Systems and methods for reconditioning alcoholic compositions and reconditioning alcoholic products

Abstract

1. A method for removing one or more congeners from an alcohol composition, comprising the steps of: placing a quantity of an alcohol composition into a pressure-controllable environment; reducing the pressure of the pressure-controllable environment; removing one or more undesirable congeners from the alcohol composition to produce a purified alcohol composition; and removing the purified alcohol composition from the pressure-controllable environment.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to pending U.S. patent application Ser. No. 16 / 939,340, filed July 27, 2020, and U.S. provisional patent applications Ser. No. 63 / 156,517, filed March 4, 2021, and Ser. No. 63 / 209,487, filed June 11, 2021.

[0002] The present disclosure relates generally to the field of alcoholic beverages, and more particularly to systems and methods for removing harmful congeners from alcoholic compositions. Aspects of the present disclosure also relate to alcoholic compositions having reduced amounts of congeners, including alcoholic compositions with improved organoleptic properties. [Background technology]

[0003] Alcoholic beverages have been a human necessity for millennia. Beer was essential in the construction of the Egyptian pyramids, not only as an inexpensive and enjoyable ration for workers, but also as a means of converting non-potable water into a rehydration source. However, despite millennia of experience in fermenting and distilling alcoholic beverages, consistently producing high-quality beer, wine, and spirits remains difficult. Indeed, the quality of wine and spirits, in particular, ranges from very rare and fine to barely drinkable.

[0004] The art of producing alcoholic beverages has long been a closely guarded art. Typically, an aqueous solution initially sweetened with fructose is fermented to produce ethyl alcohol and various congeners (trace chemical components). While some of these congeners are desirable because they provide desirable organoleptic qualities, such as a certain richness of flavor, some others, such as methanol, acetaldehyde, butanol, isobutanol, and methylbutanol, are known to cause hangover symptoms and / or impart unpleasant flavors to alcoholic beverages. While barrel-aging alcoholic beverages is known to absorb some of the larger congener molecules, thus improving the taste of the beverage, such a process is extremely time-consuming, often requiring decades.

[0005] Beverage quality can vary significantly from manufacturer to manufacturer and from batch to batch produced by a given manufacturer. This occurs in part due to inconsistent processing and in part due to variations in the source and quality of raw materials. One source of variation in beverage quality is the presence of undesirable chemical species or congeners in the beverage that arise as a side effect of the fermentation / distillation process and contribute to an off-flavor to the beverage. Summary of the Invention [Problem to be solved by the invention]

[0006] Many of these species have boiling points very close to ethanol at standard pressure and are difficult to remove by distillation without simultaneously removing significant amounts of ethanol and / or other desirable congeners. Thus, there remains a need for a means to rapidly remove undesirable congeners from alcoholic beverages while leaving behind ethanol and / or desirable congeners / flavors. The present disclosure addresses this need. [Brief explanation of the drawings]

[0007] [Figure 1A] FIG. 1 is a perspective view of an alcohol repair system according to a first embodiment of the present disclosure. [Figure 1B]FIG. 1B is a side view of the system of FIG. 1A. [Figure 1C] FIG. 1C is a cutaway view of the system of FIG. 1B taken along line A-A'. [Figure 1D] FIG. 1B is a cutaway view of the system of FIG. 1A showing the internally mounted agitator. [Figure 1E] FIG. 1B is a cutaway cross-sectional view of the alcohol repair system of FIG. 1A with a secondary opening container positioned therein. [Figure 2] FIG. 10 is a cutaway cross-sectional view of an alcohol repair system according to a second embodiment of the present disclosure. [Figure 3] FIG. 10 is a cutaway cross-sectional view of an alcohol repair system according to a third embodiment of the present disclosure. [Figure 4A] FIG. 10 is a first perspective view of an alcohol repair system according to a fourth embodiment of the present disclosure. [Figure 4B] FIG. 4B is a second perspective view of the alcohol repair system of FIG. 4A. [Figure 4C] FIG. 4B is a front view of the alcohol repair system of FIG. 4A. [Figure 4D] FIG. 4B is a first cutaway view of the alcohol repair system of FIG. 4A having smooth inner walls. [Figure 4E] FIG. 4B is a second cutaway view of the alcohol repair system of FIG. 4A having a laced inner wall. [Figure 4F] FIG. 4B is a third perspective view of the alcohol repair system of FIG. 4A. [Figure 5A] 4B is a cutaway view of the pressure vessel of the embodiment of FIG. 4A featuring a fluid inlet body (manifold) having a concave interior sidewall. [Figure 5B] FIG. 4B is a cutaway view of the pressure vessel of the embodiment of FIG. 4A having an inlet trough operatively connected to the inlet port. [Figure 6A] FIG. 10 is a perspective view of an alcohol repair system according to a fifth embodiment of the present disclosure. [Figure 6B] FIG. 6B is a cutaway view of the embodiment of FIG. 6A. [Figure 7] FIG. 1 is a schematic diagram of the method of alcohol remediation underlying the operation of the above-described embodiments. [Figure 8] 1 is a graph of the mass percentage of homologs as a function of processing pressure for an alcoholic composition (rum). [Figure 9] FIG. 1 is a graphical representation of the sensory profile of flavor balance in terms of flavor / aroma intensity as a function of time. [Figure 10] FIG. 1 is a graphical representation of alcohol peak palatability by processing pressure as a function of ethanol content. [Figure 11] FIG. 1 is a graphic representation of sharpness as a function of processing pressure for an 80 standard strength alcohol composition (vodka). [Figure 12] FIG. 1 is a graphical representation of the extrapolated relationship between ethyl acetate content in treated samples of rum and the pressure used for treatment. [Figure 13] FIG. 1 graphically illustrates the extrapolated relationship between ethyl acetate content in treated samples of bourbon and the pressure used for treatment. DETAILED DESCRIPTION OF THE INVENTION

[0008] For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made hereinafter to methods, beverage compositions, and embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the present disclosure is intended thereby, and that changes and further modifications in the illustrated devices, and further applications of the principles of the present disclosure as illustrated in the drawings, are anticipated as would normally occur to one skilled in the art to which the present disclosure pertains.

[0009] Aspects of the present disclosure relate to methods for removing undesirable congeners from alcoholic compositions and to alcoholic compositions (e.g., beverage compositions) comprising only low levels of undesirable congeners. As used herein, "alcoholic composition" refers to a composition comprising ethanol. For the avoidance of doubt, an alcoholic composition is understood to be substantially absent of any alcohol other than ethanol (e.g., methanol). For example, an alcoholic composition may comprise less than 1 percent by weight, less than 0.50 percent by weight, less than 0.25 percent by weight, less than 0.10 percent by weight, less than 0.05 percent by weight, less than 0.01 percent by weight, or less than 0.005 percent by weight of alcohol other than ethanol. For example, an alcoholic composition may comprise less than 1 percent by volume, less than 0.50 percent by volume, less than 0.25 percent by volume, less than 0.10 percent by volume, less than 0.05 percent by volume, less than 0.01 percent by volume, or less than 0.005 percent by volume of alcohol other than ethanol. As used herein, an "alcoholic composition" can refer to beer, wine, distilled spirits, or other ethanol-containing compositions suitable for human consumption. As used herein, "removing" a congener from an alcoholic composition means reducing the amount of the congener in the alcoholic composition. As used herein, it is understood that when a congener is "removed" from an alcoholic composition, the amount of the congener can be partially, substantially, completely, or virtually completely (i.e., to the point of being undetectable by one or more analytical techniques) reduced compared to the amount of the congener present in the alcoholic composition before the congener is removed. In some embodiments, after a congener is "removed" from the alcoholic composition, the congener remains detectable in the alcoholic composition by one or more analytical techniques. In some embodiments, after a congener is "removed" from the alcoholic composition, the congener is undetectable in the alcoholic composition by one or more analytical techniques.

