain all or at least a portion of the wetting fluid once the GOM is used to filter one or more second organic compounds from a second liquid (as discussed below). That is, in some implementations, wetting the GOM allows the GOM to become saturated, and this saturation may continue as one or more compounds pass through the GOM over time. In some implementations, the wetting fluid is retained in the GOM because the wetting fluid condenses between the pores (or nanopores) of the GO layer of the GOM. It should be understood that in some implementations, once the GOM is used to filter a second fluid, no wetting fluid is retained in the GOM. In some implementations, all or a portion of the wetting fluid in the GOM is replaced with one or more second organic compounds filtered from the second fluid.

[0120] In some implementations, wetting the GOM may include exposing the GOM to a wetting fluid under gravity feed. For example, the GOM may be positioned between an upper feed vessel and a lower draw vessel, where the GOM is sealed between the interface of the upper feed vessel and the lower draw vessel. In some implementations, the seal between the upper feed vessel and the lower draw vessel by the GOM prevents fluid leakage between the vessels except through the GOM. The upper feed vessel may be filled with wetting fluid, thus exposing one side of the GOM to the wetting fluid. In some implementations, gravity (in addition to capillary forces) may also cause the wetting fluid to pass from the upper feed vessel through the GOM to the lower draw vessel. In some implementations, the GOM is adequately wetted by the wetting fluid when the flow rate of the wetting fluid through the GOM reaches a substantially steady-state flow rate. It should be understood that in some implementations, the GOM may be wetted when the flow rate of the wetting fluid is less than steady-state. In some implementations, it may be sufficient to substantially wet the underside of the GOM at the interface with the lower drawer container with the wetting fluid.

[0121] In some implementations, wetting the GOM may include exposing the GOM to a wetting fluid under pressure. For example, the GOM may be positioned between a supply container and a withdrawal container, where the GOM is sealed between the supply container and the withdrawal container. In some implementations, the seal between the supply container and the withdrawal container by the GOM prevents fluid leakage between the containers except through the GOM. The supply container may be filled with wetting fluid, thus exposing one side (e.g., a first side) of the GOM to the wetting fluid. A vacuum may be applied to the withdrawal container, which forces the wetting fluid through the GOM from the supply container to the withdrawal container. In some implementations, wetting the GOM with the wetting fluid includes substantially saturating the nanoporous region of the GOM with the wetting fluid. In some implementations, wetting the GOM with the wetting fluid also includes substantially removing or replacing air or bubbles in the nanoporous region of the GOM with the wetting fluid. In some implementations, a GOM is adequately wetted by the wetting fluid when the flow rate of the wetting fluid through the GOM reaches a substantially steady-state flow rate. It should be understood that a substantially steady-state flow rate through the GOM indicates that air or bubbles in the nanoporous regions of the GOM have been substantially removed or replaced with the wetting fluid. It should also be understood that in some implementations, a GOM may be sufficiently wetted when the flow rate of the wetting fluid is less than steady-state. In some implementations, the other side of the GOM (e.g., the second side or drawer vessel side) must be substantially wetted with the wetting fluid. In some implementations, as discussed below, sufficient saturation of the drawer vessel side of the GOM prevents bubbles or air pockets from forming on the surface of the drawer vessel side of the GOM when another or third fluid is added to the drawer vessel.

[0122] In some implementations, wetting the GOM may include submerging the GOM in a wetting fluid in a vacuum bell for a suitable amount of time (eg, overnight).

[0123] In some implementations, wetting the GOM may include exposing the GOM to a wetting fluid under pressure. For example, the GOM may be positioned between a supply container and a withdrawal container, where the GOM is sealed between the supply container and the withdrawal container. In some implementations, the seal between the supply container and the withdrawal container by the GOM prevents fluid leakage between the two containers except through the GOM. The supply container may be filled with wetting fluid, thus exposing one side of the GOM to the wetting fluid. Pressure may be applied to the supply container and the wetting fluid, forcing the wetting fluid to pass through the GOM from the supply container to the withdrawal container. In some implementations, pressure is applied to the supply container using a gas. In some implementations, the gas is an inert gas such as argon. It should be understood that any suitable gas may be used to apply pressure to the supply container and the wetting fluid. In some implementations, wetting the GOM with the wetting fluid includes substantially saturating the nanoporous regions of the GOM with the wetting fluid. In some implementations, wetting the GOM with the wetting fluid also includes substantially removing or replacing air or bubbles in the nanoporous regions of the GOM with the wetting fluid. In some implementations, the GOM is adequately wetted by the wetting fluid when the flow rate of the wetting fluid through the GOM reaches a substantially steady-state flow rate. It should be understood that a substantially steady-state flow rate through the GOM indicates that air or bubbles in the nanoporous regions of the GOM have been substantially removed or replaced with the wetting fluid. It should also be understood that in some implementations, the GOM may be wetted when the flow rate of the wetting fluid is less than steady state.

[0124] In some implementations, wetting the GOM may involve pouring a quantity of wetting fluid onto one side of the membrane and applying pressure (e.g., constant pressure) until the wetting fluid is observed to coat the other side of the initially dry membrane.

[0125] In some implementations, wetting the GOM may include spraying (or spraying) a wetting fluid onto one side of the GOM to form a layer of atomized wetting fluid. Wetting may further include adding another layer of atomized wetting fluid to the same side of the GOM after a predetermined period of time. In some implementations, adding additional layers of atomized wetting fluid may continue until a predetermined amount of wetting fluid appears to have seeped through to the other side of the GOM, which may indicate that a significant number of nanopores in the GOM are saturated with wetting fluid. In some implementations, adding one or more additional layers of atomized wetting fluid may continue until the other side of the GOM appears substantially saturated with wetting fluid. In some implementations, spraying may include finely spraying the wetting fluid. One advantage of finely spraying the wetting fluid is that the wetting fluid breaks down into smaller droplets, which more easily and uniformly wet the GOM and allow the wetting fluid to penetrate and permeate the nanopores of the GOM.

[0126] In some implementations, wetting the GOM can include depositing a wetting fluid onto the film. In some implementations, depositing the wetting fluid can involve heating the wetting fluid in a vacuum in the presence of the film. In some implementations, the wetting fluid is heated to a temperature at which it transitions from a liquid phase to a gas phase (evaporates). Because the film and wetting fluid are contained in a vacuum, the wetting fluid will transition to a gas phase below its boiling point, allowing vapor particles to migrate directly to the film and condense into a liquid state. The heated wetting fluid and film are maintained in the vacuum for a suitable period of time, such as one hour. The film containing the wetting fluid is then allowed to condense for a suitable amount of time. This completes one deposition cycle. If additional wetting fluid is desired, two or more deposition cycles can be performed until the desired amount of wetting fluid has been applied to the film. In some implementations, exposure to the vaporized wetting fluid can continue until a predetermined amount of wetting fluid appears to have seeped out each side of the GOM, which may indicate that a significant number of nanopores in the GOM have been saturated with wetting fluid. In some implementations, wetting the membrane further includes finely spraying at least one layer of wetting fluid onto the membrane. In some implementations, wetting the GOM can also include drop training, where the wetting fluid is applied to the surface of the membrane and allowed to infiltrate into the membrane.

[0127] In some implementations, one advantage of vaporizing the wetting fluid may be that the wetting fluid is provided as smaller droplets, which more easily and homogeneously wet the GOM, allowing the wetting fluid to penetrate and permeate the nanopores of the GOM.

[0128] Figure 7 shows a comparison of deposition techniques, in which a nanoporous material comprising a GO layer (1 μm thick) and nylon was subjected to vapor deposition with ethanol (top line) and spray-wetting with ethanol (bottom line). For vapor deposition, the nanoporous material was exposed to ethanol vapor under vacuum at 40 °C for 1 hour. As exemplified for this particular nanoporous material, vapor deposition of the wetting fluid provided nanoporous materials with reduced ethanol content at a significantly faster rate than nanoporous materials prepared by spray-wetting. It will be appreciated that the deposition technique may be selected depending on factors such as the nanoporous material to be wetted, the dimensions (e.g., thickness) of the nanoporous material, and the wetting fluid to be applied.

[0129] In some implementations, wetting the GOM may include one or more of the above processes used in combination with each other. For example, in some implementations, the wetting fluid may be under pressure on the supply vessel side, while the withdrawal vessel side may be under vacuum. It should also be understood that for a particular compound, one or more other additional processes may be used to wet (e.g., charge) the GOM. In some implementations, one or more of the wetting steps may be performed (e.g., repeated) more than once, as desired.

[0130] In some implementations, wetting the semipermeable material may include a one-step or multi-step process. In some implementations, wetting the semipermeable material may include multiple wetting steps, where each wetting step involves exposing the membrane to a wetting fluid under conditions sufficient to allow the wetting fluid to permeate and / or saturate the membrane. In some embodiments, each wetting step may involve exposing the membrane to a different wetting fluid. In some implementations, each wetting step may involve exposing the membrane to the same wetting fluid. Each wetting step may be performed under the same, similar, or different conditions. In various implementations, wetting the semipermeable material produces a liquid-impregnated material, such as a liquid-impregnated membrane or foam.

