Pressure assisted diafiltration separation methods and systems

Abstract

Systems and processes are directed to separating organic compounds using filtration. More particularly, systems and methods are directed to separating ethanol from an alcoholic beverage, the method including a filtration stage and a permeate separation stage. In the filtration stage, the method can include passing an alcoholic beverage comprising water, ethanol, and a flavor component through a filtration system that comprises a semipermeable membrane having a desired molecular weight cutoff, applying a pressure to the filtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane, to provide a first permeate. In a permeate separation stage, the first permeate can be directed to a membrane contactor that comprises two or more internal contactor membranes, wherein a first side of the contactor membranes is contacted with the permeate, and a second side of the contactor membranes is contacted with a carrier gas..

Description

PRESSURE ASSISTED DIAFILTRATION SEPARATION METHODSAND SYSTEMSFIELD

[0001] The present disclosure relates to methods and systems for removal of an organic compound from a liquid. More particularly, the present disclosure relates to methods and systems for removal of ethanol from a solution using a two-stage process including pressure assisted diafiltration principles and membrane contactor principles.BACKGROUND

[0002] There is growing interest around the world for low alcohol and non-alcoholic adult beverages. For example, in 2002 the World Health Organization estimated that 5.3% of worldwide deaths and 5.1% of the global burden of disease and injury can be attributed to alcohol consumption. According to the Centers for Disease Control, the abuse of alcohol cost the United States $249 billion annually as of 2010. Separately, rising temperatures have resulted in grapes with higher sugar content, leading to wines that have higher ethanol. These factors have increased interest in controlling levels of ethanol in alcoholic beverages. While low alcohol and non-alcoholic adult beverages have been around for many years, available low alcohol and non-alcoholic adult beverages have yet to provide satisfactory flavor profiles that can mimic or substitute for traditional alcoholic beverages.

[0003] For example, some methods of making low alcohol or non-alcoholic beverages include suppressing alcoholic fermentation in the production process, to thereby reduce the content of alcohol produced by the fermentation. Other methods include heating an alcoholic beverage to 175 degrees Fahrenheit (about 80 °C) for 15 to 20 minutes, which causes the ethanol in the beverage to evaporate. However, these methods generally result in low alcohol or non-alcoholic beverages that do not taste like their alcoholic counterparts. In many instances, the resulting low alcohol or non-alcoholic beverages either have very little flavor or taste so bad that they are undrinkable.

[0004] Accordingly, there is a need to produce low alcohol or non-alcoholic adult beverages that provide acceptable organoleptic properties (such as taste, aroma, and mouthfeel) similar to their alcoholic counterparts and can mimic or substitute for traditional alcoholic beverages.BRIEF SUMMARY

[0005] The present disclosure is directed to systems and methods for separating organic compounds from liquids using membrane-based processes. In a general sense, methods and systems described herein can involve two filtration stages. In some aspects a first stage can utilize pressure assisted diafiltration principles and a second stage can utilize membrane contactor principles. In some implementations, different filtration systems can be used in the first and / or second filtration stages. In some aspects, a first stage comprises a filtration system that includes a semipermeable membrane and a pressure source. The combination of certain semipermeable membrane properties and pressure allows a user to selectively separate ethanol and water from an alcoholic beverage. Products of the first stage pressure assisted diafiltration include a first permeate (which comprises at least water and ethanol, and possibly small molecule flavor and / or aroma components), and a retentate (which comprises the portion of the alcoholic beverage that did not pass through the semipermeable membrane).

[0006] The first permeate can then be provided to a second stage to separate water and ethanol. In some aspects, the second stage comprises a permeate separation system that can generally include a membrane contactor, carrier gas, and a condenser. The first permeate can be provided to the membrane contactor, which utilizes a gas carrier to strip ethanol from the first permeate. The carrier gas can be condensed to provide an ethanol-enriched liquid. In some aspects, the carrier gas can be condensed in a controlled manner, so that ethanol and any flavor or aroma components may be further separated. Products of the second stage permeate separation system include at least an aqueous, dealcoholized liquid (also referred to as a “refreshed permeate”) and an ethanol-enriched liquid.

[0007] In some aspects, products of the second stage can be recycled to the first stage and / or used to provide additional products. For example, in some implementations, the refreshed permeate can be combined with the retentate from the first stage, to provide a reduced alcohol beverage. These aspects can provide a closed-loop system for producing reduced alcohol beverages. In some implementations, the refreshed permeate can be provided back to the first stage filtration system, such that it undergoes additional separation through the first and second stages of the process. In some implementations, the ethanol-enriched liquid product of the second stage can be utilized to produce other beverage products, or ethanol-containing products for industrial applications.

[0008] In some aspects, the two-stage methods and system described herein can provide benefits. For example, the first stage, the second stage, or both stages may be operated at ambient (or near ambient) conditions, thus reducing energy consumption requirements. By operating at ambient (or near ambient) conditions, the two-stage methods and system alsominimize altering or harming flavor components in the processed liquids that are susceptible to heat, which can help maintain the flavor of the reduced alcohol beverages. In some aspects, methods and systems can reduce water usage. For example, methods and systems can provide a closed-loop process that recycles solutions (such as the refreshed permeate), thereby minimizing requirements to add external water. In some aspects the second stage utilizes a carrier gas to strip ethanol (and optionally flavor and / or aroma components) from an ethanol- enriched solution, further reducing requirements for external water sources. In some aspects, use of carrier gas in the second stage can also provide a higher content ethanol-enriched liquid, as the carrier gas may be capable of taking on a higher amount of ethanol than a liquid (such as water) would be able to do. In some aspects, use of a carrier gas in the second stage can also avoid adding water or other liquid that may dilute the refreshed permeate or ethanol-enriched liquid products of the second stage filtration. In some aspects, the two-stage methods and systems can provide an elegant, self-contained system that recycles materials (e.g., water and carrier gas) while providing dealcoholization products with desirable properties (e.g., reduced alcohol beverages with organoleptic properties similar to their original counterparts, and ethanol-enriched liquids with high ABV that can be used to make other beverages). These and other features will be discussed herein.

[0009] In various implementations, systems and methods utilize a membrane comprising a selectively permeable membrane (also referred to herein as a separation membrane or semipermeable membrane). In some implementations, the membrane comprises a semipermeable membrane having a molecular weight cutoff in a range of about 75 Da to about 300 Da. In various implementations, the process utilizes pressure to cause movement of target compounds across the membrane and reduce ethanol levels in an alcoholic beverage. In various aspects, the process and system can utilize a membrane that allows one or more target compounds to be separated from a liquid while substantially inhibiting separation of flavor components from the liquid.

[0010] Various implementations of the systems and methods may include separating an organic compound (ethanol) from an alcoholic beverage, the method including one or more of the following:

[0011] - Passing an alcoholic beverage comprising water, ethanol, and a flavor component through a filtration system that comprises

[0012] - a semipermeable membrane comprising a feed side, a permeate side, and a molecular weight cutoff in a range of 75 Da to 300 Da,

[0013] - a feed inlet, and

[0014] - a permeate outlet;

[0015] - Applying a pressure to the filtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane, to provide a first permeate on the permeate side of the semipermeable membrane and a retentate on the feed side of the semipermeable membrane;

[0016] - Recovering the first permeate from the filtration system through the permeate outlet;

[0017] - Directing the first permeate to a membrane contactor comprising two or more contactor membranes having a first side and a second side,

[0018] - Contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas, thereby allowing ethanol to pass from the first permeate and through the membranes to the carrier gas, to provide a refreshed permeate; and

[0019] - Providing the refreshed permeate to the retentate to form an ethanol-reduced beverage.

[0020] The alcoholic beverage may comprise wine, beer, or liquor.

[0021] Thus, in some implementations, methods can provide continuous processes for providing ethanol-reduced beverages. In some implementations, methods can provide batch processes for providing ethanol-reduced beverages.

[0022] In some implementations, applying pressure to the filtration system comprises applying pressure in a range of 25 psia to 450 psia. In some implementations, contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas, is conducted at a temperature in a range of 10 °C to 30 °C. In some implementations, passing the alcoholic beverage through a filtration system, applying a pressure to the filtration system, recovering the first permeate from the filtration system, directing the first permeate to a membrane contactor, and providing the refreshed permeate to the retentate a desired number of times, until the retentate comprises a target concentration of ethanol and a target concentration of flavor component. In some implementations, the target concentration of flavor component is at least 80% of initial flavor component concentration in the alcoholic beverage.

[0023] In various implementations, methods may further comprises causing the alcoholic beverage to flow across the first side of the semipermeable membrane within the filtration system in a tangential direction. In some aspects, movement is caused by stirring the alcoholic beverage.

[0024] In some implementations, the semipermeable membrane comprises a plurality of pores having an average pore size of 10 nm or less. In various implementations, the semipermeable membrane comprises a plurality of pores having an average pore size in a range of 0.1 nm to about 10 nm. In some implementations, the semipermeable membrane comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose semipermeable membrane. In various aspects, the semipermeable membrane has a molecular weight cutoff in a range of 150 Da to 300 Da. In some implementations, the semipermeable membrane has a MgSCU rejection rate of at least 97% with a 1% MgSC solution. In some implementations, the semipermeable membrane has a NaCl rejection rate of at least 85% with a 1% NaCl solution.

[0025] In various aspects, applying pressure in the filtration system further comprises applying pressure with air, carbon dioxide, helium, nitrogen gas, or argon gas.

[0026] In accordance with some aspects, directing the first permeate to a permeate separation system may further comprise introducing at least a portion of the first permeate to a membrane contactor comprising a plurality of (e.g., two or more) contactor membranes. In some implementations, the contactor membranes comprise polymeric semipermeable membranes fabricated of polypropylene, a silicone polymer such as polydimethylsiloxane (PDMS), polyolefin (e.g., (CthCHRjn where R is an alkyl group), or the like. In some implementations, the polymeric semipermeable membranes of the membrane contactor may comprise a micro- porous or nonporous membrane.

[0027] In some implementations, the contactor membranes comprise hollow fiber membranes comprising a plurality of pores having an average pore size in a range of 0.002 pm to 0.2 pm. In some implementations, the contactor membranes comprise nonporous hollow fibers. In various aspects, methods further comprise maintaining a reduced pressure of 30 torr or less at a location downstream of the membrane contactor to pull carrier gas through the membrane contactor. In various aspects, the reduced pressure is in a range of 5 torr to 760 torr. In some implementations, the carrier gas comprises an inert gas. In some implementations, directing the first permeate to a membrane contactor and contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas is conducted at a temperature of 30 °C or less.

[0028] In various aspects, the flavor component comprises tartaric acid, malic acid, gallic acid, anthocyanin, reservatrol, caffeic acid, catechin, epicatechin, quercetin, quercetin glycosides, caftaric acid, malvidin glucoside, quercetin glycoside, tannin, or a combination of two or more of these.

[0029] In some implementations, the flavor component enriched or aroma component enriched composition obtained in the present methods and systems can be combined with the ethanol-reduced beverage. In these aspects, residual flavor and / or aroma compounds can be restored to the ethanol-reduced beverage. This may enhance the organoleptic properties (e.g., sensory properties such as one or more of taste, aroma, product appearance, and mouthfeel) of the ethanol-reduced beverage.

[0030] In some implementations, an assembly for separating ethanol from an alcoholic beverage is provided, the assembly comprising:

[0031] - a filtration system comprising

[0032] - a semipermeable membrane having a feed side, a permeate side, and a molecular weight cutoff in a range of 75 Da to 300 Da,

[0033] - a feed inlet, and

[0034] - a permeate outlet;

[0035] - a first vessel fluidly connected to the feed inlet;

[0036] - a controllable pressure source fluidly connected to the filtration system;

[0037] - a permeate vessel fluidly connected to the permeate outlet; and

[0038] - a permeate separation system fluidly connected to the permeate vessel, the permeate separation system comprising

[0039] - a membrane contactor comprising two or more contactor membranes having a first side and a second side,

[0040] - a permeate outlet,

[0041] - a gas supply,

[0042] - a gas inlet fluidly connected to the gas supply and configured to supply a carrier gas to a side of the contactor membranes,

[0043] - a gas outlet, and

[0044] - a condenser fluidly connected to the gas outlet.