[0010] Removal of some or all of the undesirable congeners in alcoholic compositions may be desirable because they are inherently toxic or because they (at their current concentrations) contribute to an unpleasant or unpleasant sensory experience. One congener found in alcoholic compositions is ethyl acetate (also referred to herein as "EA"). Ethyl acetate is an ester molecule formed by the esterification of ethanol (alcohol) and acetic acid (vinegar). Ethyl acetate is also a polar aprotic solvent with amphiphilic properties. As a result, consumers are highly sensitive to both small changes in ethyl acetate concentration at the olfactory receptor, which can result in a harsh peak and a sharp aftertaste, and to small changes in ethyl acetate concentration at the cellular equilibrium, which can result in a solvent-like burning sensation in the back of the mouth. Ethyl acetate has a boiling point very similar to that of ethanol. As a result, ethyl acetate is often concentrated rather than removed during the distillation of high-proof spirits, thereby leading to a false correlation by consumers between sharpness and alcohol concentration or standard strength. Indeed, it is the ethyl acetate concentration that determines the perceived "sharpness" characteristics of the peak and aftertaste of fermented foods and beverages. Ethyl acetate also acts as a polar aprotic solvent during consumption, which can aid in the detection of other flavor molecules. As a result, excessively low ethyl acetate concentrations can suppress the consumer's ability to detect other desirable flavors and aromas.

[0011] Optimizing the sensory properties of foods and beverages requires a proper balance of ethyl acetate concentration at the parts per million level. For example, very low amounts of ethyl acetate act on certain combinations of specific G protein-coupled olfactory receptors to produce a pleasant or improved sensory experience, whereas higher concentrations of ethyl acetate act on these same receptors to produce an unpleasant or negative sensory experience. Such negative sensory experiences can be characterized by a sharp taste, a burning sensation in the throat, a bitter taste, a metallic taste, a lingering aftertaste, a head-curling sensation, involuntary shudders, the induction of a gag reflex, and combinations thereof. Reducing or eliminating ethyl acetate can eliminate these negative sensory experiences, and reducing the ethyl acetate concentration to a certain level can truly improve the already desirable sensory properties of alcoholic beverages.

[0012] In some embodiments, the methods disclosed herein are applied to produce a purified alcohol composition, defined herein as an alcohol composition from which a portion of one or more undesirable congeners has been removed. For example, in some embodiments, the methods disclosed herein are applied to reduce the ethyl acetate concentration of an alcohol composition to between 1 ppm (parts per million) and 400 ppm, as measured in the liquid-phase alcohol composition by gas chromatography-mass spectrometry.

[0013] In some embodiments, the purified alcohol composition is an organoleptically improved beverage comprising ethanol prepared from a starting alcohol composition. That is, in some embodiments, the methods disclosed herein are applied to produce an organoleptically improved beverage comprising ethanol from a starting alcohol composition. In some embodiments, the methods disclosed herein are applied to produce an organoleptically improved beverage comprising ethanol from a starting alcohol-containing composition from which the beverage is derived and which has one or more undesirable organoleptic properties not found in the organoleptically improved beverage. In some embodiments, the one or more undesirable sensory characteristics are selected from the group consisting of an unpleasant aftertaste, a pungent aftertaste, a sharp aftertaste, a solvent aftertaste, an astringent aftertaste, a harsh aftertaste, a bland flavor, a hint of solvent on the peak and / or aftertaste, a dry taste on the palate, an unpleasant peak masking one or more flavors (e.g., one or more delicate flavors), a sharp taste, a burning sensation in the throat, a bitter taste, a metallic taste, a lingering aftertaste, eliciting head movements such as head arching, head shaking, head tilting, or head tension, eliciting involuntary physiological responses such as shudders, eliciting a gag reflex, and combinations thereof. In some embodiments, the methods disclosed herein are applied to produce a sensory-improved beverage comprising ethanol from a starting alcoholic composition. In some embodiments, the methods disclosed herein are applied to produce, from a starting alcoholic composition, a sensory-improved beverage comprising ethanol, the beverage having one or more desirable sensory attributes at least substantially similar to at least one corresponding desirable sensory attribute of the alcohol-containing composition from which the beverage is derived. In some embodiments, the methods disclosed herein are applied to produce, from a starting alcoholic composition, a sensory-improved beverage comprising ethanol, the beverage having one or more desirable sensory attributes that are substantially improved over one or more corresponding desirable sensory attributes of the alcoholic composition from which the beverage is derived.In some embodiments, one or more of these desirable sensory characteristics are selected from the group consisting of a mellow aftertaste, a rich aftertaste, a balanced aftertaste, a refreshing peak, a flavorful peak, a balanced peak, a balanced peak that enhances the flavor of subtle colors, and combinations thereof.

[0014] Consumers often describe the transient experience of flavor as three distinct phases, including "first taste," "peak," and "aftertaste," which follow corresponding sensory mechanisms of taste, odor, and residue detection and molecular breakdown. Each phase is dominated by a specific sensory source, and the under- or over-expression of flavor and aroma during each phase can determine the overall desirability of a food product. Consumers first taste a food or beverage on the tongue, where they can experience a combination of multiple taste attributes, including sweet, sour, bitter, savory, fatty, and salty. Taste attributes are primarily detected by multiple types and variants of receptors (commonly referred to as taste buds) found on the tongue. While some taste attributes are dominated by a single receptor type, others, such as bitterness, can be perceived through the combined signals of more than 25 receptor variants. Over- or under-expression of any one receptor can result in a consumer alarm, which reduces the perceived positive sensory attributes of the food product. As a result, consumers often refer to organoleptically desirable foods as "balanced."

[0015] During consumption, almost immediately after taste, an odor, often characterized as a peak, can follow as volatile aromas travel back down the throat and into the olfactory cavity. The additional time required for volatile compounds to travel from the oral cavity to the olfactory cavity creates a perceived time delay between the initial taste and the peak of the consumer experience. Odors are primarily transmitted through G-protein-coupled olfactory receptors, with approximately 1,000 different olfactory receptors responsible for odor, each with high sensitivity to specific molecules. Olfactory receptors are particularly selective for esters, such as ethyl acetate, a class of organic molecules that consumers often refer to as "essence." Taste and smell differ in their sensitivity. In comparison, taste can generally distinguish concentration changes in percentages, whereas smell can distinguish concentration changes as fine as parts per million. As with taste, the sensory characteristics of a food or beverage can be determined by the balance of odors experienced through receptor combinations. Over- or under-expression of any one receptor reduces the sensory balance of the food or beverage, resulting in a less desirable product.

[0016] The aftertaste of food and beverages is more complex than the initial taste or peak. During the aftertaste, molecules in the oral cavity begin to break down through various mechanisms, such as hydrolysis and catalysis; volatile compounds, increased by heat and convection within the oral cavity, continue to evaporate from the oral cavity and travel to the olfactory cavity; and the cellular balance of the oral cavity itself begins to change as a result of the food or beverage. Foods or beverages that rapidly alter the oral cavity during consumption often have aftertastes described as "hot," "spicy," or "cutting" (examples include hot sauces, shelf-stable seasonings, or high-proof spirits). At lower concentrations, these undesirable experiences can be described as "off-flavored," "smell," astringent, or strong tannins. On the other hand, foods and beverages that maintain their taste, odor, and cellular balance as they thin on the palate are often said to have aftertastes that are "fresh," "flavorful," "cutting," "round," "delicate," or "elegant" and are generally considered more desirable.

[0017] The vapor pressure and perceived concentration of ethyl acetate do not directly correspond to molecular concentration due to complex intermolecular interactions in a given food or beverage. Therefore, balance cannot be controlled simply through measurement and titration. Conversely, a properly balanced food or beverage can generate a state in which the ethyl acetate equilibrium (also referred to herein as "EAE") can be perturbed and reestablished at different concentrations. The technology of the present invention achieves this goal (perturbing and reestablishing the ethyl acetate equilibrium of an alcoholic composition at different concentrations) without changing the concentrations of other desirable molecules (e.g., ethanol) by utilizing the complex steric hindrance of the food or beverage. In this way, the sharpness and harshness typically experienced by consumers from ethyl acetate and other fermentation by-products present in the initial alcoholic composition can be rebalanced to a more sensory-friendly state in the resulting sensory-improved beverage. Through this process, the odor at the peak of the consumer experience is not at odds with ethyl acetate, and is often perceived as a more refreshing and distinct taste. The aftertaste is often perceived as a "rounder" and "more refined" taste, thereby generating more desirable sensory attributes in the resulting sensory-improved beverage.

