Pressure-assisted diafiltration separation method and system

Abstract

Systems and processes relate to separating organic compounds using filtration. More specifically, the systems and methods relate to separating ethanol from alcoholic beverages, and the methods include a filtration step and a permeate separation step. In the filtration step, the method can include passing an alcoholic beverage containing water, ethanol, and flavor components through a filtration system including a semipermeable membrane with a desired molecular weight cutoff, applying pressure to the filtration system, thereby selectively allowing ethanol and water to pass through the semipermeable membrane to provide a first permeate. In the permeate separation step, the first permeate can be directed to a membrane contactor including two or more internal contactor membranes, where a first side of the contactor membrane contacts the permeate and a second side of the contactor membrane contacts a carrier gas.

Description

[Technical Field]

[0001] The present disclosure relates to a method and system for removing organic compounds from a liquid. More particularly, the present disclosure relates to a method and system for removing ethanol from a solution using a two-stage process that includes pressure-assisted diafiltration and membrane contactor principles. [Background technology]

[0002] Interest in low- and non-alcoholic adult beverages is growing worldwide. For example, in 2002, the World Health Organization estimated that 5.3% of global deaths and 5.1% of the global burden of disease and injury could be attributed to alcohol consumption. According to the U.S. Centers for Disease Control, as of 2010, the annual cost of alcohol abuse in the United States was $249 billion. Separately, rising temperatures have led to higher sugar levels in grapes, resulting in wines with higher ethanol content. These factors have led to increased interest in controlling the ethanol concentration in alcoholic beverages. While low- and non-alcoholic adult beverages have existed for many years, available low- and non-alcoholic adult beverages have yet to offer satisfying flavors that can mimic or replace traditional alcoholic beverages.

[0003] For example, some methods for producing low-alcohol or non-alcoholic beverages involve inhibiting alcoholic fermentation during the production process to reduce the alcohol content produced by fermentation. Other methods involve heating alcoholic beverages to 175°F (approximately 80°C) for 15-20 minutes to evaporate the ethanol in the beverage. However, these methods generally result in low-alcohol or non-alcoholic beverages that do not taste like alcoholic beverages. In many cases, the resulting low-alcohol or non-alcoholic beverages either have little flavor or are so bad that they are undrinkable. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need to produce low-alcohol or non-alcohol adult beverages that provide acceptable sensory characteristics (such as taste, aroma, and mouthfeel) similar to alcoholic beverages and can mimic or replace traditional alcoholic beverages. [Means for solving the problem]

[0005] The present disclosure relates to systems and methods for separating organic compounds from liquids using membrane-based processes. Generally, the methods and systems described herein can include two filtration stages. In some embodiments, the first stage can utilize the principle of pressure-assisted diafiltration, and the second stage can utilize the principle of membrane contactors. In some embodiments, different filtration systems can be used in the first and / or second filtration stages. In some embodiments, the filtration system in the first stage includes a semipermeable membrane and a pressure source. The combination of certain semipermeable membrane properties and pressure allows users to selectively separate ethanol and water from alcoholic beverages. The product of the first-stage pressure-assisted diafiltration includes a first permeate (comprising at least water and ethanol, and optionally low-molecular-weight flavor and / or aroma components) and a retentate (comprising 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, which separates the water and ethanol. In some embodiments, the second stage includes a permeate separation system, which can generally include a membrane contactor, a carrier gas, and a condenser. The first permeate can be fed to a membrane contactor, which utilizes a gas carrier to remove ethanol from the first permeate. The carrier gas can be condensed to provide an ethanol concentrate. In some embodiments, the carrier gas can be condensed in a controlled manner so that the ethanol and any flavor or aroma components can be further separated. The product of the second stage permeate separation system includes at least an aqueous dealcoholized solution (also referred to as a "refreshed permeate") and an ethanol concentrate.

[0007] In some embodiments, the product of the second stage can be recycled to the first stage and / or used to provide additional products. For example, in some embodiments, the refreshing permeate component can be combined with the remaining components from the first stage to provide a reduced-alcohol beverage. These embodiments can provide a closed-loop system for producing a reduced-alcohol beverage. In some embodiments, the refreshing permeate component can be re-fed to the first stage filtration system to undergo further separation through the first and second stages of the process. In some embodiments, the ethanol concentrate product of the second stage can be utilized in the production of other beverage products or ethanol-containing products for industrial use.

[0008] In some embodiments, the two-stage methods and systems described herein can provide advantages. For example, the first stage, the second stage, or both stages can be operated at ambient (or near-ambient) conditions, thereby reducing energy consumption requirements. By operating at ambient (or near-ambient) conditions, the two-stage methods and systems can also minimize changes or damage to flavor components in heat-sensitive processing solutions, which can help maintain the flavor of reduced-alcohol beverages. In some embodiments, the methods and systems can reduce water usage. For example, the methods and systems can provide a closed-loop process that reuses solutions (such as refreshing infusion components), thereby minimizing the use of external water. In some embodiments, the second stage utilizes a carrier gas to remove ethanol (and optionally flavor and / or aroma components) from the ethanol concentrate, further reducing the need for an external water source. In some embodiments, the use of a carrier gas in the second stage can also provide a higher ethanol concentrate, as the carrier gas may be able to pick up more ethanol than a liquid (such as water). In some embodiments, the use of a carrier gas in the second stage can also avoid the addition of water or other liquids that could dilute the refreshment permeate component or ethanol concentrate product of the second stage filtration. In some embodiments, the two-stage method and system can provide a simple, self-contained system that recycles materials (e.g., water and carrier gas) while providing a dealcoholized product with desirable properties (e.g., a high ABV ethanol concentrate that can be used to produce reduced-alcohol beverages and other beverages with sensory properties similar to those of the original). These and other features are described herein.

[0009] In various embodiments, the systems and methods utilize a membrane comprising a selectively permeable membrane (also referred to herein as a separation membrane or semipermeable membrane). In some embodiments, the membrane comprises a semipermeable membrane having a molecular weight cutoff ranging from about 75 Da to about 300 Da. In various embodiments, the process utilizes pressure to migrate target compounds across the membrane and reduce the ethanol concentration in the alcoholic beverage. In various embodiments, the processes and systems can utilize a membrane that allows for the separation of one or more target compounds from a liquid while substantially inhibiting the separation of flavor components from the liquid.

[0010] Various embodiments of the system and method may include separating an organic compound (ethanol) from an alcoholic beverage, the method comprising: - an alcoholic beverage containing water, ethanol, and flavoring ingredients, a semipermeable membrane comprising a feed side, a permeate side, and a molecular weight cutoff in the range of 75 Da to 300 Da; - supply inlet, and - Pass-through exit and passing the mixture through a filtration system comprising: - applying pressure to the filtration system to selectively allow ethanol and water to pass through the semipermeable membrane to produce a first permeate component on the permeate side of the semipermeable membrane and a retentate component on the feed side of the semipermeable membrane; -recovering the first permeate component from the filtration system through a pass-through outlet; - directing the first permeate component to a membrane contactor including two or more contactor membranes having a first surface and a second surface; contacting a first side of the contactor membrane with a first permeate component and a second side of the contactor membrane with a carrier gas, thereby passing ethanol through the membrane from the first permeate component to the carrier gas to produce a refresh permeate component; - providing a refreshing permeating component to the remaining components to produce a reduced ethanol beverage; Contains one or more of:

[0011] Alcoholic beverages may include wine, beer, or liquor.

[0012] Thus, in some embodiments, the method can provide a continuous process for providing reduced ethanol beverages. In some embodiments, the method can provide a batch process for providing reduced ethanol beverages.

[0013] In some embodiments, applying pressure to the filtration system includes applying a pressure ranging from 25 psia to 450 psia. In some embodiments, contacting the first side of the contactor membrane with the first permeate component and contacting the second side of the contactor membrane with the carrier gas are carried out at a temperature ranging from 10°C to 30°C. In some embodiments, passing the alcoholic beverage through the filtration system, applying pressure to the filtration system, recovering the first permeate component from the filtration system, directing the first permeate component to a membrane contactor, and supplying a refreshing permeate component to the retentate component a desired number of times until the retentate component contains a target concentration of ethanol and a target concentration of flavor components. In some embodiments, the target concentration of flavor components is at least 80% of the initial flavor component concentration in the alcoholic beverage.

[0014] In various embodiments, the method may further include flowing the alcoholic beverage tangentially across a first surface of a semipermeable membrane within the filtration system. In some embodiments, the movement is caused by agitation of the alcoholic beverage.

[0015] In some embodiments, the semipermeable membrane comprises a plurality of pores having an average pore size of 10 nm or less. In various embodiments, the semipermeable membrane comprises a plurality of pores having an average pore size ranging from 0.1 nm to about 10 nm. In some embodiments, the semipermeable membrane comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose semipermeable membrane. In various embodiments, the semipermeable membrane has a molecular weight cutoff ranging from 150 Da to 300 Da. In some embodiments, the semipermeable membrane has a MgSO4 rejection rate of at least 97% in a 1% MgSO4 solution. In some embodiments, the semipermeable membrane has a NaCl rejection rate of at least 85% in a 1% NaCl solution.

[0016] In various embodiments, pressurizing the filtration system further comprises pressurizing with air, carbon dioxide, helium, nitrogen gas, or argon gas.

[0017] According to some embodiments, directing the first permeant component to the permeant separation system can further include introducing at least a portion of the first permeant component into a membrane contactor that includes a plurality (e.g., two or more) of contactor membranes. In some embodiments, the contactor membranes are made of a polypropylene, a silicone polymer such as polydimethylsiloxane (PDMS), or a polyolefin (e.g., (CHCHR) n wherein R is an alkyl group). In some embodiments, the semipermeable polymer membrane of the membrane contactor can include a microporous membrane or a non-porous membrane.

[0018] In some embodiments, the contactor membrane comprises a hollow fiber membrane comprising a plurality of pores having an average pore size ranging from 0.002 μm to 0.2 μm. In some embodiments, the contactor membrane comprises a non-porous hollow fiber. In various embodiments, the method further comprises drawing a carrier gas through the membrane contactor while maintaining a reduced pressure of 30 torr or less at a location downstream of the membrane contactor. In various embodiments, the reduced pressure ranges from 5 torr to 760 torr. In some embodiments, the carrier gas comprises an inert gas. In some embodiments, directing the first permeate component through the membrane contactor, contacting the first side of the contactor membrane with the first permeate component, and contacting the second side of the contactor membrane with the carrier gas are carried out at a temperature of 30° C. or less.

[0019] In various embodiments, 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 thereof.

[0020] In some embodiments, the flavor or aroma concentrate compositions obtained by the methods and systems of the present invention can be combined with reduced-ethanol beverages. In these embodiments, residual flavor and / or aroma compounds can be restored to the reduced-ethanol beverages. This can potentially improve the sensory properties of the reduced-ethanol beverages (e.g., sensory properties such as one or more of taste, aroma, product appearance, and mouthfeel).