[0131] In one embodiment, the wetting method may include exposing the semipermeable material to a first wetting fluid under conditions described herein to wet the semipermeable material. Thereafter, the method may include exposing the semipermeable material to a second wetting step, in which the semipermeable material is exposed to a second wetting fluid that is the same as or different from the first wetting fluid. Any number of wetting steps (e.g., one, two, three, or more) may be performed as desired. When two or more wetting steps are contemplated, the wetting fluids of the various wetting steps may be the same or different. In one embodiment, wetting the semipermeable material with a wetting fluid includes allowing the first wetting fluid (e.g., ethanol) to substantially infiltrate into the porous regions of the semipermeable material. In some implementations, the semipermeable material is exposed to the first wetting fluid for a predetermined amount of time. Thereafter, wetting the semipermeable material may include a second wetting step, in which the semipermeable material is exposed to a second wetting fluid (such as heptanol) under conditions sufficient to allow the second wetting fluid to substantially infiltrate into the porous regions of the semipermeable material.

[0132] In some implementations, wetting the semipermeable material can include first substantially filling the pores of the semipermeable material with ethanol and replacing the inserted ethanol with a second wetting fluid. The second wetting fluid can include ethanol or an alcohol different from ethanol. In some implementations, first substantially filling the pores of the semipermeable material with ethanol can help remove residual contamination and / or residual water within the semipermeable material.

[0133] Figure 10 illustrates the dealcoholization performance of GO membranes deposited using vacuum filtration and slot die coating (GO-VF and GO-SD, respectively) when wetted with various wetting fluids, including 100% ethanol (100% EtOH), mixtures of ethanol and heptanol in different ratios (50 / 50% and 75 / 25% EtOH / 1-heptanol), and 100% heptanol (100% 2-heptanol). As shown in Figure 10, GO-based membranes treated with 100% heptanol as the wetting fluid exhibited desirable separation properties (R * = 1.003, and dealcoholization rate = -0.07 (w / w) % EtOH / hr / cm 2 ).

[0134] Figure 11 illustrates the dealcoholization performance of GO-based films deposited using vacuum filtration and slot-die coating (GO-VF and GO-SD, respectively) when wetted with various wetting fluids, including 100% 2-heptanol (solid circles) and 100% 1-heptanol (shaded circles).

[0135] Figures 12A-12C illustrate GO membranes subjected to one-step and multi-step wetting processes. For all membranes shown in Figures 12A-12C, one-step wetting was achieved using only an ethanol solution, while multi-step wetting was achieved by an initial ethanol wetting step followed by wetting with 100% 1-heptanol. In Figure 12A, the ethanol separation performance of a GO membrane prepared by the slot-die method was assessed before and after wetting. The membrane was wetted with ethanol in the first stage, followed by a second charge with 1-heptanol (100%), and showed improved ethanol selectivity. Figure 12B illustrates a comparison of one-step wetting (shaded shapes) versus multi-step wetting (solid shapes). One-step wetting involved exposing the GO membrane to 100% 1-heptanol fluid. Multi-step wetting involved exposing the GO membrane to ethanol followed by exposing the membrane to 100% 1-heptanol. In Figure 12C, the GO membrane was subjected to a depressurization step. After the membrane was saturated with wetting fluid, it was placed in a low vacuum environment. The results illustrate that, in some embodiments, a multi-step wetting process can improve the membrane's ability to separate ethanol from a feed solution. The results illustrate that, in some embodiments, subjecting the wetted membrane to a low vacuum environment can improve the membrane's ability to separate ethanol from a feed solution.

[0136] Figure 13 shows the dealcoholization performance of various semipermeable material structures. In the figure, a MoS2 film deposited on a nylon substrate (deposited by vacuum filtration) (NL-MoS2(VF)) is illustrated by a square; commercial carbon foam encapsulated between two polycarbonate substrates (200 nm) is illustrated by a circle; GO foam encapsulated between two nylon substrates (NL, 450 nm) is illustrated by a triangle; and GO deposited on nylon using vacuum filtration (NL-GO(VF)) is illustrated by a square on the right side of the figure. Performance after 2 days is shown by open shapes, and performance after 5 days is shown by closed shapes. All films were similarly prepared using two steps: (1) overnight in an ethanol bath, and (2) vacuum.

[0137] According to some implementations, various macroporous semipermeable materials can be utilized for ethanol separation. Figure 14 illustrates the performance of various commercial macroporous substrates compared to GO-supported membranes. Included in the data are a PVDF membrane with a 100 nm pore size (PVDF 100 nm (no GO)), a PTFE membrane with a 450 nm pore size (PTFE 450 nm (no GO)), graphene oxide deposited on nylon using vacuum filtration (NLGO(VF)), and graphene oxide deposited on nylon using a slot-die process (NLGO(SD)). The data show that the PVDF membrane with a 100 nm pore size exhibits an R of 1.01. * , and -0.16 (w / w%) EtOH / hour / cm 2 and PTFE with a pore size of 450 nm exhibited a dealcoholization rate of R of 1.00. * value, and -0.007 (w / w%) EtOH / hour / cm 2 The dealcoholization rate was shown to be

[0138] After the semipermeable material is wetted with the wetting fluid, excess wetting fluid (e.g., fluid not contained within the semipermeable material) can be removed from at least a portion of the filtration system. In some implementations, the presence of the wetting fluid within the semipermeable material is necessary for the semipermeable material to maintain its preference for the second organic compound to be removed from the second liquid. In some implementations, the surface of the semipermeable material remains wet with the wetting fluid during the addition of the second and third fluids, as discussed below. In some implementations, the semipermeable material remains in a sealed position between the supply container and the drawer container. It should be understood that in some implementations, a sealed position between the supply container and the drawer container means that no fluid leaks between the containers except through the semipermeable material. In some implementations, the wet semipermeable material is placed in a sealed position between the new supply container and the new drawer container.

[0139] In some implementations, the semipermeable material (such as a membrane) is wetted in-line within the filter. For example, an unwetted (uncharged) semipermeable material can be placed in the filter to be used to remove or separate ethanol from a liquid. A wetting fluid is then introduced into the filter under conditions described elsewhere herein as suitable for wetting. Once the semipermeable material is suitably wetted with the wetting fluid, the filtration device can simply be used in the separation process without the need to move or manipulate the semipermeable material.

[0140] In some implementations, the semipermeable material can be periodically wetted with a wetting fluid while installed in the filter (e.g., in-line rewetting). For example, the semipermeable material can be utilized in as many filtration / removal sequences as desired, until such time as the semipermeable material begins to lose effectiveness. The second and third fluids can then be drained from the filter, and a wetting fluid can be introduced into the machine under wetting conditions described elsewhere herein to rewet (recharge) the semipermeable material. In some implementations, rewetting the semipermeable material can be performed any number of times, so long as the integrity of the semipermeable material for the separation process is maintained.

[0141] In some implementations, the system can be depressurized (e.g., by applying a low vacuum) after wetting the semipermeable material. In some implementations, such depressurization can reduce the presence of intercalated water remaining in the semipermeable material. In some implementations, depressurization can be performed in the presence of a wetting fluid.

[0142] Once wetting of the membrane occurs, the result is a semipermeable membrane containing a wetting fluid. In some implementations, the wetting fluid is stably contained within the pores of the semipermeable material. In some implementations, the wetting fluid is stably contained within the pores of the semipermeable material in a manner that prevents it from leaching out of the semipermeable material. FIGS. 4A, 4B, and 4C illustrate GOMs with a wetting fluid contained within the pores of the membrane. As illustrated in FIG. 4A, one implementation includes a membrane 305 including a substrate 310 and a GO layer 320 in a sandwich format, where the substrate layer 310 is included on each side of the GO layer 320, such that the substrate layer 310 contacts a second fluid during use of the membrane. As illustrated, the substrate layer 310 can include pores having a diameter 330. The wetting fluid 340 is shown contained (e.g., trapped) within the pores of the substrate 310. As illustrated in FIG. 4B , one implementation includes a membrane 305 including a sandwich format, in which GO layers 320 are disposed on either side of a substrate 310. Wetting fluid 340 is shown contained (e.g., trapped) within the pores of the substrate 310. FIG. 4C illustrates a further implementation, in which the membrane 305 includes a multi-layer alternating structure of GO layer 320 / first substrate 310 / second substrate 350 / GO layer 320 / first substrate 310. As shown, wetting fluid 340 can be contained within the pores of the first substrate 310 and the second substrate 350. As illustrated, the pores of the first substrate 310 differ in diameter from the pores of the second substrate 350. The illustrated membrane 305 includes a larger pore size in the second substrate 350. It is understood that the pore size can be the same or different between the substrates, as desired. In some implementations (not shown), the wetting fluid can be contained (e.g., trapped) within the pores in the GO layer. In some implementations, the wetting fluid can be contained within the pores in some or all of the individual layers of the GOM.

[0143] When the wetted semipermeable material is not immediately used to separate organic compounds, a protective layer can be applied to the wetted membrane, substrate, or membrane-substrate combination. Suitable protective layers can include polymeric films, such as any of the polymers described herein. In some embodiments, the protective polymeric film can include nylon or polycarbonate.

[0144] In some implementations, the semipermeable material can be wetted with a wetting fluid and then packaged for later use in the filtration process. Thus, in some embodiments, a kit including a pre-wetted semipermeable material can be provided. In some implementations, after the semipermeable material is wetted with a wetting fluid, the semipermeable material is removed from the filtration system and packaged. In some implementations, the presence of a wetting fluid in the semipermeable material is required for the semipermeable material to retain its preference for the second organic compound removed from the second liquid.