[0045] In some implementations, the first vessel can comprise an aqueous liquid source. In some aspects, the aqueous liquid source may be a source of water or refreshed permeate. In various aspects, the controllable pressure source is positioned between the first vessel and the filtration system. In some implementations, the condensate stream outlet may be fluidly connected to the first vessel. In some implementations, the gas outlet may be fluidly connected to the membrane contactor.

[0046] In some implementations, the semipermeable membrane comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose semipermeablemembrane. In some implementations, the semipermeable membrane has a MgSC rejection rate of at least 97% with a 1% MgSC solution. In some implementations, the semipermeable membrane has a NaCl rejection rate of at least 85% with a 1% NaCl solution.

[0047] In various implementations, the controllable pressure source comprises a source of pressure of 450 psia (3105 kPa) or less. In various implementations, the controllable pressure source comprises a source of inert gas.

[0048] In some aspects, the contactor membranes comprise hollow fiber membranes comprising a plurality of pores having an average pore size in a range of 0.002 pm to 0.2 pm. In some aspects, the contactor membranes comprise nonporous hollow fibers.

[0049] In various implementations, the permeate outlet is fluidly connected to the first vessel. In various implementations, the gas supply comprises a supply of inert gas. In some aspects, the condenser comprises multiple stages to selectively condense components of the carrier gas.

[0050] In some implementations, the ethanol-reduced beverage can have a final flavor component concentration that is at least 80%, or at least 85%, or at least 90%, or at least 95% of the initial flavor component concentration.

[0051] In various implementations, separation methods and systems do not include a draw solution to achieve permeation of target compounds across the semipermeable membrane of the filtration system. It should be appreciated that in some implementations, the various methods and apparatuses discussed herein, when applied to alcoholic beverages, can enable dealcoholization of the beverages with minimal changes to the physiochemical properties of the beverages. As used herein, “dealcoholization” involves removal of ethanol from alcoholic beverages having an initial ethanol content, to provide a beverage having a final ethanol content that is lower than the initial ethanol content (an ethanol-reduced beverage). For example, alcoholic beverages produced by fermentation (such as wine, beer, cider, mead, and the like) typically have an initial alcohol (ethanol) 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 about 20% to about 40% (v / v). In some implementations, the methods and systems discussed herein can enable removal of ethanol from alcoholic beverages to provide beverages that have a reduced level of alcohol (as compared to their initial alcohol content), while maintaining the organoleptic and nutritional values of the original beverage. In other words, in some implementations, the methods and systems discussed herein can produce an ethanol-reduced beverage that tastes the same or very similar to its original, full alcoholic counterpart and canmimic or substitute for traditional alcoholic beverages. In some implementations, dealcoholization can remove a desired amount of ethanol from an alcoholic beverage, for example, a relatively small amount of ethanol (such as about 0.5 to about 5%), a moderate amount, or even substantially all of the ethanol in the alcoholic beverage.

[0052] In some implementations, the methods and systems discussed herein enable ethanol or ethyl alcohol to be substantially removed from an alcoholic beverage while substantially preventing other compounds from being removed from the alcoholic beverage. The resulting beverage can either contain reduced alcohol, low alcohol, or substantially no alcohol, while retaining many or most of the compounds that give the original alcoholic beverage its signature taste, aroma and drinking experience. For example, if the methods and systems discussed herein are applied to an alcoholic beverage (e.g., a red wine) to produce an altered red wine, the altered red wine continues to maintain the taste characteristics of the unaltered red wine, while the altered red wine has lower or substantially no alcohol. As another example, if the methods and systems discussed herein are applied to a distilled spirit such as gin, the altered gin continues to maintain the taste and aroma characteristics of the unaltered gin, while the altered gin has low or substantially no alcohol. In other words, in some implementations, the novel methods and systems discussed herein can produce a reduced alcohol, low alcohol, or non-alcoholic beverage that tastes the same or very similar to its alcoholic counterpart and can mimic or substitute for traditional alcoholic beverages. As used herein, reduced alcohol beverages (also referred to herein as ethanol-reduced beverages) can contain 99% of the original alcohol content, or 98% of the original alcohol content, or 97% of the original alcohol content, or 95% of the original alcohol content, or 90% of the original alcohol content, or 85% of the original alcohol content. One skilled in the art will readily appreciate that the methods and systems can be used to customize the alcohol content of a beverage as desired. As used herein, low alcohol beverages can contain 2.5% or less alcohol by volume (ABV), or 2% or less ABV, or 1% or less ABV, or 0.5% or less ABV.

[0053] In various aspects, methods and systems discussed herein can enable dealcoholization of a beverage while retaining desired organoleptic properties of the original beverage. Such organoleptic properties can be provided by one or more flavor components within the original beverage. Illustrative flavor components can include flavonoids (in the case of wine), volatile flavor components (in the case of beer), and other natural components present in the original beverage that, alone or in combination, can provide the beverage with its signature taste, aroma, and / or mouthfeel. In some implementations, dealcoholization can remove a desired amount of ethanol from an alcoholic beverage while retaining a substantialamount of desired flavor components. For example, in some aspects, methods and systems can provide dealcoholized beverages that include a final flavor component concentration that is at least 80% of the initial flavor component concentration, or at least 85% of the initial flavor component concentration, or at least 90% of the initial flavor component concentration, or at least 95% of the initial flavor component concentration.

[0054] In various aspects, methods and systems discussed herein can enable dealcoholization of a beverage without the use of heat. This may be desirable, for example, in retaining flavor components of the beverage.BRIEF DESCRIPTION OF THE DRAWINGS

[0055] FIG. 1 shows a process diagram illustrating a method of filtering one or more compounds from a fluid in accordance with some implementations.

[0056] FIG. 2 shows a schematic diagram of a separation system in accordance with some implementations .

[0057] FIG. 3 shows a schematic diagram of a permeate separation system in accordance with some implementations.

[0058] FIG. 4A shows the concentration ratio of phenolic compounds in an ethanol-reduced beverage versus untreated beverage in accordance with some implementations.

[0059] FIG. 4B shows the rejection efficiency of compounds in relation to molecular weight for a selectively permeable membrane utilized in accordance with some implementations.

[0060] FIG. 5 shows tasting feedback of ethanol-reduced beverages versus untreated beverage in accordance with some implementations.

[0061] FIG. 6 shows tasting feedback relating to body of the beverage, of ethanol-reduced beverages versus untreated beverage in accordance with some implementations.

[0062] FIG. 7 shows tasting feedback in terms of similarity of ethanol-reduced beverages versus untreated beverage in accordance with some implementations.

[0063] FIG. 8 shows the change in the ratio of each composition of treated beverage versus the corresponding composition in the original (untreated) beverage in accordance with some implementations .DETAILED DESCRIPTION

[0064] Various implementations of the concepts disclosed herein relate to processes and systems to remove or separate compounds from liquids. In the context of this application, “separate” can be understood to mean to reduce the amount of a compound contained in aliquid, such that the final product or liquid has a lower amount of the compound as compared to the initial, starting liquid. In some implementations, the compound that is separated from a liquid can be partially, substantially, or even entirely removed from the liquid.

[0065] In some implementations, processes, and systems to separate organic compounds from liquid solutions are described. In some aspects, the removal or separation of organic compounds from a liquid solution includes removing or separating ethanol from a liquid solution, such as an alcoholic beverage (e.g., an alcoholic beverage produced through fermentation, brewing, distilling, and the like). Removal or separation of ethanol from a solution can be referred to as “dealcoholization” herein. In some implementations, the alcoholic beverage may include wine, beer, or liquor. In some implementations, the ethanol can be substantially or even entirely removed from an alcoholic beverage. In some implementations, the ethanol can be partially removed from an alcoholic beverage. In some implementations, when ethanol is separated from the solution, only ethanol is separated. In some implementations, when ethanol is separated from the solution, ethanol as well as one or more additional compounds or products are also separated with the ethanol. In some implementations, an additional compound or product can be any chemical species. In some implementations, an additional compound or product can be any inorganic or organic molecule. In some implementations, when ethanol is separated from the solution, ethanol and water are separated.

[0066] Dealcoholization of alcoholic beverages will be utilized to describe certain concepts, as these applications are useful to highlight features and advantages. However, it will be readily apparent that methods and systems described herein can be used to remove other organic compounds from liquids in such fields 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 apparatuses can be used in clarification of liquids (such as juices), or in refinement of liquids (such as fuels).

[0067] In various aspects, methods employ filtration principles (e.g., diafiltration principles) to separate ethanol from an alcoholic beverage. In the context of this application, “diafiltration” describes a technique that uses membranes to remove or lower the concentration of a target component (e.g., ethanol) from a starting liquid (such as an alcoholic beverage). In doing so, methods concentrate the components that remain in the solution (i.e., are not removed from the liquid by passing through the membrane). The methods utilize selectively permeable membranes to separate the components of solutions and suspensions based on their molecularsize. The selectively permeable membrane retains molecules that are larger than the pores of the membrane (the retentate) while smaller molecules such as ethanol and water freely pass through the membrane (forming a first permeate). In various aspects, systems and methods involve providing a refreshed permeate to the retentate. The refreshed permeate can be provided in an open or closed-loop method. Methods may be performed in a batch or continuous mode.

[0068] In various aspects, systems and methods may utilize a two-stage separation process. In some implementations, a first stage of separation may employ diafiltration principles to remove or lower the concentration of ethanol from an alcoholic beverage. In some implementations, the resulting permeate from diafiltration (a first permeate) may be subjected to a second stage of separation that employs membrane contactor principles to further separate one or more of ethanol, water, flavor components, and aroma components of the first permeate.

[0069] In various aspects, systems and methods employ membrane contactors to separate ethanol, water, and flavor and aroma components. In the context of this application, membrane contactors comprise devices containing polymeric membranes (e.g., porous membranes or permeable membranes) in which the objective is to promote contact between two phases, thereby transferring one or more target compounds from one phase to the other. In some implementations, the two phases are a liquid phase and a gas phase. In various aspects, selectivity of the separation is typically obtained by using a carrier gas on one side of the porous membrane. The feed stream and the carrier gas are in contact with each other along the membrane surface. In accordance with these aspects, the membrane contactor achieves liquidgas mass transfer without dispersion of one phase within another. This is accomplished by passing the feed stream and carrier gas on opposite sides of a microporous (or nonporous) membrane and controlling the pressure difference between the two phases so that one phase is immobilized in the pores of the membrane in the form of vapor or selectively diffused across the membrane.

[0070] Thus, in various aspects, the second separation stage may subject permeate from the filtration system (e.g., the first permeate) to membrane contactors, wherein the first permeate is contacted with a carrier gas to effect transfer of target compounds from the first permeate to the carrier gas. In some implementations, one or more of ethanol, flavor compounds, and aroma compounds may be transferred from the first permeate to the carrier gas, providing a refreshed permeate. In some aspects, the refreshed permeate can comprise substantially no ethanol, as the ethanol has been removed through the membrane contactor. In some implementations, the refreshed permeate may be added back to the retentate to provide a reducealcohol beverage. In some implementations, the carrier gas which now includes one or more of ethanol, flavor compounds, and aroma compounds may now be provided to a condenser to separate out the individual compounds from the carrier gas.

[0071] In various aspects, separation processes described herein can remove or separate ethanol from an alcoholic beverage, while retaining flavor components in the original, starting beverage. In the context of this application, “retain” can be understood to mean to maintain the amount of a flavor component contained in an alcoholic beverage, such that the final product or beverage has a significant amount of the flavor component as compared to the initial, starting beverage. In some implementations, the flavor component that is retained in a beverage can be substantially, or even entirely retained in the beverage.