[0021] In some embodiments, an assembly for separating ethanol from an alcoholic beverage is provided, the assembly comprising: a feed side, a permeable side, and a semipermeable membrane having a molecular weight cutoff in the range of 75 Da to 300 Da; - supply inlet, and -pass-through exit, a filtration system comprising: a first container fluidly connected to the supply inlet; a controllable pressure source fluidly connected to the filtration system; a permeant component container fluidly connected to the permeation outlet; a permeate separation system fluidly connected to a permeate container, a membrane contactor comprising two or more contactor membranes having a first surface and a second surface; - Penetration component outlet, -gas supply unit, a gas inlet fluidly connected to a gas supply and configured to supply a carrier gas to a side of the contactor membrane; -gas outlet, and a condenser fluidly connected to the gas outlet; a permeation component separation system comprising: Equipped with.

[0022] In some embodiments, the first vessel can contain an aqueous liquid source. In some embodiments, the aqueous liquid source can be a source of water or a refreshing permeate component. In various embodiments, a controllable pressure source is positioned between the first vessel and the filtration system. In some embodiments, the condensed water outlet can be fluidly connected to the first vessel. In some embodiments, the gas outlet can be fluidly connected to the membrane contactor.

[0023] In some embodiments, the semipermeable membrane comprises a cellulose acetate, cellulose triacetate, regenerated cellulose, or mixed cellulose membrane. In some embodiments, the semipermeable membrane has a MgSO4 rejection rate of at least 97% in a 1% MgSO4 solution. In some embodiments, the semipermeable membrane has a NaCl rejection rate of at least 85% in a 1% NaCl solution.

[0024] In various embodiments, the controllable pressure source comprises a pressure source of 450 psia (3105 kPa) or less. In various embodiments, the controllable pressure source comprises an inert gas source.

[0025] In some embodiments, the contactor membrane comprises a hollow fiber membrane comprising a plurality of pores having an average pore size ranging from 0.002 μm to 0.2 μm. In some embodiments, the contactor membrane comprises non-porous hollow fibers.

[0026] In various embodiments, the through-outlet is fluidly connected to the first container. In various embodiments, the gas supply includes a supply of inert gas. In some embodiments, the condenser includes multiple stages for selectively condensing components of the carrier gas.

[0027] In some embodiments, the reduced ethanol beverages 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.

[0028] In various embodiments, the separation methods and systems do not include aspiration of a solution to allow the target compounds to permeate through the semipermeable membrane of the filtration system. It should be understood that, in some embodiments, the various methods and devices discussed herein can be applied to alcoholic beverages to enable dealcoholization of the beverage while minimizing changes to the beverage's physicochemical properties. As used herein, "dealcoholization" refers to removing ethanol from an alcoholic beverage having an initial ethanol content to provide a beverage (reduced-ethanol beverage) having a final ethanol content lower than the initial ethanol content. For example, alcoholic beverages produced by fermentation (such as wine, beer, cider, and mead) 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 between about 20% and about 40% (v / v). In some embodiments, the methods and systems discussed herein can remove ethanol from alcoholic beverages, providing beverages with reduced alcohol levels (compared to the initial alcohol content) while maintaining the sensory and nutritional value of the original beverage. In other words, in some embodiments, the methods and systems discussed herein can produce reduced-ethanol beverages that taste the same as or very similar to the original full-alcohol beverage, and can mimic or replace traditional alcoholic beverages. In some embodiments, dealcoholization can remove a desired amount of ethanol from the alcoholic beverage, for example, a relatively small amount (such as about 0.5 to about 5%), a moderate amount, or even substantially all of the ethanol in the alcoholic beverage.

[0029] In some embodiments, the methods and systems discussed herein allow for the substantial removal of ethanol or ethyl alcohol from an alcoholic beverage while substantially preventing the removal of other compounds from the alcoholic beverage. The resulting beverage can contain either reduced, low, or substantially no alcohol, while retaining many or most of the compounds that impart the original alcoholic beverage's characteristic taste, aroma, and drinking experience. For example, when the methods and systems discussed herein are applied to an alcoholic beverage (e.g., red wine) to produce a modified red wine, the modified red wine retains the taste characteristics of the unmodified red wine, but the modified red wine has low or substantially no alcohol. As another example, when the methods and systems discussed herein are applied to a distilled spirit such as gin, the modified gin retains the taste and aroma characteristics of the unmodified gin, but the modified gin has low or substantially no alcohol. In other words, in some embodiments, the novel methods and systems discussed herein can produce reduced-alcohol, low-alcohol, or non-alcoholic beverages that taste the same as or very similar to alcoholic beverages, and can mimic or replace traditional alcoholic beverages. As used herein, a reduced-alcohol beverage (also referred to herein as a reduced-ethanol beverage) 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. Those skilled in the art will readily understand that the present methods and systems can be used to customize the alcohol content of a beverage as desired. As used herein, a low-alcohol beverage can include 2.5% alcohol by volume (ABV) or less, or 2% ABV or less, or 1% ABV or less, or 0.5% ABV or less.

[0030] In various embodiments, the methods and systems discussed herein can enable the dealcoholization of beverages while retaining the desired sensory characteristics of the original beverage. Such sensory characteristics can be provided by one or more flavor components in the original beverage. Exemplary flavor components include flavonoids (in the case of wine), volatile flavor components (in the case of beer), and other natural components present in the original beverage, which, alone or in combination, can impart the beverage its characteristic taste, aroma, and / or mouthfeel. In some embodiments, dealcoholization can remove a desired amount of ethanol from the alcoholic beverage while retaining a substantial amount of the desired flavor components. For example, in some embodiments, the methods and systems can provide a dealcoholized beverage comprising 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.

[0031] In various aspects, the methods and systems discussed herein may enable the dealcoholization of beverages without the use of heat, which may be desirable, for example, to preserve flavor components of the beverage. [Brief explanation of the drawings]

[0032] [Figure 1] 1 shows a process diagram illustrating a method for filtering one or more compounds from a fluid, according to some embodiments. [Figure 2] 1 shows a schematic diagram of a separation system, according to some embodiments. [Figure 3] 1 shows a schematic diagram of a permeant component separation system, according to some embodiments. [Figure 4A] 1 shows the concentration ratio of phenolic compounds in a reduced ethanol beverage versus an untreated beverage, according to some embodiments. [Figure 4B] 1 shows compound removal efficiency versus molecular weight of the selectively permeable membrane utilized, according to some embodiments. [Figure 5]1 shows tasting feedback of reduced ethanol beverages versus untreated beverages, according to some embodiments. [Figure 6] 1 shows sensory analysis results for beverage body of reduced ethanol beverages versus untreated beverages, according to some embodiments. [Figure 7] 1 shows sensory results in terms of similarity of reduced ethanol beverages versus untreated beverages, according to some embodiments. [Figure 8] 1 shows the change in the ratio of each composition of a treated beverage to the corresponding composition in the original (untreated) beverage, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0033] Various embodiments of the concepts disclosed herein relate to processes and systems for removing or separating compounds from a liquid. In the context of this application, "separation" can be understood to mean reducing the amount of a compound contained in a liquid so that the final product or liquid has a reduced amount of the compound compared to the original starting liquid. In some embodiments, the compound separated from the liquid can be partially, substantially, or completely removed from the liquid.

[0034] In some embodiments, processes and systems for separating organic compounds from a liquid solution are described. In some embodiments, removing or separating 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, distillation, etc.). Removing or separating ethanol from a solution may be referred to herein as "dealcoholization." In some embodiments, the alcoholic beverage may include wine, beer, or liquor. In some embodiments, ethanol may be substantially or completely removed from the alcoholic beverage. In some embodiments, ethanol may be partially removed from the alcoholic beverage. In some embodiments, when ethanol is separated from a solution, only ethanol is separated. In some embodiments, when ethanol is separated from a solution, not only ethanol but also one or more additional compounds or products are separated along with the ethanol. In some embodiments, the additional compound or product can be any chemical species. In some embodiments, the additional compound or product can be any inorganic or organic molecule. In some embodiments, when ethanol is separated from a solution, ethanol and water are separated.

[0035] The dealcoholization of alcoholic beverages is used to illustrate certain concepts, as these applications are useful for highlighting features and advantages. However, it will be readily apparent that the methods and systems described herein can be used to remove other organic compounds from liquids in areas such as food and beverage processing, chemical and pharmaceutical manufacturing, water treatment, fuel (e.g., oil and gas) production, and medical applications (e.g., blood treatment, such as dialysis). In some embodiments, certain methods and devices can be used to clarify liquids (e.g., juices) or purify liquids (e.g., fuels).

[0036] In various embodiments, the method uses filtration principles (e.g., diafiltration principles) to separate ethanol from an alcoholic beverage. In the context of this application, "diafiltration" refers to a technique that uses a membrane to remove or reduce the concentration of a target component (e.g., ethanol) from a starting liquid (such as an alcoholic beverage). In doing so, the method concentrates the components that remain in solution (i.e., that are not removed from the liquid by passing through the membrane). The method utilizes a selectively permeable membrane to separate components of the solution and suspension based on molecular size. The selectively permeable membrane retains molecules larger than the pores of the membrane (the retentate component), while smaller molecules, such as ethanol and water, pass freely through the membrane (forming the first permeate component). In various embodiments, the system and method include providing a refresh permeate component to the retentate component. The refresh permeate component can be provided in an open-loop or closed-loop manner. The method may be performed in a batch or continuous mode.

[0037] In various embodiments, the system and method can utilize a two-stage separation process. In some embodiments, the first stage of separation can use diafiltration principle to remove or reduce the concentration of ethanol from alcoholic beverages. In some embodiments, the permeate component (first permeate component) obtained from diafiltration can be subjected to a second stage of separation using membrane contactor principle to further separate one or more of ethanol, water, flavor components, and aroma components of the first permeate component.

[0038] In various embodiments, systems and methods use membrane contactors to separate ethanol, water, and flavor and aroma compounds. In the context of this application, a membrane contactor includes a device containing a polymeric membrane (e.g., a porous or permeable membrane), the purpose of which is to promote contact between two phases, thereby transferring one or more target compounds from one phase to the other. In some embodiments, the two phases are liquid and gas. In various embodiments, separation selectivity is typically achieved by using a carrier gas on one side of the porous membrane. The feed stream and carrier gas contact each other along the membrane surface. According to these embodiments, the membrane contactor achieves liquid-gas mass transfer without one phase dispersing into the other. This is achieved by passing the feed stream and carrier gas through opposite sides of a microporous (or non-porous) membrane and controlling the pressure difference between the two phases so that one phase is immobilized in the membrane pores in vapor form or selectively diffuses across the membrane.

[0039] Thus, in various embodiments, the second separation stage can involve subjecting the permeate component (e.g., the first permeate component) from the filtration system to a membrane contactor, where the first permeate component is contacted with a carrier gas to effect transfer of target compounds from the first permeate component to the carrier gas. In some embodiments, one or more of ethanol, flavor compounds, and aroma compounds can migrate from the first permeate component to the carrier gas to provide a refreshing permeate component. In some embodiments, the refreshing permeate component can be substantially free of ethanol because ethanol has been removed through the membrane contactor. In some embodiments, the refreshing permeate component can be added back to the remaining components to provide a reduced-alcohol beverage. In some embodiments, the carrier gas containing one or more of ethanol, flavor compounds, and aroma compounds can be fed to a condenser to separate the individual compounds from the carrier gas.