[0145] In some implementations, the wet semipermeable material includes a GO membrane and a wetting fluid contained in a package. In some implementations, the GO membrane includes a GO layer. In some embodiments, the wetting fluid is held in pores within the GO membrane. In some implementations, the GO membrane includes a GO layer and one or more substrates. In some implementations, the wetting fluid is held in pores within the GO layer and / or in pores within the substrate. It will be readily understood that any GO membrane described herein can be utilized in these embodiments. In some implementations, the wet semipermeable material includes one or more substrates (e.g., without a membrane). In some embodiments, the wetting fluid is held in pores within the substrate.

[0146] In some implementations, the wetted semi-permeable material is packaged in a suitable material that is impermeable to gases and water vapor. In various implementations, the pre-wetted nanoporous material can be sealed in an opaque material, for example, if the nanoporous material is susceptible to light-induced modifications. In some implementations, the packaging material can include foil, such as aluminum foil. In some implementations, the packaging material can include multilayer foil and plastic. In some implementations, the packaging material can include a barrier resin, such as ethylene / vinyl alcohol (EVAL), or polyamide (nylon), polyvinyl alcohol (PVAL), polyvinylidene chloride (PVDC), vapor-deposited aluminum, silicon oxide (SiO x ), or aluminum oxide (AlO x ) may include a barrier coating. Barrier packaging may be provided in forms such as pouches, vacuum bags, and trays. Barrier performance may be measured by the oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) of the barrier material. The lower the transmission rate, the higher the barrier performance. The barrier capacity level is determined by the permeation of molecular gases (O2, CO2, N2), water vapor, and other organic solvents. The barrier may consist of a monolayer film or a multilayer film. In some implementations, the barrier packaging may include multiple layers of material, such as polyethylene terephthalate (PET) in combination with polyethylene or polypropylene. In some implementations, the wet semipermeable material is packaged with a quantity of wetting fluid. Optionally, the packaged wet semipermeable material may include structural elements to protect the physical integrity of the semipermeable material (e.g., membrane, substrate, or membrane and substrate combination). Such structural elements may be bonded to the semipermeable material. In these embodiments, a structural element, such as a protective material, can be sandwiched around the semipermeable material from the outside, and the outer protective material can be removed prior to use. In some implementations, a structural element can be included in the packaging to protect the physical integrity of the semipermeable material.

[0147] In some implementations, the pre-wetted semipermeable material may include an additional amount of "free" wetting liquid within the packaging. In this context, "free" wetting liquid refers to wetting liquid that is not retained within the wet semipermeable material, but rather added to the packaging as a separate component. In some implementations, providing free wetting liquid within the packaging may help stabilize the wet semipermeable material, for example, by maintaining the semipermeable material in a moist environment until use. Optionally, as discussed elsewhere herein, the pre-wetted semipermeable material may include a protective layer.

[0148] In some embodiments, the packaged pre-wetted semipermeable material can be beneficial in the removal of organic compounds using the separation methods described herein. In some implementations, the pre-wetted GO membrane provides a ready-to-use filter for the separation or removal of organic compounds. This can be beneficial, for example, by minimizing or avoiding the cost and labor associated with preparing GO membranes. The packaged pre-wetted semipermeable material can be provided using any of the wetting fluids, membranes, and / or substrates described herein, and in any of the formats. Similarly, the packaged pre-wetted semipermeable material can be provided in any size and configuration suitable for the end use.

[0149] In some implementations, the pre-wetted semi-permeable materials can be installed in modules that can be installed as units in a filter. In some implementations, each module can contain one or more pre-wetted semi-permeable materials desired for a particular application and filter. For example, in some implementations, one or more pre-wetted semi-permeable materials can be installed in a cassette or unit configured to be installed directly into the filter. In some implementations, the modules can be removed, cleaned, and reinstalled for additional filtration applications.

[0150] In some implementations, the semipermeable material includes a substrate wetted with a wetting fluid. In some implementations, the semipermeable material includes one or more layers of a substrate and does not include a carbon-based film or a molybdenum-based film. Surprisingly, it has been found that wetting a substrate with a wetting fluid including a first organic compound can cause the substrate, when later exposed to another fluid containing a second organic compound, to preferentially allow the second organic compound to pass through the substrate more easily. In some implementations, wetting the substrate includes exposing the substrate to a wetting fluid including at least one first organic compound.

[0151] In some implementations, the semipermeable material includes a substrate as discussed above. In some implementations, the substrate may include a polymer (organic or inorganic) or a metallic material. In some implementations, the one or more other materials may include one or more layers of aerogel with a porous structure, which may provide structural support and / or create mixing action near the surface of the semipermeable material during fluid flow across the surface of the semipermeable material.

[0152] In some implementations, the substrate may include a polymer layer or a polymer sheet. In some implementations, the polymer layer or the polymer sheet may include a polymer selected from polyamide (nylon), polytetrafluoroethylene (PTFE, commonly referred to as Teflon®), polyethersulfone (PES), polycarbonate (PC), polyvinylidene fluoride (PVDF), polysulfone (PSF), polyvinyl chloride (PVC), etc., or a combination or mixture of any two or more thereof. Other suitable polymers may include, for example, cellulose acetate (CA), polyimide (PI), polyacrylonitrile (PAN), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polymethacrylic acid (PMAA), poly(arylene ether ketone) (PAEK), poly(etherimide) (PEI), polyethersulfonamide (PESA), etc., or a combination or mixture of any two or more thereof.

[0153] In some implementations, the polymer layer (such as PTFE) may or may not be laminated onto a net or nonwoven support (e.g., a polypropylene net or nonwoven polypropylene support). In some implementations, the substrate polymer may be hydrophobic. In some embodiments, "hydrophobic" refers to a polymer that is essentially nonpolar and therefore not soluble in water or other polar solvents. In some implementations, the polymer layer or polymer sheet may include a surface architecture. One suitable polymer layer that includes a surface architecture includes a polycarbonate track-etch (PCTE) membrane. In some implementations, the polymer sheet or polymer layer may include a polyamide, such as nylon.

[0154] In some implementations, the substrate may include metal mesh, aluminum, alumina (aluminum oxide), copper, or activated carbon.

[0155] Figure 9 illustrates the removal of ethanol using a semipermeable material composed of nylon (pore size 450 nm) wetted with 2-heptanol. The nylon substrate was wetted by exposing the membrane to a 10 ml solution of 50 / 50 (v / v%) heptan-2-ol in ethanol under 1 bar pressure until the wetting fluid was observed to coat the other side of the initially dry substrate. The wet nylon substrate was then exposed to 10 ml of a feed solution, a synthetic solution composed of 50 / 50 (v / v%) ethanol in water. The draw solution was 300 ml of pure water. The results, shown in Figure 9, suggest that the wetting of the nylon substrate resulted in a significant reduction of ethanol in the feed solution.

[0156] In some implementations, the semipermeable material may include a combination of a membrane and a substrate. For example, graphene oxide membranes were attached to nylon substrates using vacuum filtration and wetted with several wetting fluids listed in Table 1. The resulting wet membranes were used to separate ethanol from a synthetic mixture of 50% ethanol by volume in water. Measurement of the contained alcohol volume was achieved using an Anton Paar alcohol meter. * The values ​​were as follows:

[0157] [Table 1]

[0158] Returning to FIG. 2A , as shown in block 110, a first side of a semipermeable material (e.g., a GOM) is exposed to a second fluid, where the second fluid includes at least one second organic compound. The second fluid includes an initial concentration of the at least one second organic compound. For example, the first side of the semipermeable material can be exposed to a second fluid containing multiple compounds including water and ethanol, among other compounds. In some implementations, the second fluid can be an alcoholic beverage (e.g., gin, whiskey, vodka, wine, beer, etc.). For example, the alcoholic beverage can be placed in a supply container such that the alcoholic beverage is in physical contact with the first side of the semipermeable material.

[0159] In some implementations, the second fluid may be pre-treated prior to the step shown at 110. For example, in some implementations, the second fluid may be treated to concentrate the second organic compound. In some implementations, the second fluid is subjected to filtration or heat treatment to remove water from the second fluid (dehydration), thereby concentrating the amount of the second organic compound in the fluid. In some implementations, wine may be dehydrated to provide an increased ethanol content, and the concentrated wine may be exposed to the first side of the semipermeable material, as shown at block 110. In some implementations, beer may be dehydrated to provide an increased ethanol content, and the concentrated beer may be exposed to the first side of the semipermeable material, as shown at block 110. In some implementations, dehydration may be applied to any alcoholic beverage to be treated according to the methods described herein.

[0160] In some implementations, the filtration process may include exposing a second side (e.g., the other side or the drawer container side) of the semipermeable material to a third fluid, as shown in block 120. In some implementations, the second side of the semipermeable material may be exposed to the third fluid. In some implementations, the third fluid may be water. For example, the water may be placed in the drawer container such that the water is in physical contact with the second side of the semipermeable material. In some implementations, the water is purified water. In some implementations, the purified water is Milli-Q® water. In some implementations, the water may be tap water. In some implementations, the water may also include one or more additional compounds (e.g., salts or other minerals) that may enhance the osmotic flow of the compounds through the semipermeable material between the supply container and the drawer container. In some implementations, the third fluid is an alcoholic beverage whose ethanol content has been reduced by dealcholization. In some implementations, dealcoholization of the third fluid can be achieved by one or more methods, including heating, vacuum distillation, etc. In some implementations, the third fluid is an alcoholic beverage that has had at least a portion of its ethanol content removed through a filtration process described herein. It should be understood that block 120 can occur before, substantially simultaneously with, or after block 110.