[0018] In line with the above-mentioned concepts, yet another aspect of the present disclosure relates to methods for measuring vapor-phase ethyl acetate concentrations in alcoholic compositions and the use of these methods to optimize the sensory characteristics of alcoholic compositions. Conventional methods for measuring congener concentrations (e.g., ethyl acetate concentrations) in alcoholic compositions such as wine, beer, high-strength spirits, and fermentation by-products such as natural or distilled vinegars utilize direct infrared HPLC and / or gas chromatography-mass spectrometry of liquid-phase samples. The conventional thinking is that if the chemical composition is the same or at least very similar, the flavor should be the same or at least very similar. While these methods are very good at measuring absolute congener concentrations in beverages, they have been found to correlate only very roughly with flavor and have not been found to be consistent enough to predict the sensory characteristics of alcoholic compositions. Theory aside, one reason for the lack of correlation and / or consistency is believed to be that the consumer experience of flavor is the result of complex molecular interactions across multiple sensory phases. While the taste sensilla on the tongue are important in determining the basic flavor of a beverage, much of the subtle flavor and aromatic complexity is experienced through the sense of smell. The use of these sophisticated instruments to determine the unique characteristics of a consumer flavor experience has often been found to be inaccurate.

[0019] Aspects of the present disclosure address these issues. In some embodiments, the olfactory experience of a beverage can be accurately correlated by measuring the partial pressures of volatile molecular components collected from the atmosphere in fluid communication with a liquid-phase and / or solid-phase sample of the beverage that has reached equilibrium saturation under closed-system conditions. Atmospheric phase equilibrium can be established using a vapor-phase environment of air and / or an inert gas under ambient pressure and temperature. In some embodiments, the temperature of the sample and / or atmosphere can be adjusted to match the preferred consumption conditions of the beverage. This method allows for the control of complex molecular interactions in the liquid-phase and / or solid-phase beverage sample by establishing a pseudo-equilibrium saturation state with the vapor phase. While the liquid-phase concentration of molecular components such as ethyl acetate may vary from beverage to beverage, the ambient-phase concentration remains relatively constant and can therefore provide an accurate representation of the beverage's olfactory experience, and therefore, its sensory characteristics.

[0020] In an embodiment of the disclosed method, a 1 mL to 5 mL sample is placed in a vial having a total volume 0.5 to 5 times the sample volume, which is then sealed with a separate cap to form an isolated atmosphere. The sealed sample can be left undisturbed, or alternatively, it can be stirred, for example, for a period of 5 seconds to 5 minutes, or until equilibrium saturation between the ambient and the sample is established. A portion of the gas phase of a known volume is removed from the vessel and analyzed using gas chromatography-mass spectrometry to determine specific concentrations of molecules in the gas phase. Alternatively or additionally, this portion of the gas phase of a known volume is analyzed using one or more chemoselective sensors placed in fluid communication with the equilibrium ambient sample. For real-time analysis, the chemoselective sensors can be placed in direct ambient communication with the isolated environment, and the partial pressure concentrations of selected molecules can be detected through correlation and calibration signals. In some embodiments, the chemoselective sensors can be specialized for detecting and measuring ethyl acetate. When such an ethyl acetate-specific sensor is employed, real-time analysis of the sensory characteristics of alcoholic beverages, especially the mellow taste, can be predicted by measuring the partial pressure of ethyl acetate in the vapor phase equilibrium above the beverage sample.

[0021] Yet another aspect of the present disclosure relates to apparatus and the use of these apparatus for reducing the amount of one or more undesirable congeners in alcoholic compositions. For example, as shown in FIGS. 1A-8, an aspect of the present disclosure relates to an apparatus 20 for preferentially removing a quantity of one or more undesirable predetermined congeners (typically fermentation by-products), e.g., ethyl acetate, from alcoholic compositions such as beer, wine, spirits, and similar beverages. In one embodiment, the apparatus 20 includes a pressure vessel 25 having a liquid inlet port 30, a vapor outlet port 35, and a liquid outlet port 40, all of which are in fluid communication with an internal pressure-controllable chamber 45 defined by the pressure vessel 20. Typically, the pressure vessel 25 includes a water jacket 50 or similar temperature controller at least partially surrounding and in thermal communication with the pressure chamber 45. Typically, the liquid inlet port 30 is connected in fluid communication with a liquid pump 60, such as through a pipe 55. The pump 60 is connected in fluid communication with an alcoholic beverage source 65. Typically, at least one valve 70 is operatively connected in line between the alcoholic beverage source 65 and the liquid inlet port 30. The valve 70 may be connected between the inlet port 30 and the pump 60, between the pump 60 and the alcoholic beverage source 65, or at both of these locations.

[0022] Typically, the vapor outlet port 35 is connected in fluid communication with a vacuum pump 75, which is connected in fluid communication with a collection vessel 80. Typically, the vacuum pump 75 operates to remove vapors released from the pressure vessel 25 and direct them at a desired pressure into the collection vessel 80 for collection, and to establish a partial vacuum within the pressure-controllable chamber 45. The collection vessel 80 may be a cold capture or pressure-controlled vessel, or the like. Typically, at least one valve 70 is operatively connected in line between the collection vessel 80 and the vapor outlet port 35. The valve 70 may be connected between the vessel 45 and the pump 75, between the pump 75 and the outlet port 35, or both. The collection vessel 80 may be emptied, and the resulting distillate removed.

[0023] In particular, the liquid outlet port 40 is connected in fluid communication with a pump 85, which is connected in fluid communication with an alcoholic beverage collection tank 90. ​​Typically, at least one valve 70 is operatively connected in line between the alcoholic beverage collection tank 90 and the liquid outlet port 40. The valve 70 may be connected between the tank 45 and the pump 85, between the pump 85 and the collection tank 90, or at both locations. Typical tank 45 throughputs are about 0.025 to 1.0 liters per minute per liter of chamber volume, more typically between 0.1 and 0.8 liters per minute per liter of chamber volume, and more typically between 0.25 and 0.6 liters per minute per liter of chamber volume. [Example]

[0024] As generally shown in Figures 1A-1E, the assembly 20 described above can be implemented to process alcoholic compositions on a batch-by-batch basis. The pressure vessel 25 includes the ports 30, 35, and 40 described above, as well as a water jacket 50 or similar temperature control mechanism enclosing a pressure chamber 45 in thermal communication with the ports 30, 35, and 40. An agitator 95 is disposed within the pressure chamber 45 to facilitate stirring / vibration / foaming of the volume of alcoholic beverage contained therein. A partial vacuum within the pressure chamber 45 can be established by energizing a vacuum pump 75.