[0072] In some aspects, beverages include one or more flavor components that alone, or in combination, contribute to the aroma, taste, and / or mouthfeel of the beverage. For example, in wine, flavors can arise as the result of compounds originating from the native fruit (grapes), compounds that are formed or altered during the production process, compounds which are developed or transformed by yeast during fermentation, and compounds that arise during the aging process. In wine, illustrative flavor components can include acids and polyphenols.

[0073] In some implementations, flavor components in wine can include acids such as tartaric acid, malic acid, citric acid, acetic acid, butyric acid, lactic acid, and succinic acids.

[0074] In some implementations, flavor components in wine can comprise polyphenols, including flavonoids and non-flavonoids. In some implementations, flavonoids can include anthocyanins (e.g., malvidin glucoside, quercetin glycosides), tannins, flavonols (e.g., quercetin, myricetin, kaempferol, laricitrin, isorhamnetin, syringetin), catechins (e.g., catechin, epicatechin). In some aspects, non-flavonoids can include hydroxycinnamic acids (e.g., caftaric acid, coutaric acid, and fertaric acid), stilbenoids (e.g., reservatrol, benzoic acid, caffeic acid, cinnamic acid, and piceatannol), and phenolic acids (e.g., gallic acid, vanillin).

[0075] In beer, illustrative flavor components can include terpenes (e.g., myrcene, B- caryophyllene, limonene, humulene, a-pinene, linalool, geraniol, a-terpineol), esters (e.g., ethyl acetate, isoamyl acetate, 2-phenylethyl acetate, ethyl caproate, ethyl caprylate, ethyl hexanoate, ethyl butyrate), carbonyl compounds (e.g., acetaldehyde, 2,3-butanedione (diacetyl)), hop resins (e.g., humulone, cohumulone, adhumulone, lupulone, colupulone, adlupulone). In gin, flavor components can include terpenes (monoterpenes, sequiterpenes, and diterpenese) as well as their derivatives (terpenoids). Illustrative monoterpenes can include a-pinene, P-pinene, limonene, P-myrcene, p-cymene, y-terpinene, and sabinene. Oxygenated monoterpenes can include linalool, a-Terpineol and geranyl acetate. Illustrative sesquiterpenesinclude cadinene, 5-cadinene, caryophyllene, P-elemene, y-elemene, a-humulene, and germacrene D. Illustrative diterpenes can include retinol, retinal, and phytol.

[0076] It will be appreciated that a particular alcoholic beverage type may include flavor components derived from the specific ingredients used to formulate the beverage. The methods and systems described herein can be adapted to measure the initial concentration of selected flavor components found in a particular alcoholic beverage prior to commencing the separation process. The final concentration of the flavor component (or components) in the beverage after the separation process can be measured and compared to the initial concentration.

[0077] Many flavor components in alcoholic beverages (such as flavonoids, stilbenes, terpenes, and the like) are soluble in ethanol. Moreover, there is significant diversity in the properties of flavor components, in terms of molecular weight, affinity, interactions with other components of the beverage, and the like. Thus, in some aspects, it can be challenging to separate ethanol from a liquid, but retain many flavor components.

[0078] Concentration of flavor component can be measured using any suitable technique, such as high-performance liquid chromatography (HPLC).

[0079] In some aspects, a trained taster (such as a sommelier) can also assess the taste of a final product, as discussed herein. The final product (ethanol-reduced beverage) can be assessed with respect to aroma, flavor, and mouthfeel, as illustrated in the examples.

[0080] In a general sense, methods and systems described herein can involve the following: passing an alcoholic beverage comprising water, ethanol, and a flavor component through a filtration system that comprises a semipermeable membrane having a feed side, a permeate side, and a molecular weight cutoff in a range of 75 Da to 300 Da, a feed inlet, and a permeate outlet; and applying a pressure to the fdtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane. The process forms a retentate having a reduced amount of the one or more target solutes, and a first permeate that has an increased amount of the one or more target solutes. In some implementations, when the target solute comprises ethanol, the product of the process is a dealcoholized retentate, and a first permeate that has an increased alcohol content. In some implementations, the retentate retains a significant amount of flavor components despite the dealcoholization process. An aqueous liquid can be provided to the retentate to form an ethanol-reduced beverage.

[0081] In some implementations, methods and systems can provide one or more benefits. In some implementations, methods and systems can be performed at ambient temperatures (e.g., in a range of about 0°C to about 30°C, or about 5 °C to about 30 °C, or about 10 °C to about30 °C, or about 15 °C to about 25 °C). This can be beneficial, for example, in retaining desired organoleptic properties of the alcoholic beverage and reducing required energy input.

[0082] In some implementations, methods and systems can be performed at a pressure within a desired range, such as about 25 psia (172 kPa) to 450 psia (3105 kPa), or about 100 psia (689 kPa) to about 400 psia (about 2,760 kPa), or about 145 psia (1,000 kPa) to about 350 psia (about 2,415 kPa), or about 145 psia to about 300 psia (about 2,070 kPa), or about 145 psia to about 250 psia (about 1,725 kPa). Such conditions may be beneficial in retention of sensory (e.g., taste, aroma, color) and nutritional (e.g., vitamin) value of the original alcoholic beverage. In some aspects, methods and systems can be performed while exposed to air or inert gas (such as, carbon dioxide, helium, nitrogen, argon, or the like). In some aspects, materials utilized in the methods and systems (semipermeable membrane, membrane contactor, and refreshed permeate) are inexpensive, readily available, and food safe. In some aspects, methods and systems can separate ethanol from a solution in a controllable manner.

[0083] In various aspects, methods and systems can provide for the removal of ethanol from a beverage, while retaining desirable solutes such as flavor components within the starting material (the feed solution). Taking one illustrative example, wine is a complex mixture that includes mainly water and ethanol, but also several hundred compounds such as sugars (glycerol and polysaccharides), acids, volatile flavor and aroma compounds, pigment compounds, and tannins. It is this mixture of trace compounds that gives a wine its unique flavor, color, aroma, and individuality. Thus, in some aspects, methods and systems can provide for the removal of ethanol from a beverage, while retaining desirable solutes such as sugars, acids, volatile flavor and aroma compounds, pigment compounds, and tannins. The dealcoholized wine can thus retain its signature taste, aroma, and color.

[0084] Some implementations described herein relate to methods and systems for separating an organic compound (e.g., ethanol) from liquid solutions using a selectively permeable membrane in combination with pressure. One or more target solutes (e.g., dissolved, dispersed, or suspended components of a solvent system) can be selectively separated from one or more solvents using methods and systems described herein. Solutes may include permeable solutes that are capable of crossing the separation membrane, such as ethanol.

[0085] In some implementations, methods of separating ethanol from an alcoholic beverage are provided, the method comprising:

[0086] - Passing an alcoholic beverage comprising water, ethanol, and a flavor component through a filtration system that comprises

[0087] - a semipermeable membrane comprising a feed side, a permeate side, and a molecular weight cutoff in a range of 75 Da to 300 Da,

[0088] - a feed inlet, and

[0089] - a permeate outlet;

[0090] - Applying a pressure to the filtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane, to provide a first permeate on the permeate side of the semipermeable membrane and a retentate on the feed side of the semipermeable membrane;

[0091] - Recovering the first permeate from the filtration system through the permeate outlet;

[0092] - Directing the first permeate to a membrane contactor comprising two or more membranes having a first side and a second side,

[0093] - Contacting a first side of the membranes within the membrane contactor with the first permeate, and a second side of the membranes within the membrane contactor with a carrier gas, thereby allowing ethanol to pass from the first permeate and through the membranes to the carrier gas, to provide a refreshed permeate; and

[0094] - Providing the refreshed permeate to the retentate to form an ethanol-reduced beverage.

[0095] In some implementations, the alcoholic beverage includes a first flavor component concentration, and the ethanol-reduced beverage includes a second flavor component concentration. In some implementations, the second flavor component concentration can be at least 80% of the first flavor component concentration, or at least 85% of the first flavor component concentration, or at least 90% of the first flavor component concentration, or at least 95% of the first flavor component concentration.

[0096] In some implementations, an alcoholic beverage comprising water, ethanol, and a flavor component is introduced to a filtration system that comprises a semipermeable membrane having a feed side, a permeate side, and a MWCO in a range of 75 Da to 300 Da, a feed inlet, and a permeate outlet. The alcoholic beverage (feed solution) includes a first concentration of at least one first organic compound (e.g., ethanol). For example, a first side of the selectively permeable membrane can be exposed to an alcoholic beverage that contains a plurality of compounds including, among other compounds, water, ethanol, and a flavor component. In some implementations, the feed solution can be an alcoholic beverage such as gin, whisky, vodka, wine, beer, and the like. For example, an alcoholic beverage can beintroduced to a filtration system such that the alcoholic beverage is in physical contact with the feed side of the selectively permeable membrane.

[0097] In some implementations, methods include applying a pressure to the filtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane, to provide a first permeate on the permeate side of the semipermeable membrane, and a retentate on the feed side of the semipermeable membrane. In some implementations, the pressure can be about 25 psia (172 kPa) to 450 psia (3105 kPa), or about 100 psia (689 kPa) to about 400 psia (about 2,760 kPa), or about 145 psia (1,000 kPa) to about 350 psia (about 2,415 kPa), or about 145 psia to about 300 psia (about 2,070 kPa), or about 145 psia to about 250 psia (about 1,725 kPa). It is understood that psia is pounds per square inch absolute, or pressure relative to zero (or a perfect vacuum).

[0098] In some implementations, methods include causing a movement of the alcoholic beverage across a surface of the feed side of the semipermeable membrane for a predetermined quantity of time. In some implementations, movement of the alcoholic beverage across a surface of the feed side of the semipermeable membrane includes stirring the alcoholic beverage. In some implementations, movement of the alcoholic beverage across a surface of the feed side of the semipermeable membrane can be achieved, for example, using a pump, an impeller (e.g., as part of a rotational device), and the like. For example, a pump or impeller (such as a blade, paddle, or stir bar) can be included in the filtration system. The pump may circulate the alcoholic beverage within the filtration system, which in turn causes more of the alcoholic beverage to contact a surface of the feed side of the semipermeable membrane.

[0099] The predetermined quantity of time to continue movement of the alcoholic beverage may include 48 hours, 46 hours, 42 hours, 40 hours, 36 hours, 30 hours, 24 hours, 18 hours, 16 hours, 12 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, 45 minutes, 30 minutes, or some other suitable time period. In some implementations, the quantity of time relates to how much of the ethanol in the alcoholic beverage is desired to be removed from the alcoholic beverage and / or the volume of alcoholic beverage introduced into the filtration system.

[0100] In some implementations, the feed solution can be injected into the filtration system with a pump (e.g., the pump can be internal or external to the filtration system vessel) so that the alcoholic beverage travels across (e.g., tangentially) a surface of the feed side of the semipermeable membrane. Optionally, the feed solution may further be removed from the filtration system after traveling across a surface of the feed side of the membrane. In some implementations, the feed solution may be pumped across a surface of the feed side of the semipermeable membrane (and removed) one or more times, where each time creates a cycle.For example, if a liter of a feed solution is pumped across a surface of the feed side of the membrane and removed, the liter of the feed solution completed one cycle across the membrane. If the same liter of the feed solution is pumped across a surface of the feed side of the membrane and removed a second time, the liter of the feed solution completed a second cycle across the membrane. In some implementations, the feed solution may be cycled continuously across a surface of the feed side of the semipermeable membrane. In some implementations, the feed solution may be cycled intermittently across a surface of the feed side of the membrane. In some implementations, the flow of the feed solution across a surface of the feed side of the membrane is periodically stopped and restarted (within a cycle). In some implementations, the stopping and restarting may aid in preventing or disrupting a concentration polarization effect at or near the surface of the feed side of the membrane. In some implementations, the stopping and restarting of the feed solution flow can be accomplished with short or long pulsed flow. In some implementations, vibrations (e.g., mechanical) can be introduced to the flowing feed solution to help break up or reduce clogging of the membrane by suspended residues or the occurrence of concentration polarization phenomena at or near the surface of the separation membrane. One or more of these methods can be utilized alone or in combination to help keep the separation membrane performing at an acceptable level.