[0161] In some implementations, block 120 can be implemented in a cross-flow configuration, where exposing can include moving a fluid across a surface of the semipermeable material. For example, the third fluid can be pumped into the withdrawal container using a pump (e.g., the pump can be inside or outside the withdrawal container) so that the third fluid flows tangentially across the second side of the semipermeable material. The third fluid can also be removed from the withdrawal container after flowing tangentially across the second side of the semipermeable material. In some implementations, the third fluid can be pushed (and removed) across the second side of the semipermeable material one or more times, where each time creates a cycle. For example, if one liter of the third fluid is pushed across the second side of the semipermeable material and removed, the one liter of the third fluid has completed one cycle across the semipermeable material. If the same 1 liter of the third fluid is forced across the second side of the semipermeable material a second time and removed, the 1 liter of the third fluid has completed a second cycle across the semipermeable material. In some implementations, the third fluid may be continuously circulated across the second side of the semipermeable material. In some implementations, the third fluid may be intermittently circulated across the second side of the semipermeable material. In some implementations, the flow of the third fluid across the second side of the semipermeable material is periodically stopped and restarted (within one cycle). In some implementations, the third fluid is forced across the second side of the semipermeable material and removed, but is not returned to circulation across the second side of the semipermeable material. That is, in some implementations, a new amount of the third fluid is forced across the second side of the semipermeable material and is not recirculated across the semipermeable material.

[0162] In some implementations, the formation of air bubbles on the second side of the semipermeable material is at least partially or substantially completely avoided by ensuring that the second side of the semipermeable material remains wet with the first fluid (e.g., wetting fluid) before the third fluid is added to the withdrawal vessel. In some implementations, when the second side of the semipermeable material is wet with the first fluid when the third fluid is added to the withdrawal vessel, the physical interface between the third fluid and the second side of the semipermeable material remains substantially free of air bubbles. In some implementations, a substantially homogenous third fluid-membrane interface (e.g., free of air bubbles) can be particularly beneficial for maximizing the separation processes described below.

[0163] In some implementations, as shown in block 130, the process includes causing movement of the second fluid across the first side of the semipermeable material for a predetermined number of hours. In some implementations, the movement of the second fluid across the first side of the semipermeable material includes applying pressure to the second fluid in the supply vessel. In some implementations, the pressure can be 0.75 bar or less. In some implementations, the pressure can be greater than 0.75 bar. The predetermined number of hours for continuing movement of the second fluid can include 30 minutes, 1 hour, 8 hours, 24 hours, 48 ​​hours, or some other suitable period of time. In some implementations, the number of hours relates to how long it is desired to remove at least one compound in the second fluid from the second fluid.

[0164] In some implementations, movement of the second fluid across the first side of the semipermeable material can be achieved using, for example, a pump, pressure (in combination with a flow valve), gravity, etc. For example, a pump can be included in the supply vessel. The pump can circulate the second fluid within the supply vessel, thereby bringing more of the second fluid into contact with the first side of the semipermeable material. In some implementations, an aerator can be used in conjunction with a filtration system. For example, to create movement of the second fluid within the supply vessel, an aerator can be used to introduce gas (e.g., an inert gas or other suitable gas) into the second fluid in the supply vessel, thereby bringing more of the second fluid into contact with the first side of the semipermeable material.

[0165] In some implementations, blocks 110 and 130 may be combined in a cross-flow configuration. For example, the second fluid may be pumped into the supply container using a pump (e.g., the pump may be inside or outside the supply container) so that the second fluid flows tangentially across the first side of the semipermeable material. The second fluid may also be removed from the supply container after flowing tangentially across the first side of the semipermeable material. In some implementations, the second fluid may be pushed (and removed) across the first side of the semipermeable material one or more times, each time creating a cycle. For example, if one liter of the second fluid is pushed across the first side of the semipermeable material and removed, the one liter of the second fluid has completed one cycle across the semipermeable material. When the same 1 liter of the second fluid is forced across the first side of the semipermeable material a second time and removed, the 1 liter of the second fluid has completed a second cycle across the semipermeable material. In some implementations, the second fluid can be continuously circulated across the first side of the semipermeable material. In some implementations, the second fluid can be intermittently circulated across the first side of the semipermeable material. In some implementations, the flow of the second fluid across the first side of the semipermeable material is periodically stopped and restarted (within one cycle). In some implementations, this stopping and restarting helps prevent or break up a concentration or gel polarization layer that may form between the surface of the semipermeable material and the second fluid.

[0166] In some implementations using a cross-flow configuration, a second fluid is forced across a first side of the semipermeable material, and a third fluid is forced across a second side of the semipermeable material. In some implementations, the second and third fluids flow in the same direction. In some implementations, the second and third fluids flow in different directions (e.g., in opposite directions). In some implementations, the rate at which the third fluid passes through the second side of the semipermeable material is between 1 and 5 times faster than the rate at which the second fluid passes through the first side of the semipermeable material. In some implementations, the rate is selected based on the type of liquid used as the second fluid. For example, if the second fluid contains a high concentration of ethanol and the ethanol needs to be selectively filtered, the flow rate of the third fluid (e.g., water) needs to be kept relatively fast relative to the flow rate of the second fluid. In some implementations, a high concentration of ethanol in the second fluid that needs to be selectively filtered may result in a selected flow rate of the third fluid that is five times the flow rate of the second fluid. In some implementations, when the second fluid contains a high concentration of solids (e.g., wine or dark liquor), the flow rate of the third fluid may need to be reduced relative to the flow rate of the second fluid (e.g., three times). In some implementations, when the second fluid contains a low concentration of ethanol that needs to be selectively filtered, the flow rate of the third fluid may need to be reduced relative to the flow rate of the second fluid (e.g., two or one times). It should be understood that the flow rate of the third fluid may be varied to a suitable rate. In some implementations, the flow rate of the third fluid may be varied to compensate for variations based on the type of second fluid, the volume of the second fluid relative to the semipermeable material, and / or the flow rate of the second fluid.

[0167] It should be understood that one or more of the above mechanisms can be used in combination to cause movement of the second fluid across the first side of the semipermeable material. It should also be understood that other suitable mechanisms can be used to cause movement of the second fluid across the first side of the semipermeable material.

[0168] In some implementations, the process includes causing movement of a third fluid across the second side of the semipermeable material for a predetermined number of times, as described above. In some implementations, when a cross-flow structure is not used, movement of the third fluid across the second side of the semipermeable material can be achieved using a pump. In some implementations, a pump can be used to circulate the third fluid within the drawer vessel, thereby bringing more of the third fluid into contact with the second side of the semipermeable material. In some implementations, an aerator can be used on the drawer side of the filtration system. For example, the aerator can be used to introduce gas (e.g., an inert gas or other suitable gas) into the third fluid in the drawer vessel, thereby bringing more of the third fluid into contact with the second side of the semipermeable material. In some implementations, movement of the third fluid across the second side of the semipermeable material can include physically moving the semipermeable material.

[0169] In some implementations, as shown in block 140, when a second fluid is in the supply vessel and in contact with one side (e.g., the first side) of the semipermeable material and a third fluid is in the withdrawal vessel and in contact with the other side (e.g., the second side) of the semipermeable material, the second organic compound permeates the semipermeable material, thereby transferring at least one second organic compound from the second fluid to the third fluid through the semipermeable material. In some implementations, wetting the semipermeable material with a wetting fluid containing at least one first organic compound allows at least one second organic compound contained in the second fluid to preferentially pass through the semipermeable material from the supply vessel to the withdrawal vessel, while preventing one or more other compounds in the second fluid from passing through. This preferential passage of the at least one second organic compound is particularly surprising in situations where the second fluid contains other compounds with smaller molecules than the at least one compound. In one example where the wetting fluid is heptanol, heptanol contains larger molecules than water. When the semipermeable material is not wet, water and ethanol can pass through it, with water being preferred. However, in implementations where the semipermeable material is wet with heptanol, the semipermeable material can preferentially or selectively allow ethanol molecules to pass through its porous structure while preventing water molecules from passing through its porous structure. Thus, when an alcoholic beverage is added to the supply container, the semipermeable material allows ethanol to pass from the alcoholic beverage to the third fluid in the withdrawal container, while substantially preventing water and other compounds in the alcoholic beverage from passing through the semipermeable material.

[0170] In some implementations, the separation process may be aided by maintaining a temperature difference between the second and third fluids, hi some implementations, the separation process may be further aided by adding one or more compounds (e.g., salts or other suitable compounds) to the third fluid.