[0025] 1E, the alcoholic composition contained in the open container 43 is positioned in the pressure chamber 45. A vacuum lid 46 is then engaged with the vacuum chamber 45, thereby isolating the vacuum chamber environment from the surrounding external environment, and the pressure within the vacuum chamber 45 is reduced by energizing a vacuum pump 75 in operative communication with the vapor outlet port 35. Once the vacuum chamber pressure reaches a designated level, it is then increased to atmospheric pressure and the lid 46 is removed, after which the container 46 now contains the evacuated alcoholic composition. [Example]

[0026] As shown in Figure 2, the assembly 20 described above can be embodied to process the alcoholic composition as a continuous flow process. The liquid inlet port 30 is configured as a spray head and positioned to spray the alcoholic composition pumped from the source tank 65 into the pressure chamber 45, which has already been pumped down to a desired partial vacuum pressure. The spray of alcoholic composition travels through the pressure chamber 45 and collects or pools at the bottom of the pressure vessel 25, where it can be pumped out through the outlet port 40. In some embodiments, the inlet port 30 is configured as a nozzle, while in other embodiments, a separate nozzle is operatively connected to the inlet port 30 to accelerate and direct the incoming liquid. [Example]

[0027] As shown in Figure 3, the assembly 20 described above can be embodied to process the alcohol composition as a continuous flow process. The liquid inlet port 30 can be emptied at one end of the inclined plate 100, where the alcohol composition pumped from the source tank 65 spreads in a thin layer or sheet and slides down to the other end of the inclined plate 100, where it accumulates. When the vacuum pump 75 is activated, the flowing ethanol sheet can release congeners into the partial vacuum environment inside the pressure chamber 45. The processed alcohol composition can be pumped out of the pressure chamber 45 into a collection tank 90. [Example]

[0028] As shown in Figures 4A-4E, the assembly 20 described above can take yet another embodiment for processing alcoholic compositions as a continuous-flow process. The vessel 25 is acorn-shaped, with a circular planar cross-section whose diameter decreases from top to bottom (in this example, the planar cross-sectional profile has a cylindrical portion overlying a conical portion) and a chevron-shaped side cross-sectional profile (in this example, the side cross-sectional profile has a rectangular upper portion and a triangular lower portion). Generally, the vessel includes a water-jacketed exterior 50 encasing a pressure-controllable chamber interior 45. A liquid inlet port 30 positioned near the top of the vessel 25 injects the alcoholic composition pumped from a tank 65 into the pressure chamber 45, and upon injection, the injected alcoholic composition is under sufficient pressure to travel a spiral path along the inside of the pressure chamber 45 and eventually pool at the bottom. Typically, the alcohol composition defines a thin stream or ribbon that circulates the vessel 25 multiple times, while a partial vacuum within the vessel 25 (provided by energizing a vacuum pump 75 connected in fluid communication with the vessel 25) releases undesirable congeners from the stream or ribbon, resulting in the purified alcohol composition defined above. The purified alcohol composition accumulates at the bottom of the pressure chamber 45, from which it can be pumped by a liquid pump 85 into a collection vessel 90. In some embodiments, the interior wall 105 of the pressure chamber 45 is provided with grooves or contours 110 that help guide the alcohol composition flowing from the inlet port 30 to the outlet port 40 in a spiral path. Typically, the interior wall 105 will include a spiral groove or spiral lace 110 for guiding the inlet liquid around the interior wall several times from the inlet port 30 to the outlet port 40.

[0029] In other similar embodiments, the reservoir 25 can have a convex or concave (see FIG. 5A) internal cross-sectional profile. The concave profile slows the liquid flow after the inlet port, which may be followed by a deep cavity or reservoir formed near the outlet port 40 for liquid accumulation control.

[0030] The ports 30, 35, and 40 of a first pressure chamber 45 may be connected in fluid communication with other ports 30, 35, and 40 of other similar or identical pressure chambers 45 so that multiple pressure chambers 45 can be operated in parallel from a central vacuum pump 75 and fluid pumps 60, 85. In this embodiment, the fluids may be regulated individually or with a fluid manifold connected in fluid communication with each respective pressure chamber 45.

[0031] In some embodiments, a float valve 91 can be used to prevent the liquid reservoir at the liquid outlet port 30 from drying out and to adjust the minimum liquid reservoir level. Under actuation, the float valve 91 can open the liquid outlet port 40 when enough liquid has entered the chamber 45. If the liquid discharge pump 85 removes liquid fast enough to reduce the liquid below the float level, the float valve 91 can create a pressure gradient between the tank 45 and the liquid discharge pump 85 to prevent further liquid removal. Another benefit of the float valve 91 is that it prevents the tank atmosphere from pressurizing and back into the clean, processed liquid flowing out of the liquid outlet port 40.

[0032] A sensor 93 can be used to provide feedback to an adjusting valve 94 to maintain a positive volume above the liquid outlet port 40 and prevent depressurization of the bath atmosphere within the process fluid. The sensor 93 can be in direct communication with the bath reservoir fluid (typically a vacuum-treated alcohol composition), such as in the case of an optical, inductive, or acoustic sensor 93, or an acoustic, ultrasonic, or thermal sensor 93 around the fluid outlet port 40 can indirectly monitor the fluid level.

[0033] The liquid pumps 60, 85 discussed herein can be variable displacement pumps in the case of diaphragm or piston pumps, or fixed displacement pumps in the case of turbine pumps. The fluid pumps 75, 85 in communication with the outlet ports 35, 40 may be subjected to a negative pressure of 13 to 15 PSI and may need to be combined in series to provide sufficient suction; as used herein, "vacuum pump" can refer to a single pump unit or multiple pump units operatively connected in series. An intermediate repressurization chamber 98 can be used between multiple fluid pumps 60, 85.

[0034] The vacuum pump 75 of the present disclosure can be a variable displacement pump such as a piston pump, rotary screw pump, rotary vane pump, or a fixed displacement pump in the case of a multi-stage regenerative blower. The cold trap of the present disclosure also provides a pressure gradient and can function as a vacuum pump. The cold trap can be electrically cycled or supplied with a cryogenic medium such as dry ice or liquid nitrogen.

[0035] Fluid flow can be adjusted by adjusting the cross-sectional area of ​​the valve or by repeatedly opening and closing the valve. Automated valves can be actuated pneumatically or electrically, etc., and controlled by a PLC in operative communication with a digital pressure gauge.

[0036] A fluid inlet nozzle 30 can be connected in fluid communication with the inlet port 30 to direct the liquid flow into the vessel 45. The liquid can flow in a straight line along a gravity path or in a spiral pattern as it travels down the vessel's interior wall. A spiral path can be used to increase retention time and break the fluid's surface tension, and a nozzle 99 with a narrowing narrow passage can achieve benefits by increasing velocity before injection and providing a longer retention time for longer exposure to vacuum conditions. To prevent droplet formation and splashing, the terminal end of the fluid inlet nozzle 30 can be positioned sufficiently close to the vessel wall 105, typically less than 15 centimeters from the vessel wall 105, and typically less than 2 centimeters. A laminar flow inlet can be used to reduce splashing and volatilization during injection. Alternatively, one or more liquid inlet openings 30 can allow a quasi-uniform liquid flow to spread in a sheet along the vessel's 45 interior wall to the liquid outlet port 40.

[0037] A liquid inlet body 97 can be used to reduce the pressure drop between the pressure regulator and the vacuum vessel 45 by allowing for accumulation of liquid prior to injection (see FIG. 5A). In this case, the liquid enters a manifold 97, which is a large, tube-like volume that at least partially surrounds the upper lip of the vessel 45. The cross-sectional area of ​​the inlet body 97 is large compared to the inlet valve 31, allowing for a reduction in pressure before the fluid enters the vessel 45, thereby allowing for a lower head pressure and slower flow. In another embodiment, the liquid inlet body 97 can include a double-sided member that may or may not be integrated into the vessel lid. A double-sided separation can be used to allow for rapid disassembly.

[0038] In one embodiment, the inlet body 97 is maintained at approximately 55 Torr, and the vessel 45 is maintained at less than 55 Torr. In this case, the pressure can be substantially reduced without significantly changing the liquid composition prior to entering the bulk vessel volume. The inlet body 97 can be maintained at a pressure such as 760 Torr, 700 Torr, 500 Torr, 400 Torr, 200 Torr, 100 Torr, 75 Torr, or similar. The vessel 45 can be maintained at a pressure such as 50 Torr, 46 Torr, 45 Torr, 42 Torr, 40 Torr, or similar. In some embodiments, the vessel is maintained at a pressure between 40 Torr and 80 Torr, e.g., between 40 Torr and 60 Torr, between 40 Torr and 50 Torr, between 45 Torr and 65 Torr, between 50 Torr and 70 Torr, between 50 Torr and 65 Torr, or between 50 Torr and 60 Torr. In some embodiments, the vessel is maintained at a pressure selected based on the percent alcohol by volume (ABV) of the starting alcohol composition. For example, the vessel may be maintained at a pressure of 50 Torr for a 50% ABV alcoholic composition, a pressure of 40 Torr to 50 Torr for a 40% ABV alcoholic composition, a pressure of 55 Torr to 65 Torr for a 30% ABV alcoholic composition, a pressure of 55 Torr to 65 Torr for a 20% ABV alcoholic composition, a pressure of 50 Torr to 60 Torr for a 10% to 20% ABV alcoholic composition, or a pressure of 65 Torr to 75 Torr for a 1% to 10% ABV alcoholic composition.