[0040] In various aspects, the separation processes described herein can remove or separate ethanol from an alcoholic beverage while retaining the flavor components of the original starting beverage. In the context of this application, "retain" can be understood to mean maintaining the amount of flavor components present in the alcoholic beverage, meaning that the final product or beverage has a significant amount of flavor components compared to the original starting beverage. In some embodiments, the flavor components retained in the beverage can be substantially or completely retained in the beverage.

[0041] In some embodiments, beverages comprise one or more flavor components that contribute to the aroma, taste, and / or mouthfeel of beverages, either alone or in combination.For example, the flavor of wine can be the result of compounds derived from natural fruit (grapes), compounds that are produced or changed during production, compounds that are produced or changed by yeast during fermentation, and compounds that occur during aging.In wine, exemplary flavor components can include acids and polyphenols.

[0042] In some embodiments, flavor components in wine can include acids such as tartaric acid, malic acid, citric acid, acetic acid, butyric acid, lactic acid, and succinic acid.

[0043] In some embodiments, the flavor components of wine may include polyphenols, including flavonoids and non-flavonoids. In some embodiments, flavonoids may include anthocyanins (e.g., malvidin glucoside, quercetin glycoside), tannins, flavonols (e.g., quercetin, myricetin, kaempferol, laricitrin, isorhamnetin, syringetin), and catechins (e.g., catechin, epicatechin). In some embodiments, non-flavonoids may include hydroxycinnamic acids (e.g., caftaric acid, ctaraic acid, and fertaric acid), stilbenoids (e.g., reservatrol, benzoic acid, caffeic acid, cinnamic acid, and piceatannol), and phenolic acids (e.g., gallic acid, vanillin).

[0044] In beer, exemplary flavor components may include terpenes (e.g., myrcene, β-caryophyllene, limonene, humulene, α-pinene, linalool, geraniol, α-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)), and hop resins (e.g., humulone, cohumulone, adhumulone, lupulone, colupulone, adolfuron). Gin flavor components may include terpenes (monoterpenes, sesquiterpenes, and diterpenes) and their derivatives (terpenoids). Exemplary monoterpenes may include α-pinene, β-pinene, limonene, β-myrcene, p-cymene, γ-terpinene, and sabinene. Oxygenated monoterpenes may include linalool, α-terpineol, and geranyl acetate. Exemplary sesquiterpenes include cadinene, δ-cadinene, caryophyllene, β-elemene, γ-elemene, α-humulene, and germacrene D. Exemplary diterpenes may include retinol, retinal, and phytol.

[0045] It will be appreciated that a particular type of alcoholic beverage may contain flavor components derived from the particular ingredients used to prepare the beverage. The methods and systems described herein may be adapted to measure the initial concentrations of selected flavor components found in a particular alcoholic beverage before the separation process begins. The final concentrations of the flavor components in the beverage after the separation process may be measured and compared to the initial concentrations.

[0046] Many flavor components contained in alcoholic beverages (e.g., flavonoids, stilbenes, and terpenes) are soluble in ethanol. Furthermore, the properties of flavor components vary greatly in terms of molecular weight, affinity, and interaction with other components of the beverage. Thus, in some embodiments, it can be difficult to separate ethanol from the liquid and retain many flavor components.

[0047] The concentration of flavor components can be measured using any suitable technique, such as high performance liquid chromatography (HPLC).

[0048] In some embodiments, a trained taster (such as a sommelier) can also evaluate the taste of the final product, as discussed herein. The final product (reduced ethanol beverage) can be evaluated for aroma, flavor, and mouthfeel, as illustrated in the examples.

[0049] Generally, the methods and systems described herein may include passing an alcoholic beverage containing water, ethanol, and flavor components through a filtration system having a feed side, a pass-through side, and a semipermeable membrane with a molecular weight cutoff ranging from 75 Da to 300 Da, a feed inlet, and a pass-through outlet; and applying pressure to the filtration system to selectively allow ethanol and water to pass through the semipermeable membrane. This process forms a retentate component having a reduced amount of one or more target solutes and a first permeate component having an increased amount of one or more target solutes. In some embodiments, when the target solute includes ethanol, the products of the process are a dealcoholized retentate component and a first permeate component having an increased alcohol content. In some embodiments, despite the dealcoholization process, the retentate component retains a significant amount of flavor components. An aqueous liquid can be supplied to the retentate component to form a reduced-ethanol beverage.

[0050] In some embodiments, the methods and systems can provide one or more advantages. In some embodiments, the methods and systems can be performed at ambient temperatures (e.g., in the 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). This can be beneficial, for example, in preserving the desired organoleptic properties of the alcoholic beverage and reducing the required energy input.

[0051] In some embodiments, the methods and systems can be carried out at a pressure within a desired range, such as from about 25 psia (172 kPa) to about 450 psia (3105 kPa), or from about 100 psia (689 kPa) to about 400 psia (2,760 kPa), or from about 145 psia (1,000 kPa) to about 350 psia (2,415 kPa), or from about 145 psia to about 300 psia (2,070 kPa), or from about 145 psia to about 250 psia (1,725 ​​kPa). Such conditions can be beneficial in preserving the sensory (e.g., taste, aroma, color) and nutritional (e.g., vitamin) values ​​of the original alcoholic beverage. In some embodiments, the methods and systems can be carried out under exposure to air or an inert gas (e.g., carbon dioxide, helium, nitrogen, argon, etc.). In some embodiments, the materials used in the methods and systems (semipermeable membranes, membrane contactors, and refresh permeation components) are inexpensive, readily available, and food-safe. In some embodiments, the methods and systems are capable of separating ethanol from a solution in a controllable manner.

[0052] In various embodiments, methods and systems can provide for the removal of ethanol from beverages while retaining desirable solutes, such as flavor components, in the starting material (feed solution). For example, wine is a complex mixture primarily containing water and ethanol, but also hundreds of compounds, such as sugars (glycerol and polysaccharides), acids, volatile flavor and aroma compounds, color compounds, and tannins. It is this mixture of trace compounds that gives wine its unique flavor, color, aroma, and character. Thus, in some embodiments, methods and systems can remove ethanol from beverages while retaining desirable solutes, such as sugars, acids, volatile flavor and aroma compounds, color compounds, and tannins. In this manner, the dealcoholized wine can retain its characteristic taste, aroma, and color.

[0053] Some embodiments described herein relate to methods and systems for separating organic compounds (e.g., ethanol) from liquid solutions using selectively permeable membranes 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 the methods and systems described herein. The solutes can include permeable solutes that can pass through a separation membrane, such as ethanol.

[0054] In some embodiments, a method for separating ethanol from an alcoholic beverage is provided, the method comprising: - an alcoholic beverage containing water, ethanol, and flavoring ingredients, a semipermeable membrane comprising a feed side, a permeate side, and a molecular weight cutoff in the range of 75 Da to 300 Da; - supply inlet, and - Pass-through exit and passing the mixture through a filtration system comprising: - applying pressure to the filtration system to selectively allow ethanol and water to pass through the semipermeable membrane to produce a first permeate component on the permeate side of the semipermeable membrane and a retentate component on the feed side of the semipermeable membrane; -recovering the first permeate component from the filtration system through a pass-through outlet; - directing the first permeate component to a membrane contactor including two or more membranes having a first surface and a second surface; contacting a first side of a membrane in a membrane contactor with a first permeate component and a second side of the membrane in the membrane contactor with a carrier gas, thereby allowing ethanol to pass through the membrane from the first permeate component to the carrier gas and to produce a refresh permeate component; - providing a refreshing permeating component to the remaining components to form a reduced ethanol beverage; Includes:

[0055] In some embodiments, the alcoholic beverage comprises a first flavor component concentration and the reduced-ethanol beverage comprises a second flavor component concentration. In some embodiments, 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.

[0056] In some embodiments, an alcoholic beverage containing water, ethanol, and flavor components is introduced into a filtration system having a feed side, a pass-through side, and a semipermeable membrane having a MWCO ranging from 75 Da to 300 Da, a feed inlet, and a pass-through outlet. The alcoholic beverage (feed solution) contains 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 containing multiple compounds, including water, ethanol, and flavor components, among other compounds. In some embodiments, the feed solution can be an alcoholic beverage such as gin, whiskey, vodka, wine, or beer. For example, the alcoholic beverage can be introduced into the filtration system such that the alcoholic beverage physically contacts the feed side of the selectively permeable membrane.

[0057] In some embodiments, the method includes applying pressure to the filtration system to selectively allow ethanol and water to pass through the semipermeable membrane, providing a first permeate component to the permeate side of the semipermeable membrane and a remaining component to the feed side of the semipermeable membrane. In some embodiments, the pressure can be from about 25 psia (172 kPa) to about 450 psia (3105 kPa), or from about 100 psia (689 kPa) to about 400 psia (2,760 kPa), or from about 145 psia (1,000 kPa) to about 350 psia (2,415 kPa), or from about 145 psia to about 300 psia (2,070 kPa), or from about 145 psia to about 250 psia (1,725 ​​kPa). Psia is understood to be pounds per square inch absolute, i.e., pressure relative to zero (or a perfect vacuum).

[0058] In some embodiments, the method includes moving the alcoholic beverage across the feed surface of the semipermeable membrane for a predetermined amount of time. In some embodiments, moving the alcoholic beverage across the feed surface of the semipermeable membrane includes stirring the alcoholic beverage. In some embodiments, moving the alcoholic beverage across the feed surface of the semipermeable membrane can be achieved using, for example, a pump and an impeller (e.g., as part of a rotating device). For example, a pump or an impeller (e.g., a blade, paddle, or stir bar) can be included in the filtration system. The pump can circulate the alcoholic beverage through the filtration system, resulting in more of the alcoholic beverage contacting the feed surface of the semipermeable membrane.

[0059] The predetermined time period for continuing the 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 other suitable time period. In some embodiments, the time period depends on how much ethanol in the alcoholic beverage is to be removed from the alcoholic beverage and / or the amount of alcoholic beverage introduced into the filtration system.

[0060] In some embodiments, the feed solution can be pumped into the filtration system using a pump (e.g., the pump can be inside or outside the filtration system container) to move the alcoholic beverage across (e.g., tangentially) the feed surface of the semipermeable membrane. Optionally, the feed solution can be further removed from the filtration system after passing through the feed surface of the membrane. In some embodiments, the feed solution is pumped across (and removed from) the feed surface of the semipermeable membrane one or more times, each time being one cycle. For example, if one liter of feed solution is pumped across the feed surface of the membrane and then removed, one liter of feed solution has completed one cycle across the membrane. If the same one liter of feed solution is pumped across the feed surface of the membrane and then removed a second time, one liter of feed solution has completed a second cycle across the membrane. In some embodiments, the feed solution can be continuously circulated across the feed surface of the semipermeable membrane. In some embodiments, the feed solution can be intermittently circulated across the feed surface of the membrane. In some embodiments, the flow of the feed solution across the surface of the feed side of the membrane is stopped and restarted periodically (in cycles). In some embodiments, stopping and restarting can be useful to prevent or disrupt concentration polarization effects at or near the surface of the feed side of the membrane. In some embodiments, stopping and restarting the flow of the feed solution can be done in short or long pulses. In some embodiments, vibration (e.g., mechanical) can be introduced into the flowing feed solution to help disrupt or reduce clogging of the membrane with 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 used alone or in combination to maintain acceptable performance of the separation membrane.