[0171] The separation process may continue for any suitable period of time (e.g., circulating the second liquid and / or the third liquid across each side of the semipermeable material). The number of hours for which the separation process between the second fluid in the supply vessel and the third fluid in the withdrawal vessel continues may include 15 minutes, 20 minutes, 30 minutes, 1 hour, 8 hours, 24 hours, 48 ​​hours, or some other suitable period of time. In some implementations, the number of hours relates to how much of the at least one second compound in the second fluid is desired to be removed from the second fluid. In some implementations, the number of hours relates to how much of the at least one second organic compound is contained in the second fluid. In some implementations, the number of hours relates to the surface area used in the semipermeable material. In some implementations, a combination of factors may lengthen or shorten the suitable period of time (e.g., a low percentage of ethanol in a supply fluid in contact with a semipermeable material having an area of ​​1 square meter may require less time to remove the same percentage of ethanol as a low percentage of ethanol in a supply fluid in contact with a semipermeable material having an area of ​​0.5 square meters). In one example, when the second fluid comprises 50% ethanol by volume in water, after 24 hours the ethanol concentration may decrease and equalize to approximately 25% ethanol by volume in each fluid on either side of the GOM.

[0172] In one example, when beer is used as the second fluid in the supply vessel, the majority of the ethanol can be removed within 24 hours. Beer typically contains 3% to 7% ethanol by volume. In another example, when a similar volume of gin or other distilled beverage is used as the second fluid in the supply vessel, the separation process takes longer to remove a similar percentage of ethanol from the distilled beverage, which may range from 20% to 95% ethanol by volume. It should be understood that as part of the separation process, at least one second organic compound that is preferentially treated attempts to equalize between the supply vessel fluid and the draw vessel fluid.

[0173] In some implementations, the withdrawal vessel can be larger than the supply vessel, and thus the withdrawal vessel can hold more third fluid (by volume) than the second fluid (by volume) in the supply vessel. In some implementations, maintaining a volumetric difference between the third fluid and the second fluid causes more of the at least one second organic compound to flow from the second fluid to the third fluid during the separation process, equalizing the percentage of the at least one second organic compound between the second and third fluids. In some alternative implementations, the third fluid can be continually replaced with a new amount of third fluid, thereby achieving an imbalance of the at least one second organic compound in the withdrawal vessel similar to that achieved using a larger withdrawal vessel containing more third fluid than a supply vessel containing a smaller amount of second fluid.

[0174] In some implementations, as shown in block 150, the second fluid is recovered with at least a portion of the at least one second organic compound removed from the second fluid. In some implementations, the second fluid recovered at 150 is a dealcoholized fluid. The recovered second fluid (dealcoholized fluid) may have a final concentration of the at least one second organic compound that is 0.5% to 100% less than the initial concentration after completion of the process outlined in FIG. 2A. It should be understood that in some implementations, one or more compounds may pass through the semipermeable material from the second fluid to a third fluid during the separation process.

[0175] In some implementations, a portion of the third fluid or draw fluid can be added back into the dealcoholized second fluid. For example, a portion of the third fluid or draw fluid can be added back when the draw fluid acquires one or more flavor compounds during the infusion process. In another example, a portion of the third fluid or draw fluid can be added back when it is desired to adjust the final alcohol content of the dealcoholized second fluid.

[0176] FIG. 5A shows a cutaway view of a filtration system 401 in one implementation. The filtration system includes a semipermeable material (e.g., a membrane) 405. In some implementations, the semipermeable material 405 may include a GOM, as discussed above, or another suitable membrane, substrate, or a combination of a membrane and a substrate. In some implementations, the semipermeable material 405 includes a substrate layer 402 and a GO layer 404. It should be understood that the GO layer 404 and other descriptions of the GO layer may also include one or more layers of GO forming part of the GOM. In some implementations, the substrate layer may be formed of polycarbonate. In some implementations, the filtration system may include a supply vessel 410. The supply vessel may include one or more inlets 415. It should be understood that an inlet can also be an outlet. The supply vessel 410 may receive the wetting fluid discussed above through one or more inlets 415. The supply vessel may also receive the second fluid 417 discussed above through one or more inlets 415.

[0177] In some implementations, the filtration system 401 also includes a drawer vessel 420. The drawer vessel may include one or more outlets 425. It should be understood that an outlet may also be an inlet. The drawer vessel 420 may receive the wetting fluid that passes through the semipermeable material 405. The drawer vessel 420 may also receive the third fluid discussed above through the outlet 425. In some implementations, the drawer vessel 420 may be larger than the supply vessel 410.

[0178] Shown at 430 is a close-up of a small portion of the GO nanoporous structure. The GO may include one or more layers 435 of graphene flakes 445. The graphene flakes may include nanopores 440 of a predetermined size that enable the semipermeable material 405 to preferentially allow at least one second organic compound in the second fluid 417 to pass through the semipermeable material 405 to the third fluid 427, while allowing one or more other compounds in the second fluid 417 to remain in the supply vessel 410.

[0179] In some implementations, semipermeable material 405 creates a sealed interface between supply container 410 and drawer container 420. In some implementations, this sealed interface between the two containers does not allow fluid to pass between supply container 410 and drawer container 420 except through semipermeable material 405. While semipermeable material 405 appears to span the width of the interface between supply container 410 and drawer container 420, it should be understood that semipermeable material 405 may be smaller than the width of the interface between supply container 410 and drawer container 420.

[0180] For reference purposes, filtration system 401 may be used as discussed in connection with the filtration process described in FIG. 2A . As another abbreviated example of the method described in FIG. 2A , a wetting fluid (e.g., heptanol) may be added to supply vessel 410 through inlet 415. In some implementations, pressure may be applied to the wetting fluid through inlet 415. In some implementations, a vacuum may also be applied to outlet 425. The pressure on the wetting fluid and the vacuum on withdrawal vessel 420 will pull the wetting fluid through semipermeable material 405. In some implementations, the wetting fluid is pulled through semipermeable material 405 until the interface of the semipermeable material on the withdrawal vessel side has a steady-state flow of wetting fluid. In some implementations, the wetting fluid is pulled through semipermeable material 405 until the interface of the semipermeable material on the withdrawal vessel side is substantially wetted with the wetting fluid.

[0181] In some implementations, excess wetting fluid may be removed from supply container 410 and replaced with a second fluid (e.g., a fluid containing at least ethanol and water). In some implementations, the interface of semipermeable material 405 facing supply container 410 must remain wet with the wetting fluid. In some implementations, a third fluid (e.g., water) is also added to drawer container 420. In some implementations, the interface of semipermeable material 405 facing drawer container 420 must remain wet with the wetting fluid when the third fluid is added. In some implementations, excess wetting fluid does not necessarily need to be removed from drawer container 420. In some implementations, excess wetting fluid is removed from drawer container 420 before adding the third fluid.

[0182] In some implementations, at least one second organic compound in the second fluid in supply vessel 410 is drawn by osmotic pressure through semipermeable material 405 into the third fluid in draw vessel 420. In some implementations, the second fluid in supply vessel 410 is moved within supply vessel 410. In some implementations, pressure (e.g., using gas) is applied to the second fluid through inlet 415. As shown in other figures, alternative implementations may include a circulation pump instead of or in combination with the applied pressure. It should be understood that in some implementations, movement and / or pressure need not be applied to the second fluid for the osmotic process to work. However, in some implementations, the separation process may equilibrate or stall when movement of the second fluid is not induced across the interface between the supply vessel and semipermeable material 405. After a suitable period of time (e.g., when a sufficient amount of the at least one second organic compound has been separated / removed from the second fluid), the second fluid separated from at least a portion of the at least one second organic compound can be recovered from supply vessel 410. In some implementations, the second fluid can be recovered through inlet 415 or some other suitable interface. In some implementations, the recovered second fluid is a dealcoholized fluid.

[0183] In some implementations, when filtration system 400 is used on an alcoholic beverage with the process described in FIG. 2A , the semipermeable material (e.g., GOM) can selectively remove compounds such as ethanol from the alcoholic beverage. In some implementations, ethanol can be at least partially reduced by volume from the alcoholic beverage. In some implementations, ethanol can be substantially reduced by volume from the alcoholic beverage. In some implementations, the semipermeable material can selectively separate ethanol from the alcoholic beverage without heating the alcoholic beverage and without altering the production process (e.g., by brewing, fermentation, or distillation) of the alcoholic beverage, such that the ethanol content can be reduced or removed from the alcoholic beverage without a discernible change in flavor profile. In some implementations, filtration system 400 can be used at any desired point during the preparation of the alcoholic beverage, for example, during brewing or distillation, or after the beverage is fully prepared.

[0184] FIG. 5B shows a cutaway view of an alternative filtration system 401 of one implementation that implements a crossflow configuration from the filtration system illustrated in FIG. 5A. Many elements in FIG. 5B are the same as those in FIG. 5A and are therefore referred to using the same reference numerals. In a crossflow configuration, a feed fluid and a draw fluid are moved tangentially across separate sides of a semipermeable material (e.g., a GOM). The filtration system includes a semipermeable material 405. In some implementations, the semipermeable material 405 may include a GOM, as discussed above, or another suitable membrane, substrate, or a combination of a membrane and a substrate. In some implementations, the semipermeable material 405 includes a substrate layer 402 and a GO layer 404 (e.g., one or more layers of GO or GO flakes). In some implementations, the semipermeable material 405 includes the GO layer 404 without the substrate layer 402. In some implementations, one or more additional layers may be included in the semipermeable material 405. For example, as discussed above, an aerogel layer or another material can be included on the GO layer 404 to create a mixing action when the feed fluid is forced across the surface of the GO layer 404. In some implementations, the material that creates the mixing action of the feed fluid can be formed as a spacer on the surface of the GO layer 404. In some implementations, the substrate layer can be formed of polycarbonate.