[0039] A separate pressure letdown tank can be used to gradually reduce the pressure of the liquid before it enters tank 45. In some embodiments, it is contemplated that the pressure letdown tank will be maintained at an intermediate pressure above 50 Torr, such as 700 Torr, 500 Torr, 400 Torr, 200 Torr, 100 Torr, 75 Torr, or the like.

[0040] In another embodiment (FIG. 5B), liquid enters the vessel and accumulates in a trough 98. As the trough 98 fills, the liquid will overflow the trough and sheet down the sidewall 105 toward the reservoir 49. The trough 98 can fill to a level defined by the lip 99 until the liquid overflows the lip 99 and forms a liquid sheet through the vessel wall 105. Alternatively, the trough can include gaps at its interface with the sidewall, resulting in a "leaky" trough that is believed to result in a uniform liquid sheet forming along the sidewall as the liquid flows out the bottom of the trough.

[0041] The vessel 25 may comprise a metal such as stainless steel, copper, or aluminum, a plastic such as polycarbonate or PETG, or a combination thereof. The liquid may directly contact the interior wall 105 of the vessel 45, or may contact a face liner either positioned within and insulated from or positioned against the vessel wall 105.

[0042] The water jacket 50 may include a bulk volume defining a single thermal compartment between the vessel interior wall and the partial enclosure wall, or may include multiple thermal compartments. Multi-compartment cooling sections may be fabricated by segmentation or the use of pillow plates in the case of stainless steel.

[0043] The interior walls 105 of the vacuum chamber 45 can be smooth or even polished, or can be intentionally etched and roughened to facilitate bubble release. A smooth vessel wall 105 will facilitate liquid flow during spiral circumnavigation, whereas a rough or etched surface can retard liquid flow as the liquid follows a gravity orbit along the vessel wall 105, resulting in a longer liquid retention time.

[0044] In another embodiment of the present disclosure, the liquid flow is introduced uninterrupted from the inlet port 30 to the liquid reservoir 49 without contacting the vessel wall 105. In this case, the liquid travels straight or falls unimpeded through the vessel 45, degassing as it falls.

[0045] In yet another embodiment (see FIGS. 6A and 6B ), the pressure vessel 25 has the form of a spiral tube with a liquid inlet port and a gas outlet port at a first, generally higher, end 107 and a liquid outlet 40 positioned at the opposite end 109. Generally, the liquid is gravity-forced from one end 107 to the other 109. During operation, a predetermined amount of alcoholic composition 115, such as beer (typically before carbonation), wine, or spirits, is introduced into the pressure chamber 45. Generally, the alcoholic composition 115 enjoys a high surface-to-volume ratio while present in the pressure chamber 45, such as in the form of droplets, thin sheets, or ribbons, thereby allowing for more rapid and efficient release of predetermined undesirable congeners 120 from the alcoholic composition 115. The atmosphere within the pressure chamber 45 is less than atmospheric pressure (i.e., a partial vacuum) to facilitate the differential release of one or more undesirable congeners 120 from the solution 115. In a batch process, the liquid alcoholic composition 115 is filled into the pressure chamber 45, the pressure chamber 45 is hermetically sealed, and the pressure within the chamber is reduced to a desired partial vacuum. In a continuous flow process, the pressure within the pressure chamber 45 is maintained at a desired partial vacuum, and the alcoholic composition 115 flows through the chamber at a predetermined desired rate.

[0046] In some embodiments, ethyl acetate rapidly forms in a thin solution layer between the vessel wall and the vessel atmosphere having a thickness of less than 25 mm, e.g., less than 15 mm, less than 10 mm, or less than 5 mm.

[0047] In some embodiments, the residence time for the alcoholic composition in the pressure vessel at the target atmospheric pressure is about 60 seconds or less, about 20 seconds or less, or about 5 seconds or less. In some embodiments, the residence time for the alcoholic composition in the pressure vessel at the target atmospheric pressure is 5 to 60 seconds, e.g., 5 to 10 seconds, 5 to 15 seconds, 5 to 20 seconds, 10 to 50 seconds, 10 to 40 seconds, 10 to 30 seconds, 15 to 30 seconds, 15 to 25 seconds, or 15 to 20 seconds.

[0048] In some embodiments, the residence time at the target atmospheric pressure for the flowing alcoholic composition 115 is about 60 seconds or less, about 20 seconds or less, or about 5 seconds or less. In the case of a feed-and-forget assembly system, the residence time for the alcoholic composition 115 under vacuum may be longer. Furthermore, as the vacuum partial pressure decreases, the residence time of the alcoholic composition 115 may decrease as well.

[0049] In some embodiments, the temperature of the liquid sample in the pressure chamber can be maintained at, for example, -20 degrees Celsius to 80 degrees Celsius, e.g., 0 degrees Celsius to 60 degrees Celsius, 10 degrees Celsius to 35 degrees Celsius, 20 degrees Celsius to 30 degrees Celsius, or 20 degrees Celsius to 25 degrees Celsius. For example, in some embodiments, the temperature of the liquid sample in the pressure chamber can be 2 degrees Celsius, 22 degrees Celsius, 23 degrees Celsius, 24 degrees Celsius, or 25 degrees Celsius.

[0050] In some embodiments, the temperature of the pressure chamber can be maintained at, for example, -20 degrees Celsius to 80 degrees Celsius, e.g., 0 degrees Celsius to 60 degrees Celsius, 10 degrees Celsius to 35 degrees Celsius, 20 degrees Celsius to 30 degrees Celsius, or 20 degrees Celsius to 25 degrees Celsius. For example, in some embodiments, the temperature of the pressure chamber can be 2 degrees Celsius, 22 degrees Celsius, 23 degrees Celsius, 24 degrees Celsius, or 25 degrees Celsius. In some embodiments, the temperature of the pressure chamber is maintained (at one of the temperatures described above) using a jacket or similar temperature controller at least partially surrounding and in thermal communication with the pressure chamber. In some embodiments, the jacket is a water jacket. In some embodiments, the temperature of the liquid sample in the pressure chamber is the same as the temperature at which the pressure chamber is maintained. In some embodiments, the temperature of the liquid sample in the pressure chamber is different from the temperature at which the pressure chamber is maintained. Thus, in some embodiments, a temperature gradient may exist between the temperature of the pressure chamber (e.g., the temperature of the jacket or similar temperature controller) and the temperature of the liquid sample in the pressure chamber.

[0051] In some embodiments, the alcoholic composition 115 remains liquid throughout the vacuum treatment process and through exposure to the low-pressure environment in the pressure chamber 45. While the emitted congeners 120 change phase from liquid to gas, the alcoholic composition remains liquid, i.e., there is no distillation and / or recondensation or reconstitution of the alcoholic composition 115 during treatment in the pressure chamber.

[0052] The present disclosure utilizes complex intermolecular forces in fermentation broth at low temperature and pressure to preferentially release one or more undesirable congeners from solution. For example, conventionally, one would expect acetaldehyde to be removed before ethyl acetate under vacuum due to acetaldehyde's higher vapor pressure and lower boiling point at standard temperature and pressure (STP). In embodiments of the methods disclosed herein, the amounts of acetaldehyde and isobutanol actually remain relatively constant within the systems of the present invention, whereas ethyl acetate is selectively removed, which cannot be understood by simply comparing boiling points and vapor pressures. The present methods allow selective control over the amount of ethyl acetate removed based on temperature and vacuum pressure at a given retention time. This selectivity only occurs over a narrow pressure range. As a result, artisans can reliably adjust the ethyl acetate level in alcoholic beverages to develop desired flavor profiles. While aspects of the present disclosure relate to the removal of ethyl acetate, other undesirable congeners can be similarly removed by advantageously selecting the pressure and temperature conditions of the vacuum treatment.