[0101] It should be appreciated that one or more of the above mechanisms can be used in combination to cause movement of the feed solution across a surface of the feed side of the separation membrane of the filtration system. Facilitating movement of the feed solution within the filtration system can be advantageous, for example to reduce chance of filter cake that can lead to fouling and / or uneven flow.

[0102] Illustrative assemblies for separating liquid components (dealcoholizing) of a solution herein may generally include a filtration system that comprises a semipermeable membrane having a feed side, a permeate side, and a MWCO in a range of 75 Da to 300 Da, a feed inlet, and a permeate outlet; a feed vessel fluidly connected to the feed inlet; a controllable pressure source fluidly connected to the filtration system; a permeate vessel fluidly connected to the permeate outlet; and a permeate separation system. Illustrative permeate separation systems may generally include a membrane contactor comprising a plurality (e.g., two or more) membranes having first side (e.g., a lumenside) and a second side (e.g., shellside), a permeate outlet, a gas inlet to supply a carrier gas to a side of the membranes, a gas outlet, a condenser fluidly connected to the gas outlet, and a condensate stream outlet. Reference to a “first side” and a “second side” of the membranes is made for purposes of distinguishing the sides anddoes not imply a particular order of the membrane sides. For example, in some implementations, the first side can comprise the lumenside and the second side can comprise the shellside; in other implementations, the first side can comprise the shellside and the second can comprise the lumenside. As will be discussed in more detail elsewhere herein, one or more fluid inputs and outputs can be provided on each side of the filtration system, permeate separation system, or both.

[0103] In various implementations, when the feed solution is in contact with one side (e.g., the feed side) of the filtration system separation membrane, and a suitable pressure is applied to the system, permeation of the target solute (e.g., at least one organic compound) through the membrane causes the target solute to be transferred from the feed solution through the membrane, thereby creating a first permeate. In some implementations, more than one target solute permeates through the semipermeable membrane, e.g., ethanol and water. In some implementations, due to one or more features, the target solute contained in the feed solution preferentially passes through the membrane, to the exclusion of one or more other compounds in the feed solution. In various aspects, features can include one or more of semipermeable membrane selection, pressure applied during separation, and / or processing temperature.

[0104] The separation process may be continued for any suitable period of time (e.g., cycling the feed solution across the feed side of the semipermeable membrane). The quantity of time to continue the separation process may comprise 48 hours, 46 hours, 42 hours, 40 hours, 36 hours, 30 hours, 24 hours, 18 hours, 16 hours, 12 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, 45 minutes, 30 minutes, or some other suitable time period. In some implementations, the quantity of time relates to how much of the target solute in the alcoholic beverage is desired to be removed from the alcoholic beverage. In some implementations, the quantity of time relates to how much of the target solute is contained within the alcoholic beverage. In some implementations, the quantity of time relates to the surface area of the semipermeable membrane. In some implementations, a combination of factors can raise or lower the suitable period of time (e.g., a low percentage of ethanol in a feed solution in contact with a membrane having 1 square meter area may require less time to remove an equivalent percentage of ethanol from a low percentage of ethanol in a feed solution in contact with a membrane having 0.5 square meter area).

[0105] In one example, when red wine is supplied as the feed solution to a filtration system, a substantial portion of ethanol can be removed within 6.5 hours. Red wine typically includes between 12% and 15% of ethanol by volume. In another example, when a similar volume of gin or other distilled beverage is used as the feed solution in the feed vessel, a longer time maybe used for the separation process to remove a similar percentage of ethanol from the alcoholic beverage, where alcoholic beverages can range between 20% and 95% of ethanol by volume.

[0106] In some implementations, ethanol and water are transferred from the alcoholic beverage through the semipermeable membrane, thereby creating a retentate on the feed side of the semipermeable membrane and a first permeate (e.g., an ethanol enriched permeate) on the permeate side of the semipermeable membrane. In some implementations, an aqueous liquid may be provided to the retentate to restore volume lost through separation of water and ethanol, thereby forming an ethanol-reduced beverage. In some implementations, the aqueous liquid may comprise water (such as water treated by distillation, reverse osmosis, or similar methods). In some implementations, the aqueous liquid may comprise a product of a second stage process that utilizes a membrane contactor to separate one or more of water, ethanol, flavor components, or aroma components of the first permeate produced by the filtration system. The combined retentate and aqueous liquid can be recovered from the feed side of the semipermeable membrane, providing an alcoholic beverage having a final ethanol concentration that is lower than the initial ethanol concentration in the alcoholic beverage feed solution. The dealcoholized solution may have a final concentration of ethanol that is between 0.5% and 100% less than the initial concentration of ethanol in the feed solution (alcoholic beverage). It should be appreciated that one or more compounds may be passed through the membrane to form a first permeate during the separation process in some implementations.

[0107] In some implementations, a first permeate (e.g., an ethanol enriched permeate) can be recovered from the filtration system through a permeate outlet. Optionally, the first permeate can be utilized to formulate other alcoholic beverages. In some implementations, first permeate recovered from the filtration system can be directed to a second separation process wherein components of the first permeate are further separated. In some implementations, water can be separated from ethanol within a permeate separation system, to form an ethanol-enriched liquid and an aqueous liquid. The aqueous liquid can include low amounts of ethanol, e.g., 5% or less, or 4% or less, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less (by volume). In these aspects, for example, the aqueous liquid can comprise a refreshed permeate. In some implementations, methods include combining the refreshed permeate to retentate. This can provide a closed-loop process wherein components of the permeate can be recycled through the system. The ethanol recovered from the permeate separation system can be utilized to formulate other alcoholic beverage products, or ethanol solutions for industrial applications. Aspects of the permeate separation process will be discussed in more detail elsewhere herein.

[0108] FIG. 1 shows a process diagram illustrating a method of separating ethanol from an alcoholic beverage in accordance with some implementations. As illustrated, a separation process 100 may include a first stage 100A and a second stage 100B. In some implementations, first stage lOOAmay comprise a filtration system 120, and the second stage 100B may comprise a permeate separation system 140.

[0109] As illustrated in separation process 100, an alcoholic beverage 110 can be provided to the filtration system 120 for separation. In some implementations, the alcoholic beverage may comprise wine, beer, spirits, or the like. In some implementations, the filtration system 120 comprises a semipermeable membrane having a feed side, a permeate side, and a molecular weight cutoff (MWCO) in a range of 75 Da to 300 Da, a feed inlet, and a permeate outlet.In some implementations, a pressure can be applied to the feed side of the filtration system 120. In some implementations, the feed pressure can be in a range of about 25 psia (172 kPa) to 450 psia (3105 kPa). In some implementations, the feed pressure can be selected to maximize ethanol flux through the semipermeable membrane of the filtration system 120. In some implementations, the permeate side of the semipermeable membrane can be maintained at atmospheric pressure.

[0110] In some implementations, filtration system 120 may output a retentate 160 from which a certain amount of ethanol has been removed. For example, if the alcoholic beverage 110 comprises wine, the retentate 160 may include a more concentrated wine where a portion of ethanol and a portion of water has been removed from the starting material by the membrane of the filtration system 120. In some implementations, a substantial portion of flavor compounds and aroma compounds in the alcoholic beverage 110 remain present and are not passed through the semipermeable membrane of filtration system 120.

[0111] In some implementations, filtration system 120 also outputs a first permeate 130. In some implementations, first permeate 130 comprises a mixture of ethanol and water.

[0112] In some implementations, first permeate 130 can be further processed into a beverage 135. In some implementations, beverage 135 can comprise a hard seltzer. In some implementations, first permeate 130 can be further processed by a permeate separation system 140. In some implementations, permeate separation system 140 may comprise a membrane contactor comprising two or more membranes, a permeate outlet, a gas inlet to supply a carrier gas, a gas outlet, a condenser fluidly connected to the gas outlet, and a condensate stream outlet, as described in more detail elsewhere herein.

[0113] In some implementations, permeate separation system 140 can produce an aqueous, dealcoholized liquid 150. The aqueous dealcoholized liquid 150 can comprise a refreshedpermeate. In some implementations, permeate separation system 140 can produce an ethanol- enriched liquid 145. In some implementations, the ethanol-enriched liquid 145 may be further processed, such as further distilled, to result in a more concentrated and purer form of ethanol.

[0114] In some implementations, the aqueous dealcoholized liquid 150 may be returned to the filtration system 120 as a refreshed permeate. For example, the alcoholic beverage 110 and dealcoholized liquid (refreshed permeate) 150 can be combined and reprocessed by the filtration system 120 to produce additional quantities of first permeate 130 and additional quantities of retentate 160. It should be noted that the process of returning refreshed permeate 150 to the filtration system 120 can be repeated one or more times to further refine the feed fluid and remove the appropriate amount of ethanol while retaining the appropriate flavor compounds and aroma compounds in the feed fluid.

[0115] In some implementations, refreshed permeate may be combined with retentate 160 to produce a reduced alcohol beverage 170, wherein the concentration of ethanol has been reduced (e.g., about 0.5% to about 100% by volume), while a substantial portion of the water, flavor, and aroma compounds of the original alcoholic beverage are retained.

[0116] An illustrative assembly for removal of ethanol from a fluid is shown in FIG. 2. As illustrated, and in a general sense, assembly 200 can include a first vessel 210, a filtration system 220, a controllable pressure source 280 fluidly connected to the filtration system 220, a permeate vessel 290, and a permeate separation system 300. Controllable pressure source 280 has been indicated along a conduit 330 that fluidly connects the first vessel 210 and the filtration system 220. It is understood however, that controllable pressure source 280 can be located at any suitable location that allows the pressure source to apply a pressure to the filtration system 220.

[0117] In some aspects, the filtration system 220 includes a selectively permeable membrane 230, a feed inlet 240, and a permeate outlet 250. As illustrated, permeate outlet 250 can fluidly connect to a conduit 340 that leads to permeate vessel 290, thus providing passageway for permeate leaving the filtration system 220 to travel to permeate vessel 290. Permeate vessel 290 can be provided in a size and configuration suitable for collection of permeate (e.g., a first permeate comprising ethanol and water) that has passed through semipermeable membrane 230 in the filtration system. Permeate vessel can include one or more inlets 350 and outlets 360 for receiving and / or transporting permeate away from the permeate vessel 290.

[0118] In some implementations, permeate vessel 290 can be fluidly connected to a permeate separation system 300 via a conduit 370. In some implementations, the permeateseparation system 300 includes a membrane contactor comprising two or more internal membranes, a permeate outlet, a gas inlet to supply a carrier gas to a side of the hollow fiber membranes, a gas outlet, and a condenser fluidly connected to the gas outlet. In various implementations, a conduit 310 fluidly connects a condensate stream outlet of the permeate separation system 300 with the first vessel 210.

[0119] In some aspects, the first vessel 210 is configured to receive an aqueous liquid. In some implementations, the aqueous liquid can comprise water or refreshed permeate (discussed elsewhere herein). First vessel 210 is fluidly connected to the feed inlet 240 of filtration system 220, to thereby provide aqueous liquid to the filtration system when desired. In some implementations, filtration system 220 includes a selectively permeable membrane 230 having a feed side 260 and a permeate side 270. In use, a feed solution, such as an alcoholic beverage, is provided to the filtration system 220 via feed inlet 240. In some implementations, the feed solution can comprise wine, beer, or liquor. In some implementations the feed solution can comprise an alcoholic beverage fermented from grapes. In some aspects, the feed solution has an initial alcoholic content expressed as ABV. In some implementations, the feed solution can comprise an alcoholic beverage fermented from grapes with an initial ABV in the range of about 12% to about 16%. In some implementations, the feed solution comprises wine, such as red wine or white wine.