[0185] In some implementations, the filtration system may include a supply vessel 410. The supply vessel may include one or more inlets 415a. The supply vessel may include one or more outlets 415b. It should be understood that an inlet can also be an outlet, and an outlet can also be an inlet. The supply vessel 410 may receive the second fluid 417 discussed above through one or more inlets 415a. In some implementations, a pump (not shown) may push the second fluid 417 tangentially across the surface of the GO layer 404 of the semipermeable material 405 through the inlet 415a. The second fluid 417 may exit the supply vessel 410 through one or more outlets 415b. In some implementations, a pump or some other mechanism may be used to apply pressure to the second fluid 417 or to the supply vessel 410, such that pressure is applied to the second fluid 417 as it flows across the surface of the GO layer 404.

[0186] In some implementations, the filtration system 400 also includes a drawer vessel 420. In some implementations, the drawer vessel may include one or more inlets 425a. In some implementations, the drawer vessel may include one or more outlets 425b. It should be understood that an outlet can also be an inlet, and an inlet can also be an outlet. The drawer vessel 420 may receive the third fluid 427 discussed above through one or more inlets 425a. In some implementations, a pump (not shown) may push the third fluid 427 tangentially across the surface of the substrate layer 402 of the semipermeable material 405 through the inlet 425a. The third fluid 427 may exit the drawer vessel 420 through one or more outlets 425b. In some implementations, the drawer vessel 420 may be larger than the supply vessel 410. In some implementations, the drawer vessel 420 may be smaller than the supply vessel 410. In some implementations, the drawer bin 420 and the supply bin 410 may be the same size or substantially the same size.

[0187] In some implementations, semipermeable material 405 is sandwiched between supply container 410 and drawer container 420 to create a sealed interface between the two containers. In some implementations, this sealed interface between the two containers does not allow fluid to pass between supply container 410 and drawer container 420 except through semipermeable material 405. While semipermeable material 405 appears to span the width of the interface between supply container 410 and drawer container 420, it should be understood that semipermeable material 405 may be smaller than the width of the interface between supply container 410 and drawer container 420.

[0188] In some implementations, one or more layers of wetting fluid are sprayed or finely sprayed onto one side of semipermeable material 405 to wet the semipermeable material for selectivity of certain compounds before semipermeable material 405 is placed between supply container 410 and withdrawal container 420. For example, one or more layers of wetting fluid are sprayed or finely sprayed onto GO layer 404 as discussed above in connection with FIG. 2A (e.g., until semipermeable material 405 is sufficiently wetted with the wetting fluid to selectively filter one or more second organic compounds different from the organic compounds contained in the wetting fluid). In some implementations, semipermeable material 405 can be wetted by a spray or finely spray process while sandwiched between supply container 410 and withdrawal container 420.

[0189] For reference purposes, filtration system 400 can be used as discussed in connection with the filtration process described in FIG. 2A . As another abbreviated example of the method described in FIG. 2A , one or more layers of a wetting fluid (e.g., heptanol) can be finely sprayed across the surface of GO layer 404 of semipermeable material 405. In some implementations, pressure can be applied to supply vessel 410 to help the sprayed or finely sprayed wetting fluid pass through semipermeable material 405. In some implementations, a vacuum can also be applied to withdrawal vessel 420, which can further help the sprayed or finely sprayed wetting fluid pass from one side of semipermeable material 405 to the other. In some implementations, the wetting fluid is applied to semipermeable material 405 until the interface of the semipermeable material is sufficiently saturated with the wetting fluid. In some implementations, for example, the wetting fluid is sprayed or finely sprayed onto GO layer 404 until the interface of semipermeable material 405 on the withdrawal vessel side is substantially wetted with the wetting fluid.

[0190] In some implementations, excess wetting fluid can be removed from the surface of GO layer 404. In some implementations, the interface of semipermeable material 405 facing supply vessel 410 must remain wet with the wetting fluid. In some implementations, second fluid 417 (e.g., a fluid containing at least ethanol and water) is forced across GO layer 404 of semipermeable material 405 in supply vessel 410 through inlet 415a, as indicated by directional arrow 450a. In some implementations, second fluid 417 exits supply vessel 410 through outlet 415b, as indicated by directional arrow 450a. In some implementations, third fluid 427 (e.g., water) is forced across substrate layer 402 of semipermeable material 405 in draw vessel 420 through inlet 425a, as indicated by directional arrow 450b. In some implementations, the third fluid 427 exits the drawer receptacle 420 through outlet 425b, as indicated by directional arrow 450b. In some implementations, the interface of the semipermeable material 405 facing the drawer receptacle 420 must remain wet with the wetting fluid when the third fluid is added. In some implementations, the excess wetting fluid does not necessarily need to be removed from the surface of the substrate layer 402 in the drawer receptacle 420, as the flow of the third fluid 427 can remove the excess wetting fluid. In some implementations, the excess wetting fluid is removed from the drawer receptacle 420 before the third fluid is forced across the surface of the substrate layer 402. It should be understood that the flow rates and directions of the second and third fluids can vary, as discussed above in connection with FIG. 2A .

[0191] It should also be appreciated that the flow of either the second fluid 417 and / or the third fluid 427 may be stopped and restarted periodically. This may help break up or reduce clogging of the GOM by suspended residue or the buildup of a concentration or gel polarization layer on the GO layer 404 side of the semipermeable material 405. In some implementations, stopping and restarting the fluid flow may be achieved by short or long pulse flows. In some implementations, vibrations (ultrasonic or otherwise) may be introduced into the flowing fluid to help break up or reduce clogging of the GOM by suspended residue or the buildup of a concentration or gel polarization layer on the GO layer 404 side of the semipermeable material 405. In some implementations, the flow of the second fluid can be temporarily reversed (e.g., reverse flow of the second fluid) to help break up or reduce clogging of the GOM with suspended debris or the development and accumulation of a concentration or gel polarization layer on the GO layer 404 side of the semipermeable material 405. One or more of these methods can be utilized alone or in combination to help the GOM continue to function at an acceptable level.

[0192] Figure 8 illustrates the effect of stopping and restarting fluid flow in some implementations. In these embodiments, a membrane comprising a three-layer structure of nylon / GO layer (1 μm thick) / PC was utilized for ethanol filtration. Polycarbonate (PC) was included as a protective layer. Vapor wetting was performed by exposing the membrane to ethanol vapor under vacuum at 40°C for 1 hour. As illustrated, the initial ethanol removal rate began to slow within the first hour of the process. However, after halting fluid movement across the membrane for 30 minutes, the ethanol removal rate resumed at a faster rate.

[0193] In some implementations, positive osmotic pressure can draw the at least one second organic compound in the second fluid 417, which is forced across the surface of the GO layer 404 in the supply vessel 410, through the semipermeable material 405 into the third fluid 427, which is forced across the substrate layer 402 in the withdrawal vessel 420. After a suitable period of time (e.g., after one or more cycles of forcing the second and third fluids into their respective vessels and / or when a sufficient amount of the at least one second organic compound has been separated / removed from the second fluid), the second fluid 417 separated from at least a portion of the at least one second organic compound can be recovered. The second fluid 417 from which at least a portion or all of the at least one second organic compound has been removed can be recovered from the outlet 415b. In some implementations, the recovered second fluid comprises a dealcoholized fluid.

[0194] FIG. 6 shows a cutaway view of one implementation of a filtration system 402. Many elements in FIG. 5B are the same as those in FIG. 5A and are therefore referred to using the same reference numbers. The filtration system 402 includes a configuration in which one container is housed within another. For example, as illustrated in FIG. 6, in some implementations, a supply container 410 is housed within a drawer container 420. In some implementations, the supply container 410 includes a semipermeable material 405 on one or more sides of the supply container 410. While FIG. 6 illustrates a supply container 410 having semipermeable material 405 on only one side, it will be readily understood that any one or more sides of the supply container 410 can be configured to include semipermeable material 405. In some implementations, the supply container 410 can include semipermeable material 405 on one, two, three, four, five, or all sides of the container. In some implementations, the semipermeable material 405 may include a GOM, as discussed above, or another suitable membrane. In some implementations, the semipermeable material 405 includes a substrate layer and a GO layer. It should be understood that the GO layer and other descriptions of a GO layer may also include one or more layers of GO forming part of the GOM. In some implementations, the substrate layer may be formed of polycarbonate. The supply vessel may include one or more inlets 415c. It should be understood that an inlet can also be an outlet. The supply vessel 410 may receive the wetting fluid discussed above through one or more inlets 415c. The supply vessel may also receive the second fluid 417 discussed above through one or more inlets 415c.

[0195] In some implementations, the filtration system 402 also includes a drawer vessel 420. The drawer vessel may include one or more outlets 425c. It should be understood that an outlet may also be an inlet. The drawer vessel 420 may receive the wetting fluid that passes through the semipermeable material 405. The drawer vessel 420 may also receive the third fluid discussed above through the outlet 425c.

[0196] In some implementations, semi-permeable material 405 creates a sealed interface between supply container 410 and drawer container 420. In some implementations, this sealed interface between the two containers does not allow fluid to pass between supply container 410 and drawer container 420 except through semi-permeable material 405. While semi-permeable material 405 is shown spanning the width of the interface between supply container 410 and drawer container 420 on one side of supply container 410, it should be understood that semi-permeable material 405 may be smaller than the width of the interface between supply container 410 and drawer container 420 on one side of supply container 410.