[0053] This release of undesirable congeners takes advantage of the fact that, while such congeners have boiling points very close to those of ethanol at atmospheric pressure, the same congeners have substantially different, generally lower, boiling points than ethanol at low pressures, and the presence of multiple congeners in solution creates a relative boiling point difference between the other congeners. Thus, exposure of an alcoholic composition to low pressure (partial vacuum) over a specific temperature and pressure range allows for the differential release of certain congeners, such as ethyl acetate, while leaving ethanol unchanged, along with certain desirable lower-boiling congeners, in solution. For example, Figure 8 depicts the results of an experiment in which the mass percentages of acetaldehyde, ethyl acetate, and isobutanol were measured at varying pressures applied to an 80-proof rum sample. As shown in Figure 8, the mass percentage of ethyl acetate decreased as the pressure was reduced (i.e., as increasing vacuum levels were applied), with a steeper decline occurring as the pressure was reduced below 100 Torr. In contrast, the mass percentages of isobutanol and acetaldehyde remained steady as pressure was reduced, not exhibiting the steep decline observed for ethyl acetate when pressure was reduced below 100 Torr. These results were surprising and unexpected; as discussed above, it has traditionally been thought that when an alcohol composition containing (at least) acetaldehyde and ethyl acetate is exposed to vacuum, acetaldehyde is preferentially removed relative to ethyl acetate because it has a higher vapor pressure and lower boiling point (at STP) compared to ethyl acetate. Conversely, Figure 8 depicts the opposite result (release of ethyl acetate in preference to acetaldehyde). The apparent increase in mass percentages of acetaldehyde and isobutanol is, without theory, believed to be an analytical artifact resulting from the steep decline in mass percentage of ethyl acetate and, without theory, is not believed to reflect a physical entity.

[0054] Maintaining a low pressure atmosphere within the pressure chamber at ambient temperature and reestablishing the equilibrium of ethyl acetate in the solution can partially remove ethyl acetate from the alcoholic composition 115, resulting in a smoother-tasting, sensory-improved beverage without substantially reducing the ethanol content of the solution 115. As a non-limiting example, the operating pressure within the pressure chamber at ambient temperature can be maintained at 90 Torr to 15 Torr, e.g., 65 Torr to 15 Torr, 55 Torr to 35 Torr, 45 Torr to 40 Torr, or 42 Torr at 22°C for a 40% alcohol by volume beverage. In some embodiments, the operating pressure within the pressure chamber is a pressure or a multiple of this pressure determined to result in a sensory-optimized alcoholic beverage for a given composition. In some embodiments, the pressure determined to result in a sensory-optimized alcoholic beverage is referred to as the pressure that results in "peak palatability." FIG. 10 depicts a graph of exemplary pressures corresponding to peak palatability as a function of volume percent alcohol. In some embodiments, the operating pressure is about 0.5 to 2 times the pressure corresponding to peak palatability, e.g., 1 to 1.5 times the pressure corresponding to peak palatability, with reference to Figure 10. For example, the operating pressure may be 42 to 63 Torr for a 40% ABV alcoholic composition.

[0055] Without being bound by theory, it is believed that the ability to improve the sensory characteristics of a beverage by exposing it to a lower pressure (e.g., by exposing it to a pressure determined to produce peak palatability) may result from the fact that ethyl acetate and ethanol have similar boiling points at ambient pressure, but different boiling points, with ethyl acetate having a lower boiling point at pressures of, for example, 20 torr to 55 torr for a 40% by volume alcohol composition. Thus, by maintaining a pressure of 20 torr to 55 torr in pressure chamber 45 and controlling the temperature within the pressure chamber at approximately 22°C, the ethyl acetate equilibrium concentration can be preferentially shifted for a 40% by volume alcohol composition.

[0056] As shown in FIG. 10 , in some embodiments, the pressure range in which ethyl acetate can be selectively removed (e.g., to produce a sensory-improved beverage) may shift nonlinearly as the alcohol content of the solution shifts. Theory aside, the pressure treatment that produces peak alcohol palatability is a function of the alcohol content of the treated alcoholic beverage, and less so with the homologue composition. This functional relationship is nonlinear. For beverages having an alcohol content between 24 and 30 percent by volume at room temperature, a treatment pressure between 58 and 67 Torr may produce beverages with the mildest taste and best sensory balance. For beverages having an alcohol content between 55 and 65 percent by volume, a treatment pressure between 49 and 57 Torr may produce beverages with the mildest taste and best sensory balance. As noted above, for beverages with 40 percent alcohol by volume, a pressure treatment between 40 and 45 Torr may produce beverages with the mildest taste and best sensory balance. In some embodiments, the pressure treatment holds the nominal pressure for 5 seconds.

[0057] Without being bound by theory, it is believed that the surrounding liquid environment influences the pressure range over which a given compound (ethyl acetate in the above example) can be selectively removed. In an alcohol vapor environment, the selective pressure range (e.g., about 18 torr to 55 torr) may be lower than that required to effect an equilibrium shift in ethyl acetate concentration from another liquid, and higher than that required to effect an equilibrium shift in ethyl acetate from yet another liquid.

[0058] As shown in Figure 11, the relationship between the pressure at which a 40% alcohol by volume vodka sample is treated and "sharpness" (a sensory attribute opposite to "smoothness") is nonlinear. In other words, the sharpness of the treated alcoholic composition decreases with decreasing actuation pressure up to a point, but when the actuation pressure is further reduced, the sharpness begins to increase again.

[0059] The following example further demonstrates the selective conversion of ethyl acetate from alcohol compositions achieved by using the process disclosed herein. In one experiment, a rum sample was exposed to atmospheric pressure (760 Torr) and then to a series of lower pressures. In this experiment, the pressure was measured in a vacuum line at a point that was fluidly connected to the vacuum chamber but was nevertheless remote from it. Theory aside, it is believed that the pressure in the vacuum chamber was higher than the measured pressure. After exposure to atmospheric pressure and each lower pressure, the sample was analyzed for ethanol fraction by gas chromatography-mass spectrometry, and the amounts (measured as area percentages, referred to herein as "A%)) of seven additional analytes (acetaldehyde, ethyl acetate, ethanol, isobutanol, 2-methyl-1-butanol, acetic acid, and furfural) were measured. An additional unknown analyte was also detected and quantified. For this analysis, gas chromatography was performed using a 30 m x 0.25 mm ID, 0.25 μm film Stabilwax cylinder (Restek). The gas chromatography temperature program was 35°C for 3 minutes, ramping to 240°C at 10°C / min, with 0.5 μL samples injected at a 50:1 split ratio. Mass spectral data was acquired using an Agilent 5975C MSD. The results are summarized in Table 1. The amount of ethyl acetate is also described as parts per million (ppm). In this example, to determine the amount of ethyl acetate in the rum samples (in ppm), a calibration curve was first generated by analyzing samples of known ethyl acetate concentrations (in ppm) using the same gas chromatography-mass spectrometry method described above, which included measuring the peak areas of known ethyl acetate concentrations (in ppm) for these samples. The calibration curve provided a correlation between peak area and ethyl acetate concentration (in ppm). The ethyl acetate concentrations (in ppm) in the rum samples were then calculated based on the peak areas for ethyl acetate in the rum samples by fitting the correlation between the peak areas obtained from the calibration curve and the ethyl acetate concentrations (in ppm). For the avoidance of doubt, it is understood that the measurements ignore the water content of the sample.