[0061] It should be understood that one or more of the above mechanisms can be used in combination to cause movement of the feed solution across the feed-side surface of the separation membrane in a filtration system. Facilitating movement of the feed solution within the filtration system can be advantageous, for example, to reduce the likelihood of filter cake, which can lead to fouling and / or uneven flow.

[0062] An exemplary assembly for separating the liquid component (dealcoholization) of a solution herein may generally include a filtration system having a feed side, a permeate side, and a semipermeable membrane having a MWCO ranging from 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. An exemplary permeate separation system may generally include a membrane contactor including a plurality (e.g., two or more) membranes having a first surface (e.g., a luminal surface) and a second surface (e.g., an abluminal surface), a permeate outlet, a gas inlet for supplying a carrier gas to the membrane side, a gas outlet, a condenser fluidly connected to the gas outlet, and a condensate outlet. The terms "first surface" and "second surface" of the membrane are used to distinguish between the sides and do not imply a particular order of the membrane sides. For example, in some embodiments, the first surface may comprise the lumenside and the second surface may comprise the abluminal surface, and in other embodiments, the first surface may comprise the abluminal surface and the second surface may comprise the lumenside. As described in more detail elsewhere herein, one or more fluid inputs and outputs may be provided on each side of the filtration system, the permeate separation system, or both.

[0063] In various embodiments, when a feed solution contacts one side (e.g., the feed side) of a filtration system separation membrane and an appropriate pressure is applied to the system, permeation of a target solute (e.g., at least one organic compound) through the membrane causes the target solute to migrate from the feed solution through the membrane, thereby producing a first permeate component. In some embodiments, two or more target solutes, e.g., ethanol and water, permeate the semipermeable membrane. As one or more features in some embodiments, 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. Features in various embodiments may include one or more of the selection of the semipermeable membrane, the pressure applied during separation, and / or the processing temperature.

[0064] The separation process can continue for any suitable period of time (e.g., by circulating the feed solution across the feed side of the semipermeable membrane). The time for which the separation process continues can 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 any other suitable period of time. In some embodiments, the time depends on the amount of target solute in the alcoholic beverage to be removed from the alcoholic beverage. In some embodiments, the time depends on the amount of target solute in the alcoholic beverage. In some embodiments, the time is related to the surface area of ​​the semipermeable membrane. In some embodiments, a combination of factors can lengthen or shorten the suitable period of time (e.g., a low percentage of ethanol in the feed solution in contact with a membrane having an area of ​​1 square meter may require less time to remove the same percentage of ethanol as a low percentage of ethanol in the feed solution in contact with a membrane having an area of ​​0.5 square meters).

[0065] As an example, if red wine is used as the feed solution to a filtration system, a significant portion of the ethanol can be removed within 6.5 hours. Red wine typically contains 12% to 15% ethanol by volume. As another example, if a similar amount of gin or other distilled beverage is used as the feed solution in the supply vessel, removing a similar percentage of ethanol from the alcoholic beverage may require a longer separation process, as alcoholic beverages may contain anywhere from 20% to 95% ethanol by volume.

[0066] In some embodiments, ethanol and water are transferred from the alcoholic beverage through a semipermeable membrane, thereby producing a retentate component on the feed side of the semipermeable membrane and a first permeate component (e.g., an ethanol-enriched permeate component) on the permeate side of the semipermeable membrane. In some embodiments, an aqueous liquid can be fed to the retentate component to replace the volume lost due to the separation of water and ethanol, thereby forming a reduced-ethanol beverage. In some embodiments, the aqueous liquid can include water (e.g., water treated by distillation, reverse osmosis, or a similar method). In some embodiments, the aqueous liquid can include the product of a second-stage process utilizing a membrane contactor to separate one or more of the water, ethanol, flavor components, or aroma components of the first permeate component produced by the filtration system. The retentate component and the aqueous liquid can be collected together from the feed side of the semipermeable membrane, providing an alcoholic beverage having a final ethanol concentration lower than the initial ethanol concentration in the alcoholic beverage feed solution. The dealcoholized solution can have a final ethanol concentration 0.5% to 100% lower than the initial ethanol concentration in the feed solution (alcoholic beverage). It should be appreciated that in some embodiments, one or more compounds may pass through the membrane during the separation process to form the first permeant component.

[0067] In some embodiments, the first permeate (e.g., an ethanol-enriched permeate) can be recovered from the filtration system through a pass-through outlet. Optionally, the first permeate can be utilized in the preparation of other alcoholic beverages. In some embodiments, the first permeate recovered from the filtration system can be directed to a second separation process in which components of the first permeate are further separated. In some embodiments, water can be separated from ethanol within the permeate separation system to form an ethanol concentrate and an aqueous liquid. The aqueous liquid can contain a low amount 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 embodiments, for example, the aqueous liquid can contain a refreshing permeate. In some embodiments, the method includes blending the refreshing permeate with the remaining components. This can provide a closed-loop process in which components of the permeate can be reused through the system. Ethanol recovered from the permeate separation system can be utilized in the preparation of other alcoholic beverage products or ethanol solutions for industrial applications. Aspects of the permeate separation process are described in further detail elsewhere herein.

[0068] 1 shows a process diagram illustrating a method for separating ethanol from an alcoholic beverage, according to some embodiments. As shown, separation process 100 can include a first stage 100A and a second stage 100B. In some embodiments, first stage 100A can comprise a filtration system 120, and second stage 100B can comprise a permeate separation system 140.

[0069] As shown in separation process 100, an alcoholic beverage 110 can be provided to a filtration system 120 for separation. In some embodiments, the alcoholic beverage can include wine, beer, or distilled spirits, etc. In some embodiments, filtration system 120 includes a feed side, a permeable side, and a semipermeable membrane having a molecular weight cut-off (MWCO) in the range of 75 Da to 300 Da, a feed inlet, and a permeable outlet.

[0070] In some embodiments, pressure can be applied to the feed side of filtration system 120. In some embodiments, the feed pressure can range from about 25 psia (172 kPa) to 450 psia (3105 kPa). In some embodiments, the feed pressure can be selected to maximize ethanol flow through the semipermeable membrane of filtration system 120. In some embodiments, the pass-through side of the semipermeable membrane can be maintained at atmospheric pressure.

[0071] In some embodiments, filtration system 120 can output a retentate 160 from which a certain amount of ethanol has been removed. For example, if alcoholic beverage 110 includes wine, retentate 160 can include a more concentrated wine in which some of the ethanol and some of the water have been removed from the starting material by the membrane of filtration system 120. In some embodiments, a significant portion of the flavor and aroma compounds in alcoholic beverage 110 remain present and do not pass through the semi-permeable membrane of filtration system 120.

[0072] In some embodiments, the filtration system 120 also outputs a first osmotic component 130. In some embodiments, the first osmotic component 130 comprises a mixture of ethanol and water.

[0073] In some embodiments, first permeate component 130 can be further processed into beverage 135. In some embodiments, beverage 135 can include hard seltzer. In some embodiments, first permeate component 130 can be further processed by permeate separation system 140. In some embodiments, permeate separation system 140 can include a membrane contactor including two or more membranes, a permeate outlet, a gas inlet for supplying a carrier gas, a gas outlet, a condenser fluidly connected to the gas outlet, and a condensate outlet, as described in more detail elsewhere herein.

[0074] In some embodiments, the permeate separation system 140 can produce an aqueous dealcoholized solution 150. The aqueous dealcoholized solution 150 can include a refreshing permeate. In some embodiments, the permeate separation system 140 can produce an ethanol concentrate 145. In some embodiments, the ethanol concentrate 145 can be further processed, such as further distilled, to provide a more concentrated and purer form of ethanol.

[0075] In some embodiments, the aqueous dealcoholized solution 150 may be returned to the filtration system 120 as a refreshing permeate component. For example, the alcoholic beverage 110 and the dealcoholized solution (refreshing permeate component) 150 may be combined and reprocessed in the filtration system 120 to produce an additional amount of the first permeate component 130 and an additional amount of the residual component 160. It should be noted that the process of returning the refreshing permeate component 150 to the filtration system 120 may be repeated one or more times to further purify the feed fluid and remove an appropriate amount of ethanol while retaining appropriate flavor and aroma compounds in the feed fluid.

[0076] In some embodiments, the refreshing infusion component can be combined with the remaining components 160 to produce a reduced-alcohol beverage 170 in which the concentration of ethanol is reduced (e.g., from about 0.5% to about 100% by volume) while retaining a substantial portion of the moisture, flavor, and aroma compounds of the original alcoholic beverage.

[0077] An exemplary assembly for removing ethanol from a fluid is shown in Figure 2. As shown, assembly 200 may generally include a first container 210, a filtration system 220, a controllable pressure source 280 fluidly connected to filtration system 220, a permeate container 290, and a permeate separation system 300. Controllable pressure source 280 is shown along with a conduit 330 fluidly connecting first container 210 and filtration system 220. However, it will be understood that controllable pressure source 280 may be located in any suitable location where the pressure source is capable of applying pressure to filtration system 220.

[0078] In some embodiments, filtration system 220 includes a selectively permeable membrane 230, a feed inlet 240, and a permeate outlet 250. As shown, permeate outlet 250 can be fluidly connected to a conduit 340 leading to an osmotic component container 290, thus providing a pathway for osmotic components exiting filtration system 220 to travel to osmotic component container 290. Osmotic component container 290 can be provided in a size and configuration suitable for collecting the osmotic component (e.g., a first osmotic component comprising ethanol and water) that has passed through semipermeable membrane 230 in the filtration system. The osmotic component container can include one or more inlets 350 and outlets 360 for receiving and / or transporting the osmotic component from osmotic component container 290.

[0079] In some embodiments, permeate vessel 290 can be fluidly connected to permeate separation system 300 via conduit 370. In some embodiments, permeate separation system 300 includes a membrane contactor including two or more internal membranes, a permeate outlet, a gas inlet for supplying a carrier gas to the side of the hollow fiber membranes, a gas outlet, and a condenser fluidly connected to the gas outlet. In various embodiments, conduit 310 fluidly connects the condensate outlet of permeate separation system 300 to first vessel 210.

[0080] In some embodiments, first container 210 is configured to receive an aqueous liquid. In some embodiments, the aqueous liquid can include water or a refreshing permeation component (discussed elsewhere herein). First container 210 is fluidly connected to feed inlet 240 of filtration system 220, thereby supplying aqueous liquid to the filtration system when desired. In some embodiments, filtration system 220 includes a selectively permeable membrane 230 having a feed side 260 and a pass-through side 270. In use, a feed solution, such as an alcoholic beverage, is supplied to filtration system 220 via feed inlet 240. In some embodiments, the feed solution can include wine, beer, or liquor. In some embodiments, the feed solution can include an alcoholic beverage fermented from grapes. In some embodiments, the feed solution has an initial alcohol content, expressed as ABV. In some embodiments, the feed solution can include an alcoholic beverage fermented from grapes having an initial ABV ranging from about 12% to about 16%. In some embodiments, the feed solution includes wine, such as red wine or white wine.