[0197] For reference purposes, filtration system 402 may be used as discussed in connection with the filtration process described in FIG. 2A . As another abbreviated example of the method described in FIG. 2A , a wetting fluid (e.g., heptanol) may be added to supply vessel 410 through inlet 415c. In some implementations, pressure may be applied to the wetting fluid through inlet 415c. In some implementations, a vacuum may also be applied to outlet 425c. The pressure on the wetting fluid and the vacuum on withdrawal vessel 420 will pull the wetting fluid through semipermeable material 405. In some implementations, the wetting fluid is pulled through semipermeable material 405 until the interface of the GOM on the withdrawal vessel side has a steady-state flow of wetting fluid. In some implementations, the wetting fluid is pulled through semipermeable material 405 until the interface of the semipermeable material 405 on the withdrawal vessel side is substantially wetted with the wetting fluid.

[0198] In some implementations, excess wetting fluid may be removed from supply container 410 and replaced with a second fluid (e.g., a fluid containing at least ethanol and water). In some implementations, the interface of semipermeable material 405 facing supply container 410 must remain wet with the wetting fluid. In some implementations, a third fluid (e.g., water) is also added to drawer container 420. In some implementations, the interface of semipermeable material 405 facing drawer container 420 must remain wet with the wetting fluid when the third fluid is added. In some implementations, excess wetting fluid does not necessarily need to be removed from drawer container 420. In some implementations, excess wetting fluid is removed from drawer container 420 before adding the third fluid.

[0199] In some implementations, at least one second organic compound in the second fluid in supply vessel 410 can be drawn by osmotic pressure through semipermeable material 405 into the third fluid in draw vessel 420. In some implementations, the second fluid in supply vessel 410 is moved within supply vessel 410. In some implementations, pressure (e.g., using gas) is applied to the second fluid through inlet 415c. As shown in other figures, alternative implementations may include a circulation pump instead of or in combination with applied pressure. It should be understood that in some implementations, movement and / or pressure need not be applied to the second fluid for the osmotic process to work. However, in some implementations, the osmotic process may equilibrate or stall when movement of the second fluid is not induced across the interface between the supply vessel and semipermeable material 405. After a suitable period of time (e.g., when a sufficient amount of the at least one second organic compound has been separated / removed from the second fluid), the second fluid separated from at least a portion of the at least one second organic compound can be recovered from supply vessel 410. In some implementations, the second fluid can be recovered through inlet 415c or some other suitable interface. In some implementations, the recovered second fluid is a dealcoholized fluid.

[0200] In some implementations, when the filtration system 402 is used on an alcoholic beverage with the process described in FIG. 2A , the nanoporous GOM can selectively remove compounds such as ethanol from the alcoholic beverage. In some implementations, the ethanol can be at least partially reduced by volume from the alcoholic beverage. In some implementations, the ethanol can be substantially reduced by volume from the alcoholic beverage. In some implementations, the GOM can selectively separate ethanol from the alcoholic beverage without heating the alcoholic beverage and without altering the production process of the alcoholic beverage (e.g., by brewing, fermentation, or distillation), such that the ethanol content can be reduced or removed from the alcoholic beverage without a discernible change in the flavor profile. In some implementations, the filtration system 400 can be used at any desired point during the preparation of the alcoholic beverage, for example, during brewing or distillation, or after the beverage has been fully prepared.

[0201] In some implementations, the housed configuration illustrated in Figure 6 can be included in-line in a beverage processing machine. For example, the filtration system 402 illustrated in Figure 6 can be included in-line in the production process of a beverage, such as an alcoholic beverage. In some implementations, the housed configuration illustrated in Figure 6 can utilize the concept of the cross-flow configuration illustrated in Figure 5B.

[0202] In some implementations, when filtration system 400, 401, or 402 is used on an alcoholic beverage with the process described in FIG. 2A , the nanoporous GOM can selectively remove compounds such as ethanol from the alcoholic beverage. In some implementations, ethanol can be at least partially reduced by volume from the alcoholic beverage. In some implementations, ethanol can be substantially reduced by volume from the alcoholic beverage. In some implementations, the GOM can selectively separate ethanol from the alcoholic beverage without heating the alcoholic beverage and without altering the production process of the alcoholic beverage (e.g., by brewing, fermentation, or distillation), such that the ethanol content can be reduced or removed from the alcoholic beverage without a discernible change in flavor profile.

[0203] In some implementations, the separation method may include a regeneration or reuse process. In some embodiments, such a process may reduce water and energy usage. Some exemplary features of these embodiments are now described in more detail.

[0204] In some implementations, the third fluid (draw fluid) may be further utilized once the second compound permeates the membrane and migrates to the third fluid. Referring to FIG. 2B , in some implementations, as shown in block 160, the third fluid is recovered along with at least a portion of the at least one second organic compound migrated from the second fluid. In some implementations, this recovered third fluid may be continuously moved throughout the draw fluid side 420 of the filtration system 400 or 401, for example, when the filtration system 400 or 401 is configured as a closed-loop system. In some implementations, this recovered third fluid may be diverted from the filtration system 400 or 401 and collected in a draw fluid collector (not shown). It should be understood that in some implementations, one or more compounds may pass through the GOM from the second fluid to the third fluid during the separation process.

[0205] In some implementations, the recovered third fluid collected in the withdrawal fluid collector can be used as a membrane wetting fluid, as described elsewhere herein. In various embodiments, regeneration of the recovered third fluid removed from the withdrawal vessel can provide a beneficial wetting fluid for additional filtration and can reduce the amount of water required to perform the filtration process as described herein. In some implementations, a regeneration system can be provided in an open-loop or closed-loop configuration within the systems described herein.

[0206] In some implementations, the recovered third fluid can be removed from the drawer vessel and then used to create a beverage. For example, when the second organic compound is ethanol, the recovered third fluid includes an ethanol / water mixture. This ethanol / water mixture can be utilized to create a new beverage and can be combined with additional beverage-creating ingredients, such as carbonation to create seltzer, and / or flavorings to create an alcoholic beverage. In some implementations, the recovered third fluid can be collected and combined with the dealcoholized second fluid at 150 to fine-tune the alcohol content of the beverage.

[0207] In some implementations, the recovered third fluid can be further processed as illustrated in FIG. 2B. In some implementations, the third fluid can be subjected to further dealcoholization 170 to reduce the alcohol content in the third fluid. In these embodiments, the third fluid dealcoholized at 170 can be reused in a filtration process to help maintain osmotic pressure in the system. In some implementations, the third fluid can be dehydrated as illustrated at 180. In some implementations, the second fluid is subjected to filtration or heat treatment to remove water from the second fluid (dehydrate), thereby concentrating the amount of the second organic compound in the fluid. In some embodiments, the reclaimed water from the dehydration at 180 can be reused in a filtration method as illustrated in FIG. 2A or 2B. The concentrated second organic compound obtained from 180 can be used to adjust the final alcohol content in the beverage, as discussed in more detail below.

[0208] In some implementations, various methods and apparatus can be used to create customized beverages. For example, when the methods and apparatus are used to dealcoholize a beverage, the recovered dealcoholized fluid obtained from supply vessel 410 can contain a reduced alcohol content X. Similarly, the recovered third fluid obtained from draw vessel 420 can contain an alcohol content Y. The recovered dealcoholized fluid can be combined with the recovered third fluid to produce a final beverage having an alcohol content Z between X and Y. In this way, the alcohol content of the final beverage can be fine-tuned as desired. Similarly, the recovered third fluid obtained from draw vessel 420 can contain other compounds in addition to the removed second organic compounds (e.g., compounds that affect sensory characteristics such as aroma, mouthfeel, and flavor). In some implementations, an amount of the recovered third fluid can be added back to the dealcoholized fluid to adjust the sensory characteristics of the final beverage as desired.

[0209] In some implementations, the dealcoholized fluid produced by the methods and apparatus described herein may be blended with one or more recovered third fluids obtained from the draw vessel 420, providing the ability to adjust the properties of the final beverage.

[0210] Thus, it should be understood that the various methods and apparatus discussed herein, when applied to alcoholic beverages, enable the production of dealcoholized, low-alcohol, or substantially non-alcoholic beverages that taste like corresponding conventional alcoholic beverages. In some implementations, the methods and apparatus discussed herein enable the substantial removal of ethanol, i.e., ethyl alcohol, from the alcoholic beverage while substantially preventing the removal of other compounds from the alcoholic beverage. The resulting beverage can either contain low alcohol or be substantially alcohol-free, while retaining many or most of the compounds that give the original alcoholic beverage its characteristic taste. For example, when the methods and apparatus discussed herein are applied to a brewed alcoholic beverage (e.g., stout beer) to produce a modified stout beer, the modified stout beer will continue to taste like stout beer, while the modified stout beer will have low alcohol or substantially no alcohol. As another example, when the methods and apparatus discussed herein are applied to a distilled spirit such as gin, the modified gin will continue to taste like the original gin, while the modified gin will have low alcohol or substantially no alcohol. In other words, in some implementations, the novel methods and devices discussed herein can produce low-alcohol or non-alcoholic beverages that taste the same or very similar to the corresponding alcoholic beverages and can mimic or substitute for traditional alcoholic beverages. In some implementations, the methods and devices discussed herein can be applied to other beverages or human consumables. For example, if a nursing mother consumes alcohol, the milk she produces may contain alcohol. Previously, such a nursing mother would have been forced to discard all of the alcohol-contaminated milk. By subjecting breast milk to the various methods and devices described above, the alcohol contamination can be removed from the milk, allowing the milk to be fed to the mother's nursing child.As another example, the methods and devices discussed herein can be applied to tinctures (e.g., solutions having ethanol as their solvent). In some implementations, a tincture can be an extract of plant or animal material dissolved in ethanol. The solvent concentration of ethanol in a tincture can typically range from 25 to 60%. In some implementations, the solvent concentration of ethanol can be as high as 90%. The various methods and devices discussed herein can be applied to such tinctures to remove the ethanol, while the extract is substantially retained without alcohol. As yet another example, some consumable foods, such as flavorings (e.g., vanilla flavoring) or cannabis extract, are stored in an alcohol-based solution. The various methods and devices discussed herein can be applied to such consumables to remove the alcohol, while the consumable product is retained. Removing alcohol from such consumable products is highly desirable for people who must avoid alcohol (e.g., people with alcohol allergies, people with alcoholism problems, etc.). It should be understood that the above methods and devices can also be applied to other suitable fluids in the food and beverage industry.