[0060] Table 1. Quantities of components detected in rum samples following treatment at the indicated pressures. TIFF0007819175000001.tif78147

[0061] As shown in Table 1, treatment of ram samples during pressure reduction results in selective changes in, for example, ethyl acetate, while the amounts of acetaldehyde and ethanol remain nearly constant. As discussed above, this result is surprising and unexpected; traditionally, when an alcohol composition containing (at least) acetaldehyde and ethyl acetate is exposed to vacuum, acetaldehyde is thought to be preferentially removed compared to ethyl acetate because it has a higher vapor pressure and lower boiling point (at STP) compared to ethyl acetate. Conversely, Table 1 illustrates the opposite result (dominant release of ethyl acetate over acetaldehyde). Furthermore, it is surprising and unexpected that, in some embodiments, simply adjusting a bulk parameter, e.g., pressure in this case, can selectively remove ethyl acetate from a composition containing not only molecules with lower molecular weights than ethyl acetate but also molecules with higher molecular weights than ethyl acetate. Figure 12 is an extrapolated graph of ethyl acetate content (in ppm) versus treatment pressure, illustrating the steep drop in ethyl acetate content, particularly for pressure reductions below about 50 Torr.

[0062] In additional experiments, a sample of bourbon was exposed to atmospheric pressure (760 Torr) and then to two lower pressures. In this experiment, the pressure was measured in the vacuum line at a point that was fluidly connected to the vacuum chamber but was nevertheless remote from it. Theory aside, it is believed that the pressure in the vacuum chamber was higher than the measured pressure. After exposure to atmospheric pressure and each lower pressure, the sample's ethanol fraction was analyzed by gas chromatography-mass spectrometry, and the amounts of seven additional analytes (acetaldehyde, ethyl acetate, ethanol, isobutanol, 2-methyl-1-butanol, acetic acid, and furfural) were measured (in area percentages, referred to herein as "A%)." An additional unknown analyte was also detected and quantified. For this analysis, gas chromatography was performed using a 30 m x 0.25 mm ID, 0.25 μm film Stabilwax cylinder (Restek). The gas chromatography temperature program was 35°C for 3 minutes, ramping to 240°C at 10°C / min, with 0.5 μL of sample injected at a 50:1 split ratio. Mass spectral data were acquired using an Agilent 5975C MSD. The results are summarized in Table 2. The amount of ethyl acetate is also reported as parts per million (ppm). In this example, to determine the amount of ethyl acetate (in ppm) in the bourbon samples, a calibration curve was first generated by analyzing samples of known ethyl acetate concentrations (in ppm) using the same gas chromatography-mass spectrometry method described above, which included measuring the peak areas of known ethyl acetate concentrations (in ppm) for these samples. The calibration curve provided a correlation between peak area and ethyl acetate concentration (in ppm). The ethyl acetate concentrations (in ppm) in the bourbon samples were then calculated based on the peak areas for ethyl acetate in the bourbon samples by fitting the correlation between peak area and ethyl acetate concentration (in ppm) obtained from the calibration curve. For the avoidance of doubt, it is understood that the measurements ignore the water content of the sample.

[0063] Table 2. Quantities of components detected in rum samples following treatment at the indicated pressures. TIFF0007819175000002.tif62145

[0064] As shown in Table 2, treatment of the bourbon sample during pressure reduction results in a selective shift in ethyl acetate, for example, while the amounts of acetaldehyde and ethanol remain nearly constant. As discussed above, this result is surprising and unexpected; traditionally, when an alcoholic composition containing (at least) acetaldehyde and ethyl acetate is exposed to vacuum, acetaldehyde is thought to be preferentially removed compared to ethyl acetate because it has a higher vapor pressure and lower boiling point (at STP) compared to ethyl acetate. Conversely, Table 2 illustrates the opposite result (dominant release of ethyl acetate over acetaldehyde). Furthermore, it is surprising and unexpected that, in some embodiments, simply adjusting a bulk parameter, e.g., pressure in this case, can selectively remove ethyl acetate from a composition containing not only molecules with lower molecular weights than ethyl acetate but also molecules with higher molecular weights than ethyl acetate. Figure 13 is an extrapolated graph of ethyl acetate content (in ppm) versus treatment pressure, illustrating the steep drop in ethyl acetate content, particularly for pressure reductions below about 50 Torr.

[0065] The effect of low-pressure treatment on an alcoholic composition may be better understood as a shift in the equilibrium concentration of ethyl acetate rather than its removal through fractional distillation. As a result, solution retention at low pressure may not reduce the ethyl acetate concentration to zero. It is believed that the solution may undergo a shift in homolog concentration over a given retention time. In some embodiments, at least one-third of the ethyl acetate is preferentially removed from the alcoholic composition, or at least one-half, or at least two-thirds, or substantially all of the ethyl acetate is preferentially removed. As used herein, preferential removal of undesired homologs, such as ethyl acetate, means removing some or all of the undesired homologs from the solution without substantially removing some, most, or all of the other components of the solution. In some embodiments, at about 40 Torr and 22 degrees Celsius, between 40 and 60 percent of the initial ethyl acetate content is removed within about 5 seconds from an alcoholic composition with 40 percent alcohol by volume.

[0066] In some embodiments, the instant alcohol restoration process reduces the amount of ethyl acetate in the alcoholic composition to about 50% or less of the original ethyl acetate content in the alcoholic composition, for example, about 45% or less of the original ethyl acetate content, about 40% or less of the original ethyl acetate content, about 35% of the original ethyl acetate content, about 30% or less of the original ethyl acetate content, about 20% or less of the original ethyl acetate content, about 10% or less of the original ethyl acetate content, or about 5% or less of the original ethyl acetate content. The target amount of ethyl acetate content reduction is determined by several factors, including personal taste and the type of alcoholic beverage, ranging from 3% to 95% ethanol by volume. For example, an alcoholic beverage can have an ethanol content of 1 to 5 volume percent, 3 to 5 volume percent, 5 to 10 volume percent, 10 to 15 volume percent, 10 to 20 volume percent, 20 to 30 volume percent, 30 to 40 volume percent, 40 to 50 volume percent, 45 to 50 volume percent, 50 to 60 volume percent, 55 to 60 volume percent, 60 to 70 volume percent, 70 to 80 volume percent, 80 to 90 volume percent, or 90 to 95 volume percent. In some embodiments, the ethyl acetate content of the alcoholic composition is reduced to <1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 33.5% (i.e., one-third), 35%, 40%, 45%, 50% (i.e., half), 55%, 60%, 65%, 66.5% (i.e., two-thirds), 70%, 75%, 80%, 85%, 90%, 95%, or 99% of the original content. In some embodiments, the ethyl acetate content of the alcoholic composition is reduced to 20% to 80% of the original content, e.g., 25% to 75% or 33.5% to 66.5% of the original content.In some embodiments, including but not limited to those described in this paragraph, the reduction in the ethyl acetate content of the alcoholic composition is measured using liquid phase gas chromatography mass spectrometry.

[0067] In some embodiments, applying the methods disclosed herein, the ethyl acetate content of an alcoholic composition can be reduced by, for example, 1 ppm to 400 ppm, e.g., 1 ppm to 350 ppm, 1 ppm to 300 ppm, 1 ppm to 250 ppm, 1 ppm to 200 ppm, 1 ppm to 150 ppm, 1 ppm to 100 ppm, 1 ppm to 75 ppm, 1 ppm to 50 ppm, or 1 ppm to 25 ppm, as measured by liquid phase gas chromatography mass spectrometry. In some embodiments, the methods disclosed herein can be used to reduce the ethyl acetate content of an alcoholic composition by, for example, 10 ppm to 400 ppm, 20 ppm to 380 ppm, 25 ppm to 375 ppm, 30 ppm to 350 ppm, 35 ppm to 325 ppm, 40 ppm to 300 ppm, 45 ppm to 275 ppm, 50 ppm to 250 ppm, 55 ppm to 225 ppm, 60 ppm to 200 ppm, 65 ppm to 175 ppm, 70 ppm to 150 ppm, 75 ppm to 125 ppm, or 80 ppm to 100 ppm, as measured by liquid-phase gas chromatography-mass spectrometry. In some embodiments, the methods disclosed herein can be used to reduce the ethyl acetate content of an alcoholic composition by, for example, 3 ppm to 300 ppm, as measured by liquid-phase gas chromatography-mass spectrometry. In some embodiments, the methods disclosed herein can be applied to reduce the ethyl acetate content of an alcoholic composition, for example, from 3 ppm to 100 ppm, 3 ppm to 80 ppm, 3 ppm to 70 ppm, 3 ppm to 60 ppm, or 3 ppm to 50 ppm, as measured by liquid-phase gas chromatography-mass spectrometry. In some embodiments, the methods disclosed herein can be applied to reduce the ethyl acetate content of an alcoholic composition, for example, from 15 ppm to 200 ppm, as measured by liquid-phase gas chromatography-mass spectrometry.