[0120] In some aspects, the feed solution comprises water, ethanol, and a flavor component.

[0121] In some implementations, filtration system 220 can include one or more inlets 240 that provide channels to provide feed solution to, and / or withdraw feed solution from, the filtration system 220. In some implementations, inlets 240 can provide a closed loop system that allows recirculation of feed solution.

[0122] In some implementations, a controllable pressure source 280 is fluidly connected to the filtration system. In some implementations, the controllable pressure source 280 comprises a source of gas. In some implementations, the controllable pressure source 280 comprises a source of inert gas, such as carbon dioxide, helium, nitrogen, argon, or other suitable gas. As illustrated in FIG. 2, the controllable pressure source 280 can be located along a conduit 320 that fluidly connects first vessel 210 with the filtration system 220. In some implementations, one or more of the first vessel 210, filtration system 220, permeate vessel 290, and / or permeate separation system 300 can include one or more conduits that provide channels to provide solution to and / or from the various elements of the assembly 200.

[0123] In some implementations, the membrane 230 includes a feed side 260 having a surface that contacts the feed solution, and a permeate side 270 having a surface the contacts the permeate.

[0124] In some implementations, the membrane 230 comprises a selectively permeable membrane configured to allow passage of one or more components of the feed solution (e.g., a target solute such as ethanol) therethrough, while rejecting one or more components of the feed solution. As used herein, the sieving property of a membrane, i.e., its permeability to components of a liquid, is determined by the membrane pore size and sets the maximum size for compounds that can pass through the membrane with fluid flow. The sieving coefficient for a given substance can be described as the ratio between the substance concentration in the permeate and its concentration in the feed liquid (i.e., the alcoholic beverage), and is therefore a value between 0 and 1. Assuming that the size of a compound is proportional to its molecular weight, a common way to illustrate the properties of membranes is by building a sieving curve, which depicts the sieving coefficient as a function of the molecular weight. The expression “molecular weight cutoff” or “MWCO” or “nominal molecular weight cutoff’ as interchangeably used herein is a value for describing the retention capabilities of a membrane and refers to the molecular mass of a compound where the membranes have a retention of 90%, corresponding to a sieving coefficient of 0.1. The MWCO can alternatively be described as the molecular mass of a compound, such as, for example, water or ethanol, where the membrane allows passage of 10% of the molecules. MWCO is one membrane property (along with such values as pore size and rejected species) provided by various commercial sources to assist in selection of a membrane for a particular separation process.

[0125] In some implementations, the membrane comprises a semipermeable membrane having a MWCO of 500 Dalton (Da), or 450 Da, or 400 Da, or 350 Da, or 300 Da, or 250 Da, or 200 Da, or 150 Da, or 125 Da, or 100 Da, or 75 Da, or the like. In some implementations, semipermeable membrane 230 has a MWCO in a range of about 75 Da to about 300 Da, or about 100 Da to about 300 Da, or about 150 Da to about 300 Da.

[0126] In some aspects, the quality of separation of a selectively permeable membrane can be expressed as the rejection factor of the membrane for a given solute. The rejection factor can be defined as -Cpermlcfeed, where cperm is the permeate concentration and Cfeed is feed concentration. To arrive at a percentage rejection (“rejection rate”), the rejection factor is multiplied by 100. As used herein, rejection is defined as the amount of a compound in a feed solution that does not permeate the membrane in a separation process (i.e., that is retained in the feed solution). In some implementations, the membrane comprises a semipermeablemembrane having a MgSC rejection rate of at least 97% with a 1% MgSC solution. In some implementations, the membrane comprises a semipermeable membrane having a NaCl rejection rate of at least 85% with a 1% NaCl solution.

[0127] In some implementations, the semipermeable membrane 230 comprises a plurality of pores having an average pore size of 10 nm or less. In some implementations, membrane 230 comprises a plurality of pores having an average pore size in a range of about 0.1 nm to about 10 nm. Pore size can be measured by such well known methods as the bubble point method, mercury porosimetry, thermoporometry, permporometry, adsorption methods, as well as methods based on liquid or gas transport, microscopic methods (such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and the like).

[0128] In some implementations, the membrane 230 can be fabricated of cellulose acetate, cellulose triacetate, regenerated cellulose (pure cellulose which has been treated in a chemical bath for enhanced chemical resistance), mixed cellulose (e.g., mixtures of cellulose acetate and cellulose nitrate), or other similar non-toxic materials that can be formed into semipermeable membranes having a desired MWCO.

[0129] In some implementations, the separation or removal of organic compounds from fluids includes using a semipermeable membrane. In some implementations, a semipermeable membrane can comprise a material having an average pore size in a range of about 0.1 to about 10 nm, or about 0.1 nm to about 9 nm, or about 0.1 nm to about 8 nm, or about 0.1 nm to about 7 nm, or about 0.1 nm to about 6 nm, or about 0.1 to about 5 nm, or about 0.1 nm to about 4 nm, or about 0.1 to about 3 nm, or about 0.1 to about 2 nm, or about 0.1 to about 1 nm. In some implementations, a semipermeable membrane can comprise a material having an average pore size of about 1 nm or smaller, or about 0.9 nm or smaller, or about 0.8 nm or smaller, or about 0.7 nm or smaller, or about 0.6 nm or smaller, or about 0.5 nm or smaller, or about 0.4 nm or smaller, or about 0.3 nm or smaller, or about 0.2 nm or smaller. In some implementations, semipermeable membranes can comprise a material having an average pore size in a range of about 0.1 nm to about 1 nm. Semipermeable membranes having the above average pore size ranges will be utilized to describe certain concepts, as these applications are useful to highlight features and advantages. However, it will be readily apparent that the pore size of a material can be selected to provide a MWCO that will allow selective removal of desired organic materials from a starting fluid.

[0130] In some examples, the selectively permeable membrane may be a polymeric membrane including a polymeric material therein such as cellulose acetate (e.g., commercially available from Trisep Corporation, Pall Corporation, Sterlitech Corporation, andMilliporeSigma), cellulose triacetate, polysulfone / polyamide (e.g., commercially available from Trisep Corporation), polypiperazine- amide (e.g., commercially available from Trisep Corporation,), polyamide, polyamide thin film composite membrane (e.g. commercially available from Suez, formerly GE corporation), polyester (PE) or polypropylene (PP) composite (e.g., commercially available from Alfa Laval), aramid, poly(vinylidene fluoride), polyacrylonitrile / crosslinked dopamine, or other polymeric materials, and composite membranes formed from combinations of one or more of any of the foregoing materials. In some implementations, selectively permeable membranes useful herein can be designed for liquid food or biotechnology applications (thus providing beverage-safe contact).

[0131] In some implementations, the selectively permeable membrane may include one or more support layers supporting one or more functional layers, such as one or more polyamide thin film layers. In some examples, the selectively permeable membrane can include an array of membranes that may be arranged in parallel or in series, or in any combination of parallel and series.

[0132] Illustrative separation methods and systems disclosed herein can allow ethanol to be removed from a feed solution at ambient temperatures and mild pressure ranges, while allowing selective retention of permeable solute(s) such as water, volatile organic compounds (VOCs), sugar(s), and the like. This can provide advantages, such as reduced impact on protein structures that pertain to flavor, aroma, and taste.

[0133] In some aspects, agitation can be applied to the feed solution within the filtration system. One implementation is shown in FIG. 2, wherein agitation in the form of stirring can be applied to the feed solution within the filtration system 220. Stirring is indicated generally at 320 in FIG. 2. It will be readily appreciated that agitation can be provided to the feed solution through any suitable means, such as pumps, movement of system components, and the like. Agitation of the feed solution can be beneficial in reducing the occurrence of concentration polarization phenomena in the system. In some implementations, agitation of the feed solution can be beneficial in reducing the occurrence of concentration polarization phenomena at or near the membrane surface (e.g., the membrane surface contacting the feed solution), by creating turbulent flow of the solution.

[0134] FIG. 2 illustrates basic schematics of separation systems useful to remove an organic compound from a liquid. It will be understood that additional configurations that employ these concepts are contemplated as well. For example, FIG. 2 illustrates a flat sheet membrane configuration, wherein the membrane extends across the vessel of the filtration system 220. In some implementations, the membrane can be provided in a different moduleconfiguration. For example, flat sheet membranes can be provided in plate-and- frame or spiralwound configurations. In some implementations, flat sheet membranes can be provided in membrane holding devices (e.g., frames) that are tubular, spiral wound, or other configurations.

[0135] FIG. 2 illustrates a separation assembly 200 that includes one filtration system 220. However, it will be readily appreciated that any number of filtration systems 220 can be provided in serial configuration, so that the permeate from a filtration can be passed into a second (third, fourth, etc.) filtration system to further separate ethanol from an alcoholic beverage.

[0136] In some aspects, membranes can be provided in configurations other than a flat sheet. For example, in some implementations, membranes can be provided in capillary configurations, hollow fibers, tubular configurations, bag configurations, and the like.

[0137] In some implementations, systems can be designed on a modular basis that can provide a high degree of flexibility, as membranes can be built into modules, and modules can be built into loops, and loops can be built into systems. The design of a system can thus be customized to meet process needs and can be expanded to accommodate production requirements.

[0138] In accordance with methods and systems described herein, as ethanol and water permeate the semipermeable membrane within the filtration system 220, the liquid remaining on the feed side of the membrane (retentate) comprises compounds that did not permeate the membrane, such as one or more of flavor compounds, aroma compounds, and the like. The retentate can be directed to one or more downstream product components fluidly coupled to the filtration system. As ethanol and water pass through the membrane, a first permeate is formed on the permeate side of the semipermeable membrane. The first permeate can be directed to one or more downstream components fluidly coupled to the permeate vessel 290 of the system.

[0139] The one or more downstream product components fluidly coupled to the filtration vessel can include one or more of a pipeline, a storage tank, a point of use device, a conduit, a pressure pump, a temperature control device (such as a refrigerator), a packaging apparatus, one or more membrane separation elements, or individual packages (such as bottles, kegs, and the like). The one or more downstream components fluidly coupled to the permeate vessel can include one or more of a pipeline, a conduit, a storage tank, a pump, a temperature control device (e.g., a refrigerator), one or more permeate recovery (e.g., regeneration) apparatuses, a waste storage, a permeate storage, and the like. In some implementations, one or morepermeate recovery or regeneration apparatus can include separation elements (such as those described herein, or reverse osmosis systems), or one or more distillation apparatuses.

[0140] As illustrated in FIG. 2, assembly 200 can include a permeate separation system 300 fluidly connected to the permeate vessel. The permeate separation system can be configured to separate ethanol from the first permeate created through the filtration system. In some implementations, permeate separation system 300 can utilize membrane separation techniques (e.g., membrane contactors) to separate ethanol and water. In some implementations, permeate separation system 300 can utilize membrane separation techniques (e.g., membrane contactors) to separate ethanol, water, and one or more flavor components and / or aroma components contained in the first permeate.

[0141] In some implementations, permeate separation system 300 can comprise a membrane contactor system. In accordance with some aspects, a membrane contactor system can generally include membranes (e.g., a plurality of membranes) having a first side and a second side, a permeate outlet, a gas inlet to supply a carrier gas to a side of the membranes, a gas outlet, and a condenser fluidly connected to the gas outlet. In some implementations, the membranes comprise microporous or nonporous membranes.

[0142] Generally speaking, membrane contactor systems in accordance with present methods and systems achieve separation of water and ethanol by applying one or more of concentration, temperature, and activity as driving forces. The contacting system may be liquid-liquid or liquid-gas. In some implementations, the membrane contactor utilizes a porous membrane, which provides the surface of contact for the first permeate and either a carrier gas or carrier liquid. In some implementations, the carrier is a gas.