[0211] The present disclosure is not limited in terms of the particular implementations described herein, which are intended as examples of various aspects. Moreover, various disclosed implementations may be used interchangeably unless otherwise specified. As will be apparent to those skilled in the art, many modifications and variations may be made without departing from the spirit and scope of the present disclosure. Functionally equivalent methods and apparatuses within the scope of the present disclosure, in addition to those enumerated herein, will become apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which the appended claims are entitled. It is also to be understood that the terminology used herein is for the purpose of describing particular implementations only, and is not intended to be limiting.

[0212] With respect to the use of substantially all plural and / or singular terms herein, those skilled in the art can translate from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural permutations may also be specified herein for clarity.

[0213] In general, those skilled in the art will understand that the terms used herein, and particularly in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "including, but not limited to," etc.). Those skilled in the art will further understand that where a specific number of presented claim recitations is intended, such intention will be clearly stated in the claim, and that the absence of such statement indicates no such intention. For example, as an aid to understanding, the appended claims below may include the use of the prefaces "at least one" and "one or more" to present claim recitations. However, the use of such phrases should not be taken to imply that the presentation of a claim recitation with the indefinite article "a" or "an" limits any particular claim that includes the presented claim recitation to implementations that include only one of such recitations, even if that claim includes the preface "one or more" or "at least one" and the indefinite article "a" or "an" (e.g., "a" and / or "an" should be interpreted to mean "at least one" or "one or more"); the same applies to the use of definite articles used to present claim recitations. Additionally, even if a specific number of presented claim recitations is explicitly recited, those skilled in the art will recognize that such a recitation should be interpreted to mean at least the recited number (e.g., the recitation "two recitations" alone, without any other modifier, means at least two recitations, or more than two recitations).Furthermore, in instances where a convention similar to "such as at least one of A, B, and C" is used, such configuration is generally intended to mean that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In instances where a convention similar to "such as at least one of A, B, or C" is used, such configuration is generally intended to mean that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). Furthermore, those skilled in the art will understand that almost all disjunctive words and / or phrases in the specification, claims, or drawings that present two or more alternative terms should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B." Additionally, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is also thereby described in terms of all individual members or subgroups of members of the Markush group.

[0214] Numerous implementations have been described. Various modifications may be made without departing from the spirit and scope of the present invention. For example, various implementations of the flows shown above may be used with steps rearranged, added, or removed. Accordingly, other implementations are within the scope of the following claims. [Explanation of symbols]

[0215] 305 Membrane 310 Base material 320 GO 330 diameter 340 Wetting Fluid 401 Filtration System 402 Base material 404 GO 405 Semi-permeable material 410 Supply container 415 Entrance 420 Drawer Container 425 Exit

Claims

1. 1. A method for separating organic compounds from a fluid, comprising: - wetting the nanoporous material with a wetting fluid comprising a first compound; - moving a second fluid across a first side of the nanoporous material at a first predetermined speed for a predetermined time, wherein the second fluid is in contact with the first side of the nanoporous material, and wherein the second fluid comprises at least one second compound; - moving a third fluid across a second side of said nanoporous material at a second predetermined speed for said predetermined time; - transferring said at least one second compound from said second fluid to said third fluid through said nanoporous material; and - recovering said second fluid from which at least a portion of said at least one second compound has been removed, A method comprising:

2. The method of claim 1 , wherein the wetting fluid comprises 20% or more by volume of alcohol.

3. 2. The method of claim 1, wherein the wetting fluid is selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol (isopentyl alcohol), 2,2-dimethyl-1-propanol (neopentyl alcohol), cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenylmethanol, diphenylmethanol (diphenylcarbinol), and triphenylmethanol (triphenylmethanol), or a combination of any two or more thereof.

4. The method of claim 1, wherein the wetting fluid comprises an alcohol having a kinematic viscosity in the range of 0.55 to 15 cP at standard conditions.

5. The method of claim 3, wherein the wetting fluid comprises 2-heptanol or butan-1-ol in an amount of 20% or more by volume.

6. The method of claim 1 , wherein the second compound comprises substantially ethanol.

7. 2. The method of claim 1, wherein the second compound comprises ethanol, and wherein preferentially transporting the ethanol from the second fluid to the third fluid through the nanoporous material allows the ethanol to transport to the third fluid while substantially preventing water from transporting through the nanoporous material to the third fluid.

8. 10. The method of claim 1, wherein wetting the nanoporous material comprises providing the nanoporous material and the wetting fluid under vacuum, vaporizing the wetting fluid, and allowing the wetting fluid to contact the nanoporous material and condense on the nanoporous material.

9. The method of claim 8 , wherein one or more additional applications of vaporized wetting fluid are periodically reapplied to the nanoporous material one or more times.

10. The method of claim 1 , wherein pressure is applied to the second fluid on the first side of the nanoporous material.

11. The method of claim 1 , wherein the second fluid on the first side of the nanoporous material is pressurized with an inert gas.

12. The method of claim 1 , wherein the third fluid comprises water.

13. 10. The method of claim 1, wherein moving the second fluid across the first side of the nanoporous material at the first predetermined velocity for the predetermined time further comprises moving the second fluid tangentially across the first side of the nanoporous material.

14. 10. The method of claim 1, wherein moving the third fluid across the second side of the nanoporous material at the second predetermined velocity for the predetermined time further comprises moving the third fluid tangentially across the second side of the nanoporous material.

15. 2. The method of claim 1, wherein the second fluid is moved in a first direction across the first side of the nanoporous material and the third fluid is moved in a second direction across the second side of the nanoporous material, wherein the first direction and the second direction are the same.

16. 2. The method of claim 1, wherein the second fluid is moved in a first direction across the first side of the nanoporous material and the third fluid is moved in a second direction across the second side of the nanoporous material, wherein the first direction and the second direction are different.

17. The method of claim 1 , wherein the nanoporous material comprises a membrane.

18. 18. The method of claim 17, wherein the film comprises graphene oxide or molybdenum disulfide.

19. The method of claim 17 , wherein the nanoporous material further comprises one or more substrates.

20. The method of claim 1 , wherein the nanoporous material comprises a nanoporous substrate.

21. 21. The method of claim 20, wherein the nanoporous substrate comprises a polymer selected from polytetrafluoroethylene, polyethersulfone, polycarbonate, polyvinylidene fluoride, polysulfone, polyvinyl chloride, polyamide, cellulose acetate, nitrocellulose, polyimide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, poly(4-methyl-1-pentene), poly(dimethylsiloxane), poly(arylene ether ketone), poly(etherimide), polyethersulfonamide, and combinations or mixtures of any two or more thereof.

22. 21. The method of claim 20, wherein the nanoporous substrate comprises a metal mesh, aluminum, alumina (aluminum oxide), copper, or activated carbon.

23. The method of claim 1 further comprising the step of recovering the third fluid.

24. 24. The method of claim 23, further comprising using the recovered third fluid as a wetting fluid to wet a nanoporous material for separating organic compounds from a fluid.

25. The method of claim 1 , wherein the wetting fluid comprises ethanol.

26. A pre-wetted nanoporous material sealed in a package, comprising: graphene oxide, one or more substrates, or a combination of graphene oxide and one or more substrates; and - Wetting fluid Including, wherein the wetting fluid is contained within the graphene oxide film, within the one or more substrates, or within the graphene oxide and one or more substrates. Pre-wetted nanoporous materials.

27. 27. The pre-wetted membrane of claim 26, wherein the one or more substrates comprise one or more polymer layers or sheets selected from polyamide, polytetrafluoroethylene, polyethersulfone, polycarbonate, polyvinylidene fluoride, polysulfone, polyvinyl chloride, cellulose acetate, nitrocellulose, polyimide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, poly(4-methyl-1-pentene), poly(dimethylsiloxane), poly(arylene ether ketone), poly(etherimide), polyethersulfonamide, or a combination or mixture of any two or more thereof.

28. 27. The pre-wetted membrane of claim 26, wherein the wetting fluid is selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol (isopentyl alcohol), 2,2-dimethyl-1-propanol (neopentyl alcohol), cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenylmethanol, diphenylmethanol (diphenylcarbinol), and triphenylmethanol (triphenylmethanol), or a combination of any two or more thereof.

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