[0081] In some embodiments, the feed solution comprises water, ethanol, and a flavor component.

[0082] In some embodiments, filtration system 220 can include one or more inlets 240 that provide a flow path for supplying and / or withdrawing feed solution from filtration system 220. In some embodiments, inlets 240 can provide a closed-loop system that allows for recirculation of the feed solution.

[0083] In some embodiments, a controllable pressure source 280 is fluidly connected to the filtration system. In some embodiments, the controllable pressure source 280 comprises a gas source. In some embodiments, the controllable pressure source 280 comprises an inert gas source, 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 the first container 210 and the filtration system 220. In some embodiments, one or more of the first container 210, the filtration system 220, the permeant component container 290, and / or the permeant component separation system 300 can include one or more conduits that provide flow paths for supplying solutions to and / or from various elements of the assembly 200.

[0084] In some embodiments, membrane 230 includes a feed side 260 having a surface in contact with the feed solution and a permeate side 270 having a surface in contact with the permeate component.

[0085] In some embodiments, the membrane 230 comprises a selectively permeable membrane configured to pass one or more components of the feed solution (e.g., a target solute such as ethanol) while rejecting one or more components of the feed solution. As used herein, the sieving properties of a membrane, i.e., its permeability to a liquid component, are determined by the membrane's pore size and set the maximum size of compounds that can pass through the membrane with fluid flow. The sieving coefficient of a given substance can be described as the ratio of the substance's concentration in the permeant component to its concentration in the feed liquid (i.e., an 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 describe membrane properties is to construct a sieving curve that plots the sieving coefficient as a function of molecular weight. The terms "molecular weight cutoff" or "MWCO" or "nominal molecular weight cutoff," used interchangeably herein, are values ​​used to describe the retention capacity of a membrane and refer to the molecular weight of a compound at which the membrane has 90% retention, corresponding to a sieving coefficient of 0.1. MWCO can also be expressed as the molecular weight of a compound, such as water or ethanol, at which the membrane allows 10% of its molecules to pass. MWCO is one of the membrane properties (along with values ​​such as pore size and target substance removal) provided by various commercial sources to aid in the selection of a membrane for use in a particular separation process.

[0086] In some embodiments, the membrane comprises a semipermeable membrane with a MWCO of 500 Daltons (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, etc. In some embodiments, semipermeable membrane 230 has a MWCO ranging from about 75 Da to about 300 Da, or from about 100 Da to about 300 Da, or from about 150 Da to about 300 Da.

[0087] In some embodiments, the separation quality of a selectively permeable membrane can be expressed as the rejection coefficient of the membrane for a given solute. The rejection coefficient is 1-c perm / c feed where c permis the concentration of the permeant, and c feed is the feed concentration. To determine the percentage of rejection ("rejection"), multiply the rejection factor by 100. As used herein, rejection is defined as the amount of compound in a feed solution that does not permeate the membrane (i.e., is retained in the feed solution) during a separation process. In some embodiments, the membrane comprises a semipermeable membrane with a MgSO4 rejection of at least 97% in a 1% MgSO4 solution. In some embodiments, the membrane comprises a semipermeable membrane with a NaCl rejection of at least 85% in a 1% NaCl solution.

[0088] In some embodiments, semipermeable membrane 230 comprises a plurality of pores having an average pore size of 10 nm or less. In some embodiments, membrane 230 comprises a plurality of pores having an average pore size in the range of about 0.1 nm to about 10 nm. Pore size can be measured by known methods such as bubble point analysis, mercury porosimetry, thermoporometry, permoporometry, adsorption methods, as well as methods based on liquid or gas transport and microscopy (e.g., scanning electron microscopy (SEM) and transmission electron microscopy (TEM)).

[0089] In some embodiments, membrane 230 may be made of cellulose acetate, cellulose triacetate, regenerated cellulose (pure cellulose treated in a chemical bath to enhance chemical resistance), mixed cellulose (e.g., a mixture of cellulose acetate and cellulose nitrate), or other similar non-toxic materials that can be formed into a semipermeable membrane having a desired MWCO.

[0090] In some embodiments, the separation or removal of organic compounds from a fluid involves the use of a semipermeable membrane. In some embodiments, the semipermeable membrane can comprise a material having an average pore size ranging from about 0.1 to about 10 nm, or from about 0.1 to about 9 nm, or from about 0.1 to about 8 nm, or from about 0.1 to about 7 nm, or from about 0.1 to about 6 nm, or from about 0.1 to about 5 nm, or from about 0.1 to about 4 nm, or from about 0.1 to about 3 nm, or from about 0.1 to about 2 nm, or from about 0.1 to about 1 nm. In some embodiments, the semipermeable membrane can comprise a material having an average pore size of about 1 nm or less, or about 0.9 nm or less, or about 0.8 nm or less, or about 0.7 nm or less, or about 0.6 nm or less, or about 0.5 nm or less, or about 0.4 nm or less, or about 0.3 nm or less, or about 0.2 nm or less. In some embodiments, the semipermeable membrane may comprise a material having an average pore size ranging from about 0.1 nm to about 1 nm. Semipermeable membranes having the above average pore size range are used to illustrate certain concepts, as they are useful applications for highlighting features and advantages. However, it should be readily apparent that the pore size of the material can be selected to provide a MWCO that can selectively remove desired organics from the starting fluid.

[0091] In some examples, the selectively permeable membrane may be a polymeric membrane, including cellulose acetate (e.g., commercially available from Trisep Corporation, Pall Corporation, Sterlitech Corporation, and MilliporeSigma), 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 any one or more combinations of the foregoing materials. In some embodiments, the selectively permeable membranes useful herein may be designed for liquid food or biotechnology applications (thus providing safe contact with beverages).

[0092] In some embodiments, the selectively permeable membrane may include one or more support layers that support one or more functional layers, such as one or more thin polyamide layers. In some examples, the selectively permeable membrane may include an array of membranes that may be arranged in parallel or in series, or any combination of parallel and series.

[0093] Exemplary separation methods and systems disclosed herein may be capable of removing ethanol from feed solutions at ambient temperatures and moderate pressure ranges while allowing selective retention of permeable solutes such as water, volatile organic compounds (VOCs), and sugars, which offers benefits such as reduced impact on flavor, aroma, and taste-related protein structures.

[0094] In some embodiments, agitation can be applied to the feed solution in the filtration system. One embodiment of this is shown in FIG. 2, where agitation in the form of stirring can be applied to the feed solution in the filtration system 220. The agitation is generally indicated at 320 in FIG. 2. It will be readily understood that agitation can be imparted to the feed solution by any suitable means, such as pumps and movement of system components. Agitation of the feed solution can be effective in reducing the occurrence of concentration polarization phenomena in the system. In some embodiments, agitation of the feed solution can be beneficial for reducing the occurrence of concentration polarization phenomena at or near the membrane surface (e.g., the membrane surface in contact with the feed solution) by creating turbulence in the solution.

[0095] FIG. 2 shows a basic schematic of a separation system useful for removing organic compounds from a liquid. It will be understood that other configurations employing these concepts are contemplated. For example, FIG. 2 shows a flat membrane configuration, in which the membrane extends across the vessel of the filtration system 220. In some embodiments, the membranes can be provided in different modular configurations. For example, flat membranes can be provided in plate-and-frame or spiral-wound configurations. In some embodiments, flat membranes can be provided in a membrane holder (e.g., a frame) in a tubular, spiral-wound, or other configuration.

[0096] 2 illustrates a separation assembly 200 that includes one filtration system 220. However, it will be readily understood that any number of filtration systems 220 may be provided in a series configuration, and the permeate from the filtration may be passed through a second (third, fourth, etc.) filtration system to further separate ethanol from the alcoholic beverage.

[0097] In some embodiments, the membranes may be provided in configurations other than flat, for example, in some embodiments, the membranes may be provided in capillary configurations, hollow fiber configurations, tubular configurations, pouch configurations, and the like.

[0098] In some embodiments, the system can be designed on a modular basis, providing a high degree of flexibility, as membranes can be incorporated into modules, modules can be incorporated into loops, and loops can be incorporated into systems, allowing the system design to be customized to meet process needs and scale to meet production requirements.

[0099] According to the methods and systems described herein, as ethanol and water permeate the semipermeable membrane in the filtration system 220, the liquid remaining on the feed side of the membrane (the retentate) includes one or more compounds that did not permeate the membrane, such as flavor compounds and aroma compounds. The retentate can be directed to one or more downstream product components fluidly connected to the filtration system. As the ethanol and water pass through the membrane, a first permeate component is formed on the permeate side of the semipermeable membrane. The first permeate component can be directed to one or more downstream components fluidly connected to the permeate component container 290 of the system.

[0100] The one or more downstream product components fluidly coupled to the filtration vessel may 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 device, one or more membrane separation elements, or individual packages (such as bottles and kegs). The one or more downstream components fluidly coupled to the permeate vessel may 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) devices, a waste reservoir, a permeate reservoir, etc. In some embodiments, the one or more permeate recovery or regeneration devices may include a separation element (such as those described herein or a reverse osmosis system), or one or more distillation devices.

[0101] As shown in FIG. 2 , assembly 200 can include a permeate separation system 300 fluidly connected to the permeate container. The permeate separation system can be configured to separate ethanol from the first permeate produced through the filtration system. In some embodiments, permeate separation system 300 can utilize membrane separation technology (e.g., a membrane contactor) to separate ethanol and water. In some embodiments, permeate separation system 300 can utilize membrane separation technology (e.g., a membrane contactor) to separate ethanol, water, and one or more flavor and / or aroma components contained in the first permeate.

[0102] In some embodiments, the permeate separation system 300 can include a membrane contactor system. According to some embodiments, the membrane contactor system can generally include a membrane (e.g., multiple membranes) having a first side and a second side, a permeate outlet, a gas inlet for supplying a carrier gas to the side of the membrane, a gas outlet, and a condenser fluidly connected to the gas outlet. In some embodiments, the membrane includes a microporous membrane or a non-porous membrane.

[0103] Generally, the membrane contactor system according to the method and system of the present invention achieves 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 embodiments, the membrane contactor utilizes a porous membrane, which provides the interface between the first permeate component and either a carrier gas or a carrier liquid. In some embodiments, the carrier is a gas.

[0104] An exemplary permeate separation system 300 is shown in FIG. 3. FIG. 3 shows a schematic diagram of one possible permeate separation system 300 shown in FIG. 2. As shown, a first permeate is transported into the permeate separation system 300 via conduit 370 and enters the membrane contactor 410 through a permeate inlet 450. In some embodiments, the membrane contactor 410 includes a gas inlet 430, a gas outlet 440, a permeate inlet 450, and a permeate outlet 460. In some embodiments, the membrane contactor includes two or more internal semipermeable membranes. In some embodiments, the semipermeable membranes may include microporous or non-porous membranes. In some embodiments, the membranes are provided as hollow fiber membranes. In some embodiments, a first permeate is introduced into the 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 embodiments, applying a carrier gas to the outside of the hollow fiber creates a difference in gas concentration levels between the inside (lumen surface) and outside (abluminal surface) of the membrane. This concentration difference can facilitate the migration of ethanol from the first permeate liquid stream. In some embodiments, the liquid and gas sides of the membrane can be reversed, with a carrier gas flowing inside the hollow fibers (the luminal surface) and a liquid first permeate applied to the outside of the fibers (the abluminal surface). Thus, in a general aspect, a first side of the membrane in the membrane contactor 410 can be in contact with a liquid, and a second side of the membrane in the membrane contactor 410 can be in contact with a gas. The first and second sides can include the luminal and abluminal surfaces. Flow through the membrane contactor can be parallel, radial, and / or transverse. In some embodiments, baffles can be included to increase membrane surface area contact.