[0143] An illustrative permeate separation system 300 is shown in FIG. 3. FIG. 3 illustrates one schematic representation of a possible permeate separation system 300 identified in FIG. 2. As shown, first permeate is transported to the permeate separation system 300 via conduit 370 and passes into membrane contactor 410 through permeate inlet 450. In some implementations, membrane contactor 410 comprises a gas inlet 430, a gas outlet 440, permeate inlet 450, and permeate outlet 460. In some implementations, membrane contactor comprises two or more internal semipermeable membranes. In some implementations, the semipermeable membranes can comprise microporous or nonporous membranes. In some implementations, membranes are provided as hollow fiber membranes. In some implementations, first permeate is introduced into permeate separation system 300 and flows through the hollow fiber membranes while a carrier gas is applied to the outside of the hollow fiber membranes. In some implementations, applying a carrier gas to the outside of the hollowfibers creates a difference in the gas concentration levels between the inside (lumenside) and outside (shellside) of the membrane. This concentration difference may drive transfer of ethanol from the first permeate liquid stream. In some implementations, liquid and gas sides of the membrane can be reversed, and carrier gas my flow through the inside (lumenside) of the hollow fiber, while liquid first permeate is applied on the outside (shellside) of the fibers. Thus, in general aspects, a first side of the membranes within membrane contactor 410 can be contacted with a liquid, while a second side of the membranes within membrane contactor 410 can be contacted with a gas. The first and second sides can comprise the lumenside and shellside. Flow through the membrane contactor can be parallel, radial, and / or transverse. In some implementations, a baffle can be included to increase membrane surface area contact.

[0144] In some implementations, porous hollow fiber membranes can comprise a plurality of pores having an average pore size of 10 nm or less. In some implementations, membranes within membrane contactor may comprise a plurality of pores having an average pore size in a range of about 0.002 pm to about 10 pm, or about 0.002 pm to about 5 pm, or about 0.002 pm to about 4 pm, or about 0.002 pm to about 3 pm, or about 0.002 pm to about 2 pm, or about 0.002 pm to about 1 pm, or about 0.002 pm to about 0.5 pm, or about 0.002 pm to about 0.2 pm. Pore size can be measured by such well known methods as the bubble point method, mercury porosimetry, thermoporometry, permporometry, adsorption methods, as well as methods based on liquid or gas transport, microscopic methods (such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and the like). In some implementations, membranes within membrane contactor can be nonporous.

[0145] In some implementations, a reduced pressure may be maintained downstream of the membrane contactor in order to pull carrier gas through the membrane contactor. In some implementations, the reduced pressure downstream of the contactor may be 1 atmosphere (760 torr) or less. In accordance with some implementations, a pressure in a range of about 5 torr to about 760 torr, or about 5 torr to about 700 torr, or about 5 torr to about 600 torr, or about 5 torr to about 500 torr, or about 5 torr to about 400 torr, or about 5 torr to about 300 torr, or about 5 torr to about 200 torr, or about 5 torr to about 100 torr, or about 5 torr to about 30 torr may be maintained at a location downstream of the membrane contactor to pull carrier gas through the membrane contactor.

[0146] In various implementations, the permeate separation system may be maintained at ambient temperatures for removing ethanol and one or more flavor components and aroma components from the first permeate. In some aspects, steps of directing the first permeate to a membrane contactor can be performed at ambient temperatures. In some implementations, thepermeate separation system may be maintained at a temperature in a range of about 0°C to about 30°C, or about 5 °C to about 30 °C, or about 10 °C to about 30 °C, or about 15 °C to about 25 °C.

[0147] In various implementations, permeate separation system 300 comprises a gas source 400. Gas source 400 may supply carrier gas to the membrane contactor 410. In various implementations, carrier gas may comprise carbon dioxide (CO2), helium (He), nitrogen (N2), argon (Ar), or other inert gas.

[0148] In some implementations, hollow fiber membranes within the membrane contactor can be fabricated from polypropylene, PDMS, polyolefin, or the like. The hollow fiber membranes can be provided in a variety of configurations within the separation system housing. Illustrative membrane contactors are commercially available, for example, through 3M™ Company (for example, the Liqui-Cel™ Membrane Contactor product line), PermSelect™ (for example, PermSelect™ Silicone Gas Exchanger product line), Mitsubishi Chemical Aqua Solutions Company (for example, Sterapore™ product line), and Nagasep Nagayanagi Co., Ltd.

[0149] In various implementations, gas leaving the membrane contactor 410 at gas outlet 440 has become concentrated with components that are capable of permeating the membrane (e.g., ethanol), while the liquid leaving the device at permeate outlet 460 is enriched in components that do not permeate the membrane as readily (e.g., water).

[0150] In some implementations, gas leaving the membrane contactor 410 at gas outlet 440 comprises a gas mixture that may now pass to a condenser 470 to condense compounds present in the gas mixture. In some implementations, condenser 470 can provide one or more condensation stages, such that as the gas mixture is cooled, components of the mixture can be separated. In some implementations, components of the gas mixture having a first boiling point can be condensed in a first stage (such as ethanol), thereby providing an ethanol-enriched liquid. The ethanol can be collected at 480. In some implementations, ethanol-enriched liquid can have a higher alcohol content than the starting alcoholic beverage. In some implementations, ethanol-enriched liquid can comprise an alcohol content of about 40% to about 80% by volume. Optionally, a second stage can be included in the condenser 470 to condense components of the gas mixture that have a second boiling point, such as residual flavors and aromas. These residual flavors and aromas can be collected in a vessel within 480.

[0151] In some implementations, once residual flavors and / or aromas, and ethanol, have been separated from the gas, the gas can be recycled to gas inlet 430, thereby providing a closed system.

[0152] In various implementations, liquid leaving the membrane contactor 410 at permeate outlet 460 may comprise an aqueous liquid 510. This liquid can, in some implementations be reused as a refreshed permeate in the separation methods and systems described herein. Thus, in some implementations, the aqueous liquid 510 can be provided to the filtration system as a refreshed permeate.

[0153] In some implementations, residual flavors and aromas collected at 480 can be combined with aqueous liquid 510. In these aspects, residual flavors and / or aromas can be recovered and reconstituted to the dealcoholized beverage.

[0154] In some implementations, the separation methods and systems described herein can be used at any desirable point during formulation of an alcoholic beverage, for example, during distillation, or after the beverage has been fully prepared.

[0155] In various implementations, methods and systems can utilize continuous flow separation. In these aspects, products of the permeate separation system (ethanol-enriched solution and aqueous liquid) can be continuously removed from the system. In some implementations, the aqueous liquid produced by the permeate separation system can include low amounts of ethanol (e.g., 5% or less, or 4% or less, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less by volume). In these aspects, for example, the aqueous liquid can comprise a refreshed permeate. In some implementations, methods include adding the refreshed permeate directly to the retentate, thereby providing a reduced alcohol beverage. In some implementations, refreshed permeate can be utilized in the filtration system. These aspects can provide a closed-loop process wherein components of the permeate can be recycled through the system. The ethanol recovered from the permeate separation system can be utilized to formulate other alcoholic beverages, or ethanol-containing solutions for industrial applications. In some implementations, permeate is repeatedly refreshed and reused. In this mode, the refreshed permeate can be recirculated by combining the refreshed permeate with the retentate obtained in the first stage. In some aspects, such processes can reduce water and energy usage, since refreshed permeate can be repeatedly generated within the overall system, reducing the need for fresh water to be added to the system.

[0156] In some implementations, the contained configurations illustrated in the figures can be included inline in a beverage processing machine. For example, the separation system 200 illustrated in FIG. 2 can be included inline within the production process for a beverage, such as an alcoholic beverage. In some implementations, the contained configuration illustrated in FIG. 2 can utilize concepts of the cross flow configuration described herein. In some implementations, the contained configurations illustrated in the figures can be included asstand-alone units for processing alcoholic beverages. For example, the separation system 200 illustrated in FIG. 2 can be provided as a separate, stand-alone unit that can be used at any time after an alcoholic beverage has been prepared. In some examples, stand-alone separation units can be utilized at the point where a user wishes to open an alcoholic beverage and remove some or all of the ethanol before drinking the beverage (point of use).

[0157] It should therefore be appreciated that the various methods and systems discussed herein, when applied to alcoholic beverages, enable the production of dealcoholized, low alcohol, or substantially non-alcoholic beverages that taste like their traditional alcoholic beverage counterparts. In some implementations, the methods and apparatuses discussed herein enable ethanol or ethyl alcohol to be substantially removed from an alcoholic beverage while substantially preventing other compounds from being removed from the alcoholic beverage. The resulting beverage can either contain low alcohol or substantially no alcohol, while retaining many or most of the compounds that give the original alcoholic beverage its signature taste. For example, if the methods and apparatuses discussed herein are applied to a brewed alcoholic beverage (e.g., a stout beer) to produce an altered stout beer, the altered stout beer continues to taste like the stout beer, while the altered stout beer has low or substantially no alcohol. As another example, if the methods and apparatuses discussed herein are applied to a distilled spirit like gin, the altered gin continues to taste like the original gin, while the altered gin has low or substantially no alcohol. In other words, in some implementations, the novel methods and apparatuses discussed herein can produce a low alcohol or non-alcoholic beverage that tastes the same or very similar to their alcoholic counterparts and can mimic or substitute for traditional alcoholic beverages. In some implementations, the methods and apparatuses discussed herein can be applied to other beverages or human consumable items. For example, if a lactating mother consumed alcohol, the milk the mother produces may contain alcohol. Previously, such a lactating mother may be inclined to throw out any milk contaminated with alcohol. When the mother’s milk is applied to the various methods and apparatuses noted above, the mother’s milk can have the alcohol contamination removed from the milk and enable the milk to be provided to the mother’s nursing child. As another example, the methods and apparatuses discussed herein can be applied to tinctures (e.g., a solution that has ethanol as its solvent). In some implementations, a tincture can be an extract of plant or animal material dissolved in ethanol. Solvent concentrations of ethanol in the tinctures can typically range between 25% and 60%. In some implementations, the solvent concentrations of ethanol can run as high as 90%. The various methods and apparatuses discussed herein can be applied to such tinctures to remove the ethanol, while substantially retaining the extractwithout the alcohol. As yet another example, some consumable food products such as flavoring (e.g., vanilla flavoring) or cannabis extracts are stored in an alcohol-based solution. The various methods and apparatuses discussed herein can be applied to such consumable products to remove the alcohol, while retaining the consumable item. Removing alcohol from such consumable items is highly desirable for people that must avoid alcohol (e.g., people that are allergic to alcohol, people with alcohol addiction problems, etc.). It should also be appreciated that the above methods and apparatuses can be applied to other suitable fluids in the food and beverage industry.

[0158] The present disclosure is not to be limited in terms of the particular implementations described in this application, which are intended as illustrations of various aspects. Moreover, the various disclosed implementations can be interchangeably used with each other, unless otherwise noted. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall 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 such 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.

[0159] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity.

[0160] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies 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 “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that theintroduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to implementations containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., “a” and / or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities 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.” In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0161] A number of implementations have been described. Various modifications may be made without departing from the spirit and scope of the invention. For example, various forms of the methods illustrated above may be used, with steps re-ordered, added, or removed. Accordingly, other implementations are within the scope of the following claims.EXAMPLES

[0162] Example 1. Dealcoholization of Red Wine.

[0163] Ethanol was removed from a red wine sample as follows. Red Wine Sample A (The Prisoner 2019 Cabernet Sauvignon) with an initial ABV of 15% was chosen as the feed liquid. Red Wine Sample A in an amount of 300 ml was added to a filtration system that included a cellulose acetate based nanofiltration membrane having a MWCO of 150-300 g / mol. The effective membrane diameter was 76mm, and the operation temperature was approximately 22 °C (room temperature). The applied pressure of 40 psia (276 kPa) was supplied by filtered air. After 6.5 hours, it was observed that the feed side volume was reduced to 247ml, meaning that 53 ml liquid passed through the membrane as permeate. The overall permeance was 0.04517 l / m2 / h / psia (LMH / psia), extrapolated to a flux of 13.1 LMH at 20 bar.