[0105] In some embodiments, the porous hollow fiber membrane can contain a plurality of pores having an average pore size of 10 nm or less. In some embodiments, the membrane in the membrane contactor can contain a plurality of pores having an average pore size ranging from about 0.002 μm to about 10 μm, or from about 0.002 μm to about 5 μm, or from about 0.002 μm to about 4 μm, or from about 0.002 μm to about 3 μm, or from about 0.002 μm to about 2 μm, or from about 0.002 μm to about 1 μm, or from about 0.002 μm to about 0.5 μm, or from about 0.002 μm to about 0.2 μm. Pore size can be measured by known methods such as bubble point analysis, mercury porosimetry, thermoporometry, permoporometry, and adsorption methods, as well as by methods based on liquid or gas transport and microscopy (e.g., scanning electron microscopy (SEM) and transmission electron microscopy (TEM)). In some embodiments, the membrane in the membrane contactor can be non-porous.

[0106] In some embodiments, a reduced pressure can be maintained downstream of the membrane contactor to draw a carrier gas through the membrane contactor. In some embodiments, the reduced pressure downstream of the contactor can be 1 atmosphere (760 torr) or less. According to some embodiments, a pressure ranging from about 5 torr to about 760 torr, or from about 5 torr to about 700 torr, or from about 5 torr to about 600 torr, or from about 5 torr to about 500 torr, or from about 5 torr to about 400 torr, or from about 5 torr to about 300 torr, or from about 5 torr to about 200 torr, or from about 5 torr to about 100 torr, or from about 5 torr to about 30 torr can be maintained downstream of the membrane contactor to draw a carrier gas through the membrane contactor.

[0107] In various embodiments, the permeate separation system can be maintained at ambient temperature to remove ethanol and one or more flavor and aroma components from the first permeate. In some embodiments, directing the first permeate to the membrane contactor can be performed at ambient temperature. In some embodiments, the permeate separation system can be maintained at a temperature ranging from about 0°C to about 30°C, or from about 5°C to about 30°C, or from about 10°C to about 30°C, or from about 15°C to about 25°C.

[0108] In various embodiments, the permeate separation system 300 includes a gas source 400. The gas source 400 can provide a carrier gas to the membrane contactor 410. In various embodiments, the carrier gas can include carbon dioxide (CO), helium (He), nitrogen (N), argon (Ar), or other inert gases.

[0109] In some embodiments, the hollow fiber membranes in the membrane contactor can be made of polypropylene, PDMS, polyolefin, or the like. The hollow fiber membranes can be provided in various configurations within the separation system housing. Exemplary membrane contactors are commercially available from, for example, 3M™ Company (e.g., Liqui-Cel™ membrane contactor product line), PermSelect™ (e.g., PermSelect™ silicone gas exchanger product line), Mitsubishi Chemical Aqua Solutions (e.g., Sterapore™ product line), and Nagasep Nagayanagi Corporation.

[0110] In various embodiments, the gas exiting the membrane contactor 410 at gas outlet 440 is enriched in components that can permeate the membrane (e.g., ethanol), while the liquid exiting the device at permeate outlet 460 is enriched in components that do not readily permeate the membrane (e.g., water).

[0111] In some embodiments, the gas exiting membrane contactor 410 at gas outlet 440 comprises a gas mixture that can be sent to condenser 470 to condense compounds present in the gas mixture. In some embodiments, condenser 470 can provide one or more condensation stages so that components of the mixture can be separated as the gas mixture cools. In some embodiments, components of the gas mixture having a first boiling point can be condensed in the first stage (e.g., ethanol), thereby providing an ethanol concentrate. The ethanol can be collected in 480. In some embodiments, the ethanol concentrate can have a higher alcohol content than the starting alcoholic beverage. In some embodiments, the ethanol concentrate can comprise an alcohol content of about 40% to about 80% by volume. Optionally, condenser 470 can include a second stage to condense components of the gas mixture having a second boiling point, such as residual flavors and aromas. These residual flavors and aromas can be collected in a container in 480.

[0112] In some embodiments, once the residual flavors and / or aromas and ethanol are separated from the gas, the gas is recycled to the gas inlet 430, thereby providing a closed system.

[0113] In various embodiments, the liquid exiting the membrane contactor 410 at the permeate outlet 460 may include the aqueous liquid 510. This liquid may, in some embodiments, be reused as a refresher permeate in the separation methods and systems described herein. Thus, in some embodiments, the aqueous liquid 510 may be provided to a filtration system as a refresher permeate.

[0114] In some embodiments, the residual flavors and aromas collected in 480 can be combined with aqueous liquid 510. In these embodiments, the residual flavors and / or aromas can be recovered and reconstituted into a dealcoholized beverage.

[0115] In some embodiments, the separation methods and systems described herein can be used at any desired point during the preparation of an alcoholic beverage, such as during distillation or after the beverage has been fully prepared.

[0116] In various embodiments, the method and system can utilize continuous-flow separation. In these embodiments, the products of the permeate separation system (ethanol concentrate and aqueous liquid) can be continuously removed from the system. In some embodiments, the aqueous liquid produced by the permeate separation system can contain low amounts of ethanol (e.g., 5% or less by volume, or 4% or less, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less). In these embodiments, for example, the aqueous liquid can contain a refreshing permeate. In some embodiments, the method includes adding the refreshing permeate directly to the residual component, thereby providing a reduced-alcohol beverage. In some embodiments, the refreshing permeate can be utilized in a filtration system. These embodiments can provide a closed-loop process in which components of the permeate can be reused throughout the system. Ethanol collected from the permeate separation system can be utilized in the preparation of other alcoholic beverages or ethanol-containing solutions for industrial applications. In some embodiments, the permeate can be repeatedly refreshed and reused. In this mode, the refreshing permeate can be recycled by combining the refreshing permeate with the residual component obtained in the first stage. In some embodiments, such a process can reduce water and energy usage. This is because the refreshing infusion components are repeatedly generated throughout the system, reducing the need to add new water to the system.

[0117] In some embodiments, the containment configuration depicted in and included in the figures can be included in a production line of a beverage production facility. For example, the separation system 200 depicted in FIG. 2 can be included in a production line of a beverage production process, such as an alcoholic beverage. In some embodiments, the configuration depicted in and included in FIG. 2 can utilize the concepts of cross-flow configurations described herein. In some embodiments, the configuration depicted in and included in the figures can be included as a stand-alone unit for processing an alcoholic beverage. For example, the separation system 200 depicted in FIG. 2 can be provided as a stand-alone, separate unit that can be used any time after the alcoholic beverage is prepared. In some examples, the stand-alone separation unit can be used at the point of use when a user opens an alcoholic beverage and desires to remove some or all of the ethanol before drinking the beverage.

[0118] Therefore, it should be understood that the various methods and systems discussed herein can be applied to alcoholic beverages to produce dealcoholized, low-alcohol, or substantially non-alcoholic beverages that have a taste similar to that of traditional alcoholic beverages. In some embodiments, the methods and devices discussed herein allow for the substantial removal of ethanol or ethyl alcohol from an alcoholic beverage while substantially preventing the removal of other compounds from the alcoholic beverage. The resulting beverage may contain either low alcohol or substantially no alcohol, while retaining many or most of the compounds that give the original alcoholic beverage its characteristic taste. For example, when the methods and devices discussed herein are applied to a brewed alcoholic beverage (e.g., stout beer) to produce a modified stout beer, the modified stout beer will have a stout-like taste, but the modified stout beer will have a low or substantially no alcohol content. As another example, when the methods and devices discussed herein are applied to a distilled spirit such as gin, the modified gin will have a gin-like taste, but the modified gin will have a low or substantially no alcohol content. In other words, in some embodiments, the novel methods and devices discussed herein can produce low-alcohol or non-alcoholic beverages that taste the same as or very similar to alcoholic beverages, thereby mimicking or replacing traditional alcoholic beverages. In some embodiments, the methods and devices discussed herein can be applied to other beverages or products for human consumption. For example, if a nursing mother consumes alcohol, the breast milk she produces may contain alcohol. Previously, such nursing mothers may have tended to discard alcohol-contaminated milk. Applying the various methods and devices described above to breast milk can remove alcohol contamination from the breast milk, allowing it to be offered to the mother's nursing child. As another example, the methods and devices discussed herein can be applied to tinctures (e.g., solutions using ethanol as a solvent). In some embodiments, the tincture can be an extract of a plant or animal material dissolved in ethanol.The solvent concentration of ethanol contained in tinctures typically ranges from 25% to 60%. In some embodiments, the solvent concentration of ethanol can be as high as 90%. The various methods and devices discussed herein can be applied to such tinctures to remove the ethanol and substantially preserve the alcohol-free extract. As yet another example, some ingestible foods, such as flavorings (e.g., vanilla flavoring) or cannabis extracts, are preserved in an alcohol-based solution. The various methods and devices discussed herein can be applied to such ingestible products to remove the alcohol while preserving the ingestible substance. Removing alcohol from such ingestible products is highly desirable for people who must avoid alcohol (e.g., people with alcohol allergies, people with alcoholism problems, etc.). It should also be understood that the above-described methods and devices can be applied to other suitable fluids in the food and beverage industry.

[0119] The present disclosure is not limited in terms of the specific embodiments described in this application, which are intended as illustrations of various aspects. Moreover, the various disclosed embodiments may be used interchangeably unless otherwise specified. Many modifications and variations are possible without departing from the spirit and scope of the present disclosure, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the present disclosure, in addition to those recited herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be encompassed by 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. Therefore, it is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0120] With respect to the use of virtually any plural and / or singular term herein, those skilled in the art can translate from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural permutations may be expressly set forth herein for clarity.

[0121] In general, those skilled in the art will understand that the terms used in this specification, and particularly in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "comprises" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "comprises" should be interpreted as "including but not limited to," etc.). Those skilled in the art will further understand that if a specific number of introduced claim recitations are intended, such intention will be explicitly set forth in the claim; in the absence of such recitation, no such intention exists. For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more" to introduce the claim recitations. However, the use of such phrases should not be construed to mean that the introduction of a claim recitation with the indefinite article "a" or "an" limits any particular claim containing such an introduced claim recitation to embodiments containing only one such recitation, nor should the use of a definite article used to introduce a claim recitation, even when the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" and / or "an" should be interpreted to mean "at least one" or "one or more"). Furthermore, even when a specific number of introduced claim recitations 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 "two recitations" without any other modifier means at least two recitations, or two or more recitations).Furthermore, in instances where a convention similar to "such as at least one of A, B, and C" is used, generally such a configuration is intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, and / or a combination of A, B, and C, etc.). In instances where a convention similar to "such as at least one of A, B, or C" is used, generally such a configuration is intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, and / or a combination of A, B, and C, etc.). Those skilled in the art will further appreciate that whether in the specification, claims, or drawings, virtually any conjunction word and / or phrase presenting two or more alternative terms should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B." Additionally, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is thereby also described in terms of any individual component or subgroup of components of the Markush group.

[0122] A number of embodiments have been described. Various modifications may be made without departing from the spirit and scope of the invention. For example, steps may be rearranged, added, or deleted, and various forms of the methods set forth above may be used. Accordingly, other embodiments are within the scope of the following claims. [Example]

[0123] Example 1. Dealcoholization of red wine. 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 selected as the feed liquid. A volume of 300 ml of red wine sample A was added to a filtration system containing a cellulose acetate-based nanofiltration membrane with a MWCO of 150–300 g / mol. The effective membrane diameter was 76 mm, and the operating temperature was approximately 22°C (room temperature). The applied pressure was 40 psia (276 kPa), and filtered air was supplied. After 6.5 hours, the volume of the feed side was observed to have decreased to 247 ml, meaning that 53 ml of liquid had passed through the membrane as a permeate. The overall permeance was 0.04517 l / m. 2 / h / psia (LMH / psia), which was extrapolated to a flux of 13.1 LMH at 20 bar.

[0124] After restoring the lost volume by adding 53 ml of deionized water to the remaining components, the ABV level of product (A1) was determined to be approximately 12.3%, representing an 18% reduction from the original wine sample A. The product was evaluated after processing only through a filtration system, without undergoing a permeation separation system. Product A1 and untreated red wine sample A were sent to professional sommeliers, who randomly tasted the wines and evaluated the differences between Product A1 and untreated red wine sample A. A score of "5" was used to evaluate similarity to the original wine, with "1" being the least similar. Feedback revealed that the reduced wine product A1 was overall very similar to the untreated wine, with a detailed comparison shown in Table 1. These samples were also tasted by external tasters. Surprisingly, some tasters preferred the reduced version (i.e., product A1) due to its higher ethanol concentration and perceived intensification of untreated red wine sample A.

[0125] [Table 1]

[0126] Example 2. Dealcoholization of red wine. 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 selected as the feed wine. An initial volume of 300 ml of red wine sample B was added to a filtration system containing a cellulose acetate-based nanofiltration membrane with a MWCO of 150–300 g / mol. The effective membrane diameter was 76 mm, and the operating temperature was approximately 22°C. The applied pressure was 40 psia (276 kPa), and filtered air was supplied. The separation process was stopped at the expected volume loss on the feed side. The volume loss ranged from 10–80% based on the initial feed volume.

[0127] The volume lost in the retentate was restored by adding an equal volume of deionized water to the retentate, yielding product (B1). The product was evaluated after processing only through the filtration system, not through the permeation separation system. The resulting samples were analyzed for chemical composition profiles, including ethanol concentration, pH, volatile acids, fructose, and glucose, as shown in Table 2. The actual reduction was determined by the actual ABV of the reduced sample (1 - actual ABV of the reduced sample / actual ABV of the untreated wine, in %). Because the molecular weight cutoff (MWCO) of the membrane used in this study was 150-300 g / mol, the concentrations of components below this range (e.g., tartaric acid, fructose, and glucose in Table 2) decreased with increasing alcohol reduction. The apparent increase in glucose and fructose in samples B4 and B5 was likely due to inconsistencies in the analytical process. However, slight changes in acid concentration did not affect the pH.

[0128] [Table 2]

[0129] Similar results were observed for other compounds, such as phenolic compounds. Both the reduced products B1–B5 and the untreated wine sample B were analyzed by high-performance liquid chromatography (HPLC) to determine the phenolic compound profile. The phenolic compound concentration ratios between the reduced product B5 and the untreated wine sample B were calculated and are shown in Figure 4A, along with the removal efficiencies. Figure 4A shows the concentration ratio of phenolic compounds in a 60% reduced wine (product B5). Figure 4B shows the removal efficiency of several compounds as a function of molecular weight, calculated based on the weight in the permeate / weight in the feed. The results showed that compounds in wine, particularly tannins, which are known to cause astringency in wine, were better retained by the separation membrane as molecular weight increased. It is noteworthy that the actual concentrations of these investigated compounds in Figure 4A are related to the degree of reduction, with higher reductions resulting in lower compound concentrations.

[0130] The cellulose acetate membrane utilized was found to partially retain compounds with molecular weights in the 150–300 Da range in the source wine, while other compounds of interest, such as tannins, phenols, and anthocyanins, were well retained. By moderately reducing the alcohol content, the flavor profile was adequately maintained.

[0131] To obtain sensory data, alcohol-reduced products B1–B5 and untreated red wine sample B were sent to professional sommeliers and / or wine lovers for blind wine tasting. Similarity was assessed on a 5-point scale, with a score of "5" indicating identical and "1" indicating the least similar. The feedback indicated that after a 30% reduction in alcohol content (i.e., from 14% to 10% ABV), the reduced samples were very similar to the original red wine sample B, and that alcohol-reduced products B1–B5 retained their aroma, flavor, and body. Further reduction resulted in unfavorable sensory experiences, such as a "watery" or "watered-down" perception, likely due to the partial loss of non-alcoholic low-molecular-weight substances in the wine. The tasting feedback was consistent with the results of the chemical analysis: higher reductions resulted in lower levels of wine-derived compounds.

[0132] Some correlations between reduction and various taste feedback of the samples are shown in Figures 5 and 6. Figure 5 shows the tasting feedback of reduced ethanol products B1 to B5 and untreated red wine sample B in terms of fruity aroma. The images in the figure show the types of fruity aroma perceived by the tasters. Figure 6 shows the tasting feedback regarding body of reduced ethanol products B1 to B5 and untreated red wine sample B. As a result, the fruity taste and body were well maintained in the ethanol-reduced samples.

[0133] Example 3. Dealcoholization of red wine. Ethanol was removed from red wine as follows. Red wine sample C (Oak Ridge 2020 Lodi Estates Cabernet Sauvignon) with an initial ABV of 14.4% was selected as the source wine. An initial volume of 300 ml of red wine sample C was added to a filtration system containing a cellulose acetate-based nanofiltration membrane with a MWCO of 150–300 Da. The effective membrane diameter was 76 mm, and separation was performed at room temperature (approximately 22°C). The applied pressure was 40 psia (276 kPa), and filtered air was supplied. The separation process was terminated when the alcohol ABV was reduced by approximately 30%. An equal volume of deionized water was added to the remaining components, resulting in a reduced sample designated Product C1. The actual ABV of Product C1 was 10.3%, as determined by an FTIR-based wine analyzer.

[0134] In another batch, a sample expected to achieve 50% reduction was prepared in a similar manner, but the reduction was achieved in a two-stage process. In the first stage, the ABV of the wine was reduced by approximately 30%, providing a retentate product, Product C1. The same volume of distilled water was then added to restore the volume of C1. This restored retentate was used as the feed for the second-stage pressure-assisted diafiltration process, using 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 for this stage). After restoring the volume to the retentate with distilled water, the final product, designated Product C2, showed a 49% reduction (calculated based on the measured ethanol concentrations of Sample C2 and untreated Sample C). To examine the effect of atmospheric oxidation, N2 was used in the two-stage process and compared with results using pressure-fed filtered air. The products were evaluated after processing only through the filtration system, not through the permeation separation system.

[0135] Both samples (products C1 and C2) were analyzed in a blind wine tasting by professional sommeliers and wine lovers, with untreated red wine sample C as a control. Tasters were informed that these samples had been reduced, but received no further information. Tasters had to rate the similarity of the provided samples to the control sample, with a value of "5" indicating the samples were identical and a value of "1" indicating the samples were least similar. Tasters were also prompted to estimate how much the samples had been reduced.

[0136] Typical tasting feedback for products C1 and C2 compared with untreated red wine sample C is shown in Figure 7. The 30% reduction product C1 was considered very close to untreated wine sample C, with most rated as 4 or 4.5. Furthermore, tasters commented, "It has a nice aroma and taste. It's really well-balanced. If I didn't know it was a reduced-ABV sample, I might think it was the original." For the 50% reduction sample, one taster considered it only 15% reduced, while another estimated it to be 30%, which was much lower than the actual reduction rate (i.e., 49%). This demonstrates that the separation process using a cellulose-based semipermeable membrane can achieve high retention of flavor compounds that contribute to sensory satisfaction, resulting in a reduced-ABV sample with excellent taste.

[0137] Example 4. Dealcoholization of red wine. In batch mode for ABV reduction, a 300mL aliquot of Oak Ridge Estate Crown 2021 Cabernet Sauvignon wine was diluted to approximately 0.00453ml. 2The dialysis was performed in a filtration system containing a cellulose acetate membrane with an effective membrane area of ​​1000 psi. Separation was performed at room temperature and equilibrated at 60 psi (pressure was increased from 40 psi to maintain differentiation between the reservoir and the membrane cell). After 64 hours, the wine's flavor compounds were concentrated upstream, and the total volume of the wine was subsequently restored. Theoretically, if flavor loss during dialysis was minimal, the wine would have the same flavor concentration as the feed wine. Volume restoration was initially performed manually, and the dialysis experiment was stopped at the desired ABV reduction, calculated from the volume change of the original alcohol: ABV reduction = 1-300 / [V]. i -V f ]+300, in the formula, V i and V f are the initial and final volumes of the water reservoir, respectively. During the process, the pressure difference between the filtration vessel and the water reservoir due to volume changes led to the introduction of water from the water reservoir into the filtration vessel (the retentate) to maintain the liquid volume at 300 ml. This process is typically characterized by a constant increase in solute concentration, which can easily cause changes in the state of flavor substances in the ethanol / water mixture, resulting in the formation of soluble precipitates accompanied by partial precipitation of insoluble components. To address this issue, a continuous separation process and system was designed. Theoretically, the flavor concentration can be maintained constant by feeding the permeate from the filtration system to a permeate separation process and removing ethanol from the permeate to create a refresher permeate. The refresher permeate, which contains an aqueous liquid, is continuously fed to the wine in the filtration system, maintaining a constant volume.

[0138] A slight drop in internal pressure within the filtration system vessel due to volume loss of feed solution will cause aqueous liquid from the aqueous liquid source (either the feed or refresh permeate from the permeate separation process) to flow into the filtration system vessel to compensate for the volume loss and again reach pressure equilibrium. As shown in Examples 4(i) and 4(ii), it has been observed that separation can last up to 40 hours.

[0139] Example 4(i). A red wine sample (300 ml of J. Lohr's Cabernet Sauvignon, 13.9% ABV) was analyzed by a chromatographic method with a molecular weight cutoff of 150 Da (EFA 0.00454-m 2 The filtration system, shown in Figure 1, was constructed by placing distilled water in vessel 210. Pressure was supplied from compressed air filtered through a 10 nm filter, and the process was initiated at 50 psi (345 kPa) at room temperature. After a total of 46 hours, the total volume of permeate in the permeate vessel was 520 mL, while the residual component remaining in the filtration system 220 (Figure 1) remained at 300 mL. The volume of distilled water in vessel 210 had decreased from 750 mL to 230 mL. The residual component in the filtration system 220 and the first 130 permeate components (Figure 1) were analyzed for the full phenolic panel, an indicator of flavor retention. The final ABV of the reduced-ethanol wine product was 1.8% v / v.