[0164] After restoring the volume lost by adding 53 ml deionized water to the retentate, the product (Al) was determined to have an ABV level of about 12.3 %, representing an 18% reduction from the initial Wine Sample A. Product was not subjected to a permeate separation system, but was assessed after processing through the filtration system only. The product Al and untreated Sample Wine A were sent to a professional sommelier for randomized wine tasting, to assess the differences between product Al and untreated Red Wine Sample A. The closeness was graded into 5 levels, with a score of “5” being identical to the original wine, and “1” being the least similar. The feedback revealed that the reduced wine product Al was very close to the untreated wine overall, with detailed comparison shown in Table 1. These samples were also tasted by an external taster. Surprisingly, some tasters preferred the reduced version (i.e., product Al), due to the high ethanol level and intensive perception experience of the untreated Red Wine Sample A.Table 1. Red Wine Sample A versus product Al

[0165] Example 2. Dealcoholization of Red Wine.

[0166] Ethanol was removed from a red wine sample as follows. Red Wine Sample B (J Lohr 2020 Cabernet Sauvignon) with an initial ABV of 14.1% was chosen as the feed wine. An initial volume of 300 ml of Red Wine Sample B was added to a filtration system that included a cellulose acetate based nanofiltration membrane having a MWCO of 150-300 g / mol. The effective membrane diameter was 76mm, and the operating temperature was approximately 22 °C. The applied pressure was 40 psia (276 kPa) supplied by filtered air. The separation process was stopped at expected volume loss at the feed side. The loss of volume ranged from 10 to 80% based on the initial feed volume.

[0167] The volume lost in the retentate was restored by adding an equal amount of deionized water to the retentate, providing product (Bl). Product was not subjected to a permeate separation system, but was assessed after processing through the filtration system only. The obtained samples were analyzed for the chemical composition profiles, including ethanol level, pH, volatile acid, fructose, glucose, and the like, as shown in Table 2. The actual reduction was determined by the actual ABV of the reduced samples (7 - actual ABV in reduced sample / actual ABV in untreated wine, unit: %). Since the membrane employed in this example had a molecular weight cutoff (MWCO) of 150~300g / mol, the concentrations of components smaller than this range (such as tartaric acid, fructose, and glucose in Table 2) decreased withthe higher degree of alcohol reduction. The apparent increase in glucose and fructose in samples B4 and B5 were likely due to analytical process discrepancy. Nevertheless, the pH values remains the same regardless the slight change in acid concentration.Table 2 Chemical composition profiles of reduced samples and untreated B.Reduction ABV Volatile Tartaric Fructose Glucose amp £(%) (%) acid (g / L) acid (g / L) (g / L) (g / L)PIteratedQ M 1 Q 64 6J 0 51 < Q 3 3 6?wine BProduct ” 8.5 12.9 0.60 5.7 < 0.3 < 0.3 3.36 1P nrouuduuct18 4 n 5 0 51 5 3 0 58 < () 3 3 59B2Product ” 39 8.6 0.31 4.4 0.7 1.28 3.51B3Product ” 51 6.9 0.17 3.8 1.52 2.14 3.46B4P nrouuduuct61 5 5 0 Q4 3 4 2 35 2 953 43B5

[0168] Similar results were also observed for other compounds, such as phenolic compounds. Both reduced Products Bl to B5 and untreated Wine Sample B were analyzed by high performance liquid chromatography (HPLC) to determine the phenolic compound profile. The phenolic compound concentration ratio between the reduced Product B5 and the untreated Wine Sample B was calculated and presented in FIG. 4A, as well as the rejection efficiency. FIG. 4A illustrates the concentration ratio of phenolic compounds in a 60% reduced wine (Product B5). FIG. 4B illustrates the rejection efficiency of some compounds with a function of molecular weight, calculated based on weight amount in permeate / weight amount in feed. Results indicated that, with increasing molecular weight, the compounds in wine were well retained by the separation membrane, especially tannins, well known for the astringency taste notes in wine. It is worth noting that the actual concentration of these investigated compounds in FIG. 4A is related to the degree of reduction, and a high reduction degree leads to a low concentration of the compound.

[0169] It was found that for the cellulose acetate membrane utilized, compounds having a molecular weight in the range of 150-300 Da were partially retained in the feed wine, whilst other compounds of interest, such as tannins, phenolics, anthocyanins were well preserved. At a modest degree of alcohol reduction, the flavor profile was reasonably maintained.

[0170] To obtain sensory data, the alcohol-reduced products B1-B5 and untreated Red Wine Sample B were sent to professional sommeliers or / and oenophiles for blinded wine tasting. The closeness was graded into 5 levels, with a score of “5” being identical and a score of “1” being least similar. The feedback revealed that up to a reduction of 30% (i.e., a reduction from 14% ABV to 10% ABV), the reduced samples were highly similar to the original Red Wine Sample B, the alcohol-reduced products B1-B5 demonstrated a preserved aroma, flavor, and body. While a further reduction led to some unpreferred perception experiences, such as “watery” or “watered down” perceptions, this was possibly due to a partial loss of low molecular weight substances in wine besides alcohol. The tasting feedback matched the results from the chemical analysis, i.e., that a high reduction degree leads to low levels of compounds originated in wine.

[0171] Some correlations between the reduction and various tasting feedback of the samples are illustrated in FIG. 5 and FIG. 6. FIG. 5 illustrates tasting feedback of the reduced Products B1-B5 and the untreated Red Wine Sample B in terms of fruity aroma. The images in in the figures refer to the type of fruity aromas tasters sensed. FIG. 6 illustrates tasting feedback of reduced Products B1-B5 and the untreated Red Wine Sample B in terms of body. Results indicated that fruity taste and body were well preserved in the ethanol-reduced samples.

[0172] Example 3. Dealcoholization of Red Wine.

[0173] Ethanol was removed from a red wine as follows. Red Wine Sample C (Oak Ridge 2020 Lodi Estates Cabernet Sauvignon) with an initial ABV of 14.4% was chosen as the feed wine. An initial volume of 300 ml of Red Wine Sample C was added to a filtration system that included a cellulose acetate based nanofiltration membrane having a MWCO of 150-300 Da. The effective membrane diameter was 76mm, and the separation was conducted at room temperature (approximately 22 °C). The applied pressure was 40 psia (276 kPa) supplied by filtered air. The separation process was terminated at an alcohol reduction of about 30% ABV. After adding an equal volume of deionized water to the retentate, a reduced sample, named Product Cl, was obtained. The actual ABV level of Product Cl was 10.3%, determined by FTIR-based wine analyzer.

[0174] Another batch of samples, with an expected 50% reduction, were prepared in a similar manner, except the reduction was achieved by a two-stage process. In the first stage, the wine was reduced by approximately 30% ABV to provide a retentate product Cl. The volume of Cl was then restored by adding an equal amount of distilled water. This restored retentate was employed as the feed for a second stage of pressure-assisted diafiltration process, with the same process parameters as the first stage. The second stage was also stopped at a 30%reduction in ABV (based on the initial feed of this stage). After restoring volume by adding distilled water to the retentate, the final product, named Product C2, exhibited a reduction of 49% (calculated based on measured ethanol levels in the sample C2 and untreated sample C). To determine the effect of atmospheric oxidation, N2 was employed in the two-stage processes and compared with the results from filtered air for pressure supply. Product was not subjected to a permeate separation system, but was assessed after processing through the filtration system only.

[0175] Both samples (Products Cl and C2) were analyzed by professional sommeliers and oenophiles for blinded wine tasting, with the untreated Red Wine Sample C as the control. The tasters were informed that these samples were reduced, but without further information. The tasters were required to evaluate the closeness to control sample of the provided sample, with the value “5” indicating the samples were identical, and the value “1” indicating the samples were the least similar. Additionally, tasters were encouraged to guess how much the samples had been reduced.

[0176] The typical tasting feedback of Product Cl and Product C2 as compared to untreated Red Wine Sample C is presented in FIG. 7. The 30% reduced Cl products were believed to be very close to the untreated Wine Sample C, as most parts were graded as 4 or 4.5. Moreover, the taster commented "Nice aroma and flavor. Really good balance. Without knowing it is reduced sample, 1 may think it is original.” In terms of the 50% reduced sample, one taster thought the product was only 15% reduced, and another taster guessed that it was reduced by 30%, which was much lower than the actual reduction (i.e., 49%). This demonstrated that the separation process using a cellulose based semipermeable membrane can achieve a high retention of flavor compounds contributing to perception satisfaction, and thus provide ABV reduced samples with great taste.

[0177] Example 4. Dealcoholization of Red Wine.

[0178] In a batch mode of ABV reduction, a fixed volume of 300-mL 2021 Cabernet Sauvignon from Oak Ridge Estate Crown wine was placed in a filtration system including a cellulose acetate membrane having an effective membrane area of approximately 0.00453 m2. The separation was conducted at room temperature and pressure of 60 psi at equilibrium (pressure was ramped from 40 psi to keep incremental differentiation between the reservoir and membrane cell). After 64 hours, the wine flavor compounds were concentrated at the upstream followed by the restoration of the total wine volume, theoretically resulted in the same flavor concentration as the feed wine if the loss of flavors during the dialysis was minimal. Volume restoration was initially done manually by stopping the dialysis experimentat a desired ABV reduction, calculated by volume change of the original alcohol: ABV reduction = 1 - 300 / [Vi - Vy] + 300, where V / and Vy are the initial and final volume of the water reservoir, respectively. During the process, water in reservoir was introduced to the filtration vessel (retentate) to maintain the liquid volume at 300 ml due to pressure differential between the filtration vessel and water reservoir as a result of volume change. This process is usually characterized by a constant increase in solute concentration that may easily cause a change in the state of flavor substances in ethanol / water resulting in soluble fractions with partial precipitation of insoluble components. To address this issue, a continuous separation process and system was designed, which, in theory, will help to maintain the flavor concentration constant by providing the permeate from the filtration system to a permeate separation process, and removing ethanol from the permeate to create a refreshed permeate. The refreshed permeate, which comprises an aqueous liquid, can be continuously provided to the wine within the filtration system, to maintain a constant volume.

[0179] A slight decrease in inner pressure within the vessel of the filtration system due to feed solution volume loss will drive aqueous liquid from an aqueous liquid source (feed source or refreshed permeate from the permeate separation process) to flow into the filtration system vessel to make up the volume loss, so to reach an equilibrium in pressure again. It was observed that separation can last up to 40 hours as illustrated in example 4(i) and example 4(ii).

[0180] Example 4(i). Red wine sample (300 ml of Cabernet Sauvignon from J. Lohr, marked ABV 13.9%) was supplied to the vessel of a filtration system equipped with a cellulose acetate membrane having a molecular weight cutoff of 150 Da (EFA 0.00454-m2). The filtration system included distilled water in vessel 210 as illustrated in FIG. 1. The process started at 50-psi (345 kPa) at room temperature with the pressure supplied from a compressed air filtered through 10-nm filters. After a total of 46 hours, the total amount of permeate in the permeate vessel was 520-mL, whereas the retentate remaining in the filtration system 220 (FIG. 1) remained at 300-mL and the volume of distilled water in vessel 210 was reduced from 750-mL to 230-mL. The retentate in the filtration system 220 and first permeate at 130 (FIG. 1) were analyzed for the complete phenol panel as the indicator of flavor retention. The ABV of the final ethanol-reduced wine product was determined to be 1.8% v / v.