[0140] Example 4(ii). A red wine sample (302.8 grams of J. Lohr's Cabernet Sauvignon, ABV 13.9% v / v) was diluted with 150 Da MWCO (EFA 0.00454-m 2The filtration system was then fed into a vessel equipped with a cellulose acetate membrane (210). The filtration system was charged with distilled water in vessel 210. Pressure was supplied from compressed air filtered through a 10 nm filter, and the process was initiated at 50 psi (345 kPa) at room temperature. After a total of 42 hours, the total volume of permeate was 582.6 grams, while the residual components remaining in filtration system 220 remained at 300 mL, resulting in a total volume of distilled water withdrawn from vessel 210 of 582.6 grams. The residual components in filtration system 220 were analyzed for the complete phenol panel as an indicator of flavor retention. The ABV of the reduced-ethanol wine product was 2.9% v / v. This corresponds to an 80.5% reduction in ABV, exceeding the value for a 65.8% volume reduction. This indicates that the process of pressure dialysis in continuous mode also improved selectivity. Figure 8 shows the change in the proportions of each component in the treated wine relative to the corresponding composition of the original wine freshly opened in this example. As a result, the separation membrane showed excellent retention efficiency for most flavor components except for caffeic acid and quercetin.

[0141] Figure 8 clearly shows a significant contrast in flavor concentrations between wine's residual and permeate components, demonstrating the effectiveness of the separation membrane, system, and method in preserving the desired flavor profile, with these phenolic substances representing typical flavor profiles. Due to the wide variation in concentrations of various flavor compounds in wine and the limitations of analytical techniques, measurements of each component may yield different standard deviations, especially at ultralow concentrations or even trace concentrations that reach analytical limits and resolution. These data are presented as highlights and should not be used to draw conclusions. Further examination of the list of molecules analyzed by molecular weight revealed a decline in retention as molecular weights decreased below 150–300 daltons.

[0142] Example 5. Ethanol removal from red wine as follows: A red wine (Cabernet Sauvignon, J. Lohr) with an initial ABV of 13.9% was selected as the feed wine. The MWCO was 150 Da and the effective membrane area was 0.00454 m 2 An initial volume of 300 ml of red wine was added to a filtration system containing a cellulose acetate-based nanofiltration membrane. The applied pressure was 40 psia (276 kPa) and was supplied with compressed air filtered through a 0.1 μm filter. After a total of 16 hours, a total of 131 gm (or 134 ml) of permeate (ethanol in water) was present in the permeate container. Distilled water was added to bring the volume to 302 mL to correct for residuals. The ethanol-reduced wine was determined to have a 43.7% v / v reduction in ABV.

[0143] Example 6. Ethanol was removed from red wine as follows. Cabernet Sauvignon (J. Lohr) red wine with an initial ABV of 13.9% was selected as the feed wine. The MWCO was 150 Da and the effective membrane area was 0.00454 m. 2 An initial volume of 200 ml of red wine was added to a filtration system containing a cellulose acetate-based nanofiltration membrane. The applied pressure for filtration was 33 psi (228 kPa) supplied with 0.1 μm filtered nitrogen. After a total of 18.6 hours, a total of 41 grams (134 ml) of permeate (ethanol in water) was present in the permeate container. The remaining permeate was restored to the original volume of 200 ml by adding distilled water. The ethanol-reduced wine was determined to have a 20.5% v / v reduction in ABV.

[0144] Example 7. Red wine C (Oak Ridge 2020 Lodi Estates Cabernet Sauvignon) with an initial ABV of 14.4% was selected as the feed wine with an initial volume of 600 ml. The membrane used was a cellulose acetate membrane with a MWCO of 150 Da. The effective membrane diameter was 76 mm, and the test was conducted at room temperature. The applied pressure was 40 psia, and sterilized air was supplied. The experiment was terminated when the volume of the remaining components was reduced to two-thirds of the initial volume.

[0145] The recovered permeate components were further processed in a membrane contactor containing a non-porous PDMS membrane. The permeate components were introduced onto the outer surface of the non-porous membrane, and gas (air) was introduced onto the inner surface of the non-porous membrane. Separation of the permeate components was carried out at room temperature. The pressure on the upstream side (liquid side) of the membrane contactor was maintained at 1 atmosphere, and the pressure on the downstream side (gas side) was maintained at approximately 5 torr, and gas was aspirated through the membrane contactor. The flow rate of the permeate components passing through the membrane contactor was approximately 40-45 cm. 3 The flow rate was 1 / min. The separation was carried out for 6.5 hours, yielding two products: a dealcoholized aqueous liquid containing ethanol and flavor components, and a carrier gas. The dealcoholized aqueous liquid showed a decrease in ABV from 14.4% (before entering the membrane contactor) to 6.6% (refresh permeate). The carrier gas was then passed through a condenser, and an alcohol concentrate with an ethanol content of approximately 25% vol. was recovered. The ABVs of the liquid and the alcohol concentrate were monitored by refractometer.

[0146] The dealcoholized aqueous liquid was then mixed with the remaining components in a volume ratio of 3:2 (i.e., 60 vol% of the alcohol-reduced refreshing infusion components mixed with 40 vol% of the remaining components), designated Product C3. The final ABV of Product C3 was 9.7% (i.e., a 33% reduction) as measured by an FTIR-based wine analyzer.

[0147] In a similar manner, a 50% reduction sample (C4, 7.2% ABV) was prepared by mixing the same retentate from the membrane contactor with the reduced alcohol filtrate. In this case, the ethanol concentration of the filtrate was stripped to 4.12%, and the volume ratio of the retentate to the aqueous refresh permeate was 3:7.

[0148] Both samples C3 and C4 were presented to professional sommeliers and wine lovers for sensory evaluation, which elicited favorable comments, some of which are listed below. Sample C3: "This sample is full-bodied and aromatic. It smells and tastes of alcohol. I like it." Sample C4: "This sample has a stronger attack, more fruit and acidity. A bit too acidic for me." Comment after being informed of the actual ABV of sample C4: "Wow, this is very promising. I would buy and drink such a low-alcohol wine if it were available commercially." [Explanation of symbols]

[0149] 200 Assembly 210 First Container 220 Filtration System 230 Semi-permeable membrane 240 Supply Inlet 250 Passage Exit 260 Supply Side 270 Passing side 280 Controllable Pressure Source 290 Penetrating ingredient container 300 Permeation Component Separation System 400 Gas supply unit 410 Membrane Contactor 430 Gas inlet 440 Gas Outlet 460 Penetration component outlet 470 Condenser

Claims

1. 1. A method for separating ethanol from an alcoholic beverage, comprising: - an alcoholic beverage containing water, ethanol, and flavoring ingredients, - a semipermeable membrane (230) comprising a feed side (260), a permeate side (270) and a molecular weight cut-off in the range of 75 Da to 300 Da; a feed inlet (240), and - passage exit (250), and passing the mixture through a filtration system (220) comprising: - applying pressure to the filtration system to selectively allow ethanol and water to pass through the semipermeable membrane, providing a first permeant component to the pass side of the semipermeable membrane and a remainder component to the feed side of the semipermeable membrane; - withdrawing the first permeate component from the filtration system through the pass-through outlet; - directing said first permeate component to a membrane contactor (410) comprising two or more contactor membranes having a first surface and a second surface; contacting a first side of the contactor membrane with the first permeate component and a second side of the contactor membrane with a carrier gas, thereby allowing ethanol to pass from the first permeate component through the contactor membrane and into the carrier gas to provide a refresh permeate component; - providing said refreshing permeating component to said remaining components to form a reduced ethanol beverage; A method comprising:

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 a pressure in the range of 25 psia to 450 psia.

4. 10. The method of claim 1, wherein contacting the first side of the contactor membrane with the first permeate component and contacting the second side of the contactor membrane with a carrier gas is carried out at a temperature ranging from 10°C to 30°C.

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

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

7. 10. The method of claim 1, further comprising flowing the alcoholic beverage tangentially across the first surface of the semipermeable membrane within the filtration system.

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

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

10. 10. The method of claim 9, wherein the semi-permeable membrane comprises a plurality of pores having an average pore size in the 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. 10. The method of claim 1, wherein the semipermeable membrane has a molecular weight cutoff in the range of 150 Da to 300 Da.

13. The semipermeable membrane is 1% MgSO ４ At least 97% MgSO in solution ４ The method of claim 1 having a removal rate.

14. 10. The method of claim 1, wherein the semipermeable membrane has a NaCl rejection rate of at least 85% in a 1% aqueous 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. 10. The method of claim 1, wherein the contactor membrane comprises a hollow fiber membrane containing a plurality of pores having an average pore size in the range of 0.002 μm to 0.2 μm.

17. The method of claim 1 , wherein the contactor membrane comprises non-porous hollow fibers.

18. 10. The method of claim 1, further comprising maintaining a vacuum of 30 torr or less at a location downstream of said membrane contactor to draw a carrier gas through said membrane contactor.

19. 19. The method of claim 18, wherein the reduced pressure ranges from 5 torr to 760 torr.

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

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

22. 10. 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 thereof.

23. 1. An assembly (200) for separating ethanol from an alcoholic beverage, comprising: a filtration system (220), - a feed side (260), a permeate side (270) and a semipermeable membrane (230) with a molecular weight cut-off ranging from 75 Da to 300 Da; a feed inlet (240), and - passage exit (250), a filtration system (220) comprising: a first container (210) fluidly connected to said supply inlet; a controllable pressure source (280) fluidly connected to said filtration system; a permeating component container (290) fluidly connected to said through-outlet; a permeant separation system (300) fluidly connected to said permeant container, a membrane contactor (410) comprising two or more contactor membranes having a first surface and a second surface; - osmotic component outlet (460); - gas supply (400), a gas inlet (430) fluidly connected to a gas supply and configured to supply a carrier gas to the side of said contactor membrane; a gas outlet (440), and a condenser (470) fluidly connected to the gas outlet (440); a permeation component separation system (300) comprising: An assembly (200) comprising:

24. 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 semipermeable membrane (230) is 1% MgSO ４ At least 97% MgSO in solution ４ 24. The assembly of claim 23, having a removal rate.

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

27. 24. The assembly of claim 23, wherein the controllable pressure source (280) comprises a pressure source of up to 450 psia (3105 kPa).

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

29. 24. The assembly of claim 23, wherein the contactor membrane comprises a hollow fiber membrane containing a plurality of pores having an average pore size in the range of 0.002 μm to 0.2 μm.

30. 24. The assembly of claim 23, wherein the contactor membrane comprises non-porous hollow fibers.

31. 24. The assembly of claim 23, wherein the permeant outlet (460) is fluidly connected to the first container (210).

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

33. 24. The assembly of claim 23, wherein the condenser (470) comprises multiple stages for selectively condensing components of the carrier gas.

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