[0181] Example 4(ii). Red wine sample (302.8-gram of Cabernet Sauvignon from J. Lohr, marked ABV 13.9% v / v) was supplied to the vessel of a filtration system equipped with a cellulose acetate membrane having a MWCO of 150 Da (EFA 0.00454-m2). The filtration system included distilled water in vessel 210. The process started at 50 psi (345 kPa) at room temperature with the pressure supplied from a compressed air filtered through 10-nm filters.After a total of 42 hours, the total amount of permeate was 582.6-gram, whereas the retentate remaining in the filtration system 220 remained at 300-mL, and the total distilled water withdrawn from vessel 210 was 582.6 gram. The retentate in the filtration system 220 was analyzed for the complete phenol panel as the indicator of flavor retention. The ABV of the ethanol-reduced wine product was determined to be 2.9% v / v. This is equivalent of 80.5% reduction in ABV, higher than a value of 65.8% volume reduction, which means the process of pressured dialysis in a continuous mode has resulted in an improvement of selectivity as well. FIG. 8 illustrates the change in the ratio of each composition of treated wine versus the corresponding composition in the original wine freshly opened in this Example. Results indicated that the separation membrane had excellent retention efficiency toward most of the flavor components, with the exception of caffeic acid and quercetin.

[0182] From FIG. 8, it was evident that flavor concentrations in wine retentate and permeate present a significant contrast that demonstrate the effectiveness of the separation membrane, systems, and methods in retaining the desired flavors, with these phenolic substances representing typical flavors. Due to drastically different concentrations of various flavor compounds in wine and the limitations of analytical methods, the measurement of each component may lead to different standard deviations, especially ones with an ultra-low or even at trace concentrations reaching the analytical limits and resolution. These data were highlighted and were not weighed as much to draw conclusions. Further examination of the list of molecules analyzed by molecular weight did show that retention became less effective as the molecular weight went below 150 to 300 Dalton.

[0183] Example 5. Ethanol was removed from a red wine as follows. Red Wine (Cabernet Sauvignon, J. Eohr) with an initial ABV of 13.9% was chosen as the feed wine. An initial volume of 300 ml of the Red Wine was added to a filtration system that included a cellulose acetate based nanofiltration membrane having a MWCO of 150 Da having an effective membrane area of 0.00454 m2. The applied pressure was 40 psia (276 kPa) supplied by compressed air filtered with O.lum filter with water / oil removal. After a total of 16 hours, a total of 131 gm (or 134 ml) of permeate (ethanol in water) was present in the permeate vessel. The retentate was corrected by adding distilled water to achieve a volume of 302-mE. The ethanol-reduced wine product was determined to have a reduction in ABV by 43.7% v / v.

[0184] Example 6. Ethanol was removed from a red wine as follows. Red Wine Cabernet Sauvignon (J. Lohr) with an initial ABV of 13.9% was chosen as the feed wine. An initial volume of 200 ml of the Red Wine was added to a filtration system that included a cellulose acetate based nanofiltration membrane having a MWCO of 150 Da having an effectivemembrane area of 0.00454 m2. The applied pressure for filtration was 33 psi (228 kPa) supplied by 0.1-um filtered nitrogen. After a total of 18.6 hours, a total of 41 gram (134 ml) of permeate (ethanol in water) was present in the permeate vessel. The retentate was restored to its original volume of 200-mL by adding distilled water. The ethanol-reduced wine was determined to have a reduction in ABV by 20.5% v / v.

[0185] Example 7. Red wine C (Oak Ridge 2020 Lodi Estates Cabernet Sauvignon) with an initial ABV of 14.4% was chosen as the feed wine with an initial volume of 600 ml. The employed membrane was a cellulose acetate membrane having a MWCO of 150 Da. The effective membrane diameter was 76mm, and the test was conducted at room temperature. The applied pressure was 40 psia supplied by sanitized air. The experiment was terminated when the retentate’ s volume reduced to 2 / 3 of the initial volume.

[0186] The collected permeate was further treated by a membrane contactor that included nonporous PDMS membranes. The permeate was introduced to the shell side of the nonporous membranes, while gas (air) was introduced to the lumenside of the nonporous membranes. Permeate separation was conducted at room temperature. Pressure upstream of the membrane contactor (liquid side) was maintained at 1 atmosphere, while downstream pressure (gas side) was maintained at approximately 5 torr to pull the gas through the membrane contactor. Flow rate of permeate through the membrane contactor was about 40-45 cm3 / minute. Separation was performed for 6.5 hours, resulting in two products, namely an aqueous, dealcoholized liquid and carrier gas that included ethanol and flavor components. The aqueous, dealcoholized liquid exhibited an ABV reduction from 14.4% (prior to introduction to the membrane contactor) to 6.6% (refreshed permeate). The carrier gas was then passed to a condenser to recover an alcohol-enriched liquid, which exhibited an ethanol content of about 25%vol. The ABV of liquid and alcohol-enriched liquid were monitored by refractometers.

[0187] The aqueous, dealcoholized liquid was then mixed with the retentate with a volume ratio of 3:2 (i.e., 60 vol% alcohol-reduced refreshed permeate mixed with 40%vol retentate), named as Product C3. The Product C3 had a final ABV of 9.7% (i.e.: 33% reduced), determined by FTIR-based wine analyzer.

[0188] In a similar manner, a 50% reduced sample (C4, 7.2% ABV) was prepared by mixing the same retentate and alcohol-reduced filtrate obtained from the membrane contactor. In this case, the ethanol level of the filtrate was stripped down to 4.12%, and the volume ratio between the retentate and aqueous refreshed permeate was 3:7.

[0189] Both sample C3 and C4 were presented to professional sommeliers and oenophiles for the perception evaluation, which obtained encouraging comments. Some of the comments were listed below:

[0190] Sample C3: “This sample has nice full bodied, and good aroma. Can smell and taste the alcohol. I like this one. ”

[0191] Sample C4: “This sample has more bite and fruit and more acid. Slightly too tang for me. ”

[0192] After being informed the actual ABV of Sample C4: “Oh wow. This is very promising. I would buy and drink these half-strength wine if they are available in the market. ”

Claims

CLAIMSWe claim:

1. A method of separating ethanol from an alcoholic beverage, the method comprising:Passing an alcoholic beverage comprising water, ethanol, and a flavor component through a filtration system (220) that comprises a semipermeable membrane (230) comprising a feed side (260), a permeate side (270), and a molecular weight cutoff in a range of 75 Da to 300 Da, a feed inlet (240), and a permeate outlet (250);Applying a pressure to the filtration system, thereby allowing ethanol and water to selectively pass through the semipermeable membrane, to provide a first permeate on the permeate side of the semipermeable membrane and a retentate on the feed side of the semipermeable membrane;Recovering the first permeate from the filtration system through the permeate outlet;Directing the first permeate to a membrane contactor (410) comprising two or more contactor membranes having a first side and a second side,Contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas, thereby allowing ethanol to pass from the first permeate and through the contactor membranes to the carrier gas, to provide a refreshed permeate; andProviding the refreshed permeate to the retentate to form an ethanol-reduced beverage.

2. The method of claim 1 wherein the alcoholic beverage comprises beer, wine, or liquor.

3. The method of claim 1 wherein applying pressure to the filtration system comprises applying pressure in a range of 25 psia to 450 psia.

4. The method of claim 1 wherein contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas, is conducted at a temperature in a range of 10 °C to 30 °C.

5. The method of claim 1 comprising passing the alcoholic beverage through a filtration system, applying a pressure to the filtration system, recovering the first permeate from the filtration system, directing the first permeate to a membrane contactor, and providing therefreshed permeate to the retentate a desired number of times, until the retentate comprises a target concentration of ethanol and a target concentration of flavor component.

6. The method of claim 5 wherein the target concentration of flavor component is at least 80% of initial flavor component concentration in the alcoholic beverage.

7. The method of claim 1 further comprising causing the alcoholic beverage to flow across the first side of the semipermeable membrane within the filtration system in a tangential direction.

8. The method of claim 7 wherein movement is caused by stirring the alcoholic beverage.

9. The method of claim 1 wherein the semipermeable membrane comprises a plurality of pores having an average pore size of 10 nm or less.

10. The method of claim 9 wherein the semipermeable membrane comprises a plurality of pores having an average pore size in a range of 0.1 nm to about 10 nm.

11. The method of claim 1 wherein the semipermeable membrane comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose semipermeable membrane.

12. The method of claim 1 wherein the semipermeable membrane has a molecular weight cutoff in a range of 150 Da to 300 Da.

13. The method of claim 1 wherein the semipermeable membrane has a MgSC rejection rate of at least 97% with a 1% MgSC solution.

14. The method of claim 1 wherein the semipermeable membrane has a NaCl rejection rate of at least 85% with a 1% NaCl solution.

15. The method of claim 1 wherein applying pressure further comprises applying pressure with air, carbon dioxide, helium, nitrogen gas, or argon gas.

16. The method of claim 1 wherein the contactor membranes comprise hollow fiber membranes comprising a plurality of pores having an average pore size in a range of 0.002 pm to 0.2 pm.

17. The method of claim 1 wherein the contactor membranes comprise nonporous hollow fibers.

18. The method of claim 1 further comprising maintaining a reduced pressure of 30 torr or less at a location downstream of the membrane contactor to pull carrier gas through the membrane contactor.

19. The method of claim 18 wherein the reduced pressure is in a range of 5 torr to 760 torr.

20. The method of claim 1 wherein the carrier gas comprises an inert gas.

21. The method of claim 1 wherein directing the first permeate to a membrane contactor and contacting a first side of the contactor membranes with the first permeate, and a second side of the contactor membranes with a carrier gas is conducted at a temperature of 30 °C or less.

22. The method of claim 1 wherein the flavor component comprises tartaric acid, malic acid, gallic acid, anthocyanin, reservatrol, caffeic acid, catechin, epicatechin, quercetin, quercetin glycosides, caftaric acid, malvidin glucoside, quercetin glycoside, tannin, or a combination of two or more of these.

23. An assembly (200) for separating ethanol from an alcoholic beverage, the assembly comprising:- a filtration system (220) comprising a semipermeable membrane (230) having a feed side (260), a permeate side (270), and a molecular weight cutoff in a range of 75 Da to 300 Da, a feed inlet (240), and a permeate outlet (250); a first vessel (210) fluidly connected to the feed inlet; a controllable pressure source (280) fluidly connected to the filtration system; a permeate vessel (290) fluidly connected to the permeate outlet; and a permeate separation system (300) fluidly connected to the permeate vessel, the permeate separation system comprising a membrane contactor (410) comprising two or more contactor membranes having a first side and a second side, a permeate outlet (460), a gas supply (400), a gas inlet (430) fluidly connected to the gas supply and configured to supply a carrier gas to a side of the contactor membranes, a gas outlet (440), and a condenser (470) fluidly connected to the gas outlet (440).

24. The assembly of claim 23 wherein the semipermeable membrane (230) comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose semipermeable membrane.

25. The assembly of claim 23 wherein the semipermeable membrane (230) has a MgSC rejection rate of at least 97% with a 1% MgSC solution.

26. The assembly of claim 23 wherein the semipermeable membrane (230) has a NaCl rejection rate of at least 85% with a 1% NaCl solution.

27. The assembly of claim 23 wherein the controllable pressure source (280) comprises a source of pressure of 450 psia (3105 kPa) or less.

28. The assembly of claim 23 wherein the controllable pressure source (280) comprises a source of inert gas.

29. The assembly of claim 23 wherein the contactor membranes comprise hollow fiber membranes comprising a plurality of pores having an average pore size in a range of 0.002 pm to 0.2 pm.

30. The assembly of claim 23 wherein the contactor membranes comprise nonporous hollow fibers.

31. The assembly of claim 23 wherein the permeate outlet (460) is fluidly connected to the first vessel (210).

32. The assembly of claim 23 wherein the gas supply (400) comprises a supply of inert gas.

33. The assembly of claim 23 wherein the condenser (470) comprises a plurality of stages to selectively condense components of the carrier gas.

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