[0068] In some embodiments, applying the methods disclosed herein to an alcoholic composition having an ethanol content of 40% to 60% by volume can reduce the ethyl acetate content of the alcoholic composition, for example, to 3 ppm to 250 ppm, e.g., 5 ppm to 100 ppm, 10 ppm to 250 ppm, 20 ppm to 225 ppm, 10 ppm to 80 ppm, 3 ppm to 100 ppm, 5 ppm to 75 ppm, or 10 ppm to 60 ppm, as measured by liquid-phase gas chromatography-mass spectrometry. In some embodiments, applying the methods disclosed herein can reduce the ethyl acetate content of the alcoholic composition, thereby providing the alcoholic composition with improved sensory characteristics compared to the starting alcoholic composition. In some embodiments, applying the methods disclosed herein to an alcoholic composition having an ethanol content of 40% to 60% by volume can reduce the ethyl acetate content of the alcoholic composition, for example, to 5 to 100 ppm, as measured by liquid-phase gas chromatography-mass spectrometry, thereby providing the alcoholic composition with improved sensory characteristics compared to the starting alcoholic composition.

[0069] In some embodiments, applying the methods disclosed herein to an alcoholic composition having an ethanol content of 10% to 20% by volume, the ethyl acetate content of the alcoholic composition is, for example, 3 ppm to 200 ppm, e.g., 3 ppm to 175 ppm, 3 ppm to 150 ppm, 3 ppm to 75 ppm, 3 ppm to 65 ppm, 3 ppm to 60 ppm, 10 ppm to 200 ppm, 10 ppm to 175 ... The ethyl acetate content of an alcoholic composition can be reduced from 10 ppm to 150 ppm, 10 ppm to 125 ppm, 10 ppm to 100 ppm, 10 ppm to 80 ppm, 12 ppm to 100 ppm, 12 ppm to 80 ppm, 12 ppm to 70 ppm, 12 ppm to 60 ppm, 15 ppm to 50 ppm, 15 ppm to 45 ppm, 20 ppm to 60 ppm, 20 ppm to 50 ppm, 25 ppm to 45 ppm, 30 ppm to 60 ppm, 30 ppm to 50 ppm, or 20 ppm to 40 ppm. In some embodiments, the methods disclosed herein can be applied to reduce the ethyl acetate content of an alcoholic composition, thereby providing the alcoholic composition with improved sensory properties compared to the starting alcoholic composition. In some embodiments, applying the methods disclosed herein to an alcoholic composition having an ethanol content of 10% to 20% by volume can reduce the ethyl acetate content of the alcoholic composition to, for example, 10 to 90 ppm as measured by liquid-phase gas chromatography-mass spectrometry, thereby imparting improved sensory properties to the alcoholic composition compared to the starting alcoholic composition.

[0070] As an additional representative, but non-limiting example, the methods disclosed herein can be applied to a rum sample having an initial ethyl acetate content of 55 to 60 ppm, as measured by liquid-phase gas chromatography-mass spectrometry, to reduce the ethyl acetate content to less than 40 ppm, e.g., less than 35 ppm, less than 30 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 4 ppm, each as measured by liquid-phase gas chromatography-mass spectrometry. For example, the methods disclosed herein can be applied to a rum sample having an initial ethyl acetate content of 55 to 60 ppm, as measured by liquid-phase gas chromatography-mass spectrometry, to reduce the ethyl acetate content to, e.g., 50 to 60 ppm, 25 to 35 ppm, 15 to 25 ppm, 5 to 15 ppm, or 1 to 5 ppm, each as measured by liquid-phase gas chromatography-mass spectrometry. As a further representative, but non-limiting example, the methods disclosed herein can be applied to a bourbon initially having 210 to 230 ppm of ethyl acetate, as measured by, for example, liquid-phase gas chromatography-mass spectrometry, to reduce the ethyl acetate content to, for example, less than 100 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, or less than 25 ppm, each as measured by liquid-phase gas chromatography-mass spectrometry. For example, the methods disclosed herein can be applied to a bourbon sample initially having 200 to 250 ppm of ethyl acetate, as measured by liquid-phase gas chromatography-mass spectrometry, to reduce the ethyl acetate content to, for example, 50 to 75 ppm, 55 to 65 ppm, 15 to 35 ppm, or 15 to 25 ppm, each as measured by liquid-phase gas chromatography-mass spectrometry.

[0071] Other congeners can be similarly selectively removed by selecting other process temperature / pressure / residence time combinations. In some embodiments, temperature, pressure, and / or chemical sensors (or combinations thereof) are disposed in thermal communication with the interior of the vessel 25, the water jacket, and / or the steam outlet port (or combinations thereof). These sensors can be operatively connected to an electronic controller, which can also be connected to the pumps 60, 75, 85, ports 30, 35, 40, valve 70, and / or agitator 95 (if present), to provide feedback-based process control to maintain the process within predetermined parameter ranges and / or a predetermined pressure / temperature profile. In some embodiments, the temperature and pressure within the chamber can be varied during the residence time of the alcoholic composition 115 to selectively target and remove multiple undesirable congeners 120, a technique likely best suited to feedstock processes. In other embodiments, the alcohol composition 115 can be sequentially flowed through multiple pressure vessels 25, each having a pressure chamber 45 characterized by a different predetermined vacuum partial pressure and temperature, to target one or more specific congeners 120.

[0072] While the new technology has been illustrated and described in detail in the drawings and foregoing description, such illustration and description should be considered exemplary in character and not restrictive. It is to be understood that the foregoing specification has shown and described embodiments that meet best mode and feasible requirements. It is to be understood that those skilled in the art could readily make an almost infinite number of imaginative variations and modifications to the above-described embodiments, and that it would be impractical to attempt to describe all such variations and modifications herein. It is to be understood, therefore, that it is desired to protect all variations and modifications that come within the spirit of the new technology. [Explanation of symbols]

[0073] 20 Apparatus for preferential removal of ethyl acetate 25 Pressure Tank 30 Liquid Inlet Port 35 Steam outlet port

Claims

1. 1. A method for removing ethyl acetate from an alcoholic composition, comprising: a) placing a quantity of an alcoholic composition in a pressure-controllable environment; b) reducing the pressure of the pressure-controllable environment to a pressure between 80 and 40 Torr; c) maintaining the pressure of the pressure-controllable environment between 90 and 35 Torr for a first predetermined period of time; d) removing ethyl acetate from the alcoholic composition to provide a first purified alcoholic composition; e) removing the first purified alcohol composition from the pressure-controllable environment; A method comprising:

2. 10. The method of claim 1, wherein the alcohol composition contains from 3% to 95% ethanol by volume.

3. f) cooling the pressure-controllable environment after b) and before e); 10. The method of claim 1, further comprising:

4. 10. The method of claim 1, wherein the temperature of the pressure-controllable environment is maintained between -20 degrees Celsius and 80 degrees Celsius.

5. 10. The method of claim 1, wherein the temperature of the pressure-controllable environment is maintained between 10 degrees Celsius and 35 degrees Celsius.

6. 2. The method of claim 1, wherein the first predetermined period is five seconds.

7. 2. The method of claim 1, wherein the ethyl acetate concentration of the first purified alcoholic composition is one-third, one-half, or two-thirds of the ethyl acetate concentration of the alcoholic composition.

8. 2. The method of claim 1, wherein the ethyl acetate concentration of the first purified alcoholic composition is one-third of the ethyl acetate concentration of the alcoholic composition.

9. 10. The method of claim 1, wherein the first purified alcohol composition has an ethyl acetate concentration of 1 ppm to 400 ppm as measured by liquid-phase gas chromatography-mass spectrometry.

10. 10. The method of claim 1, wherein the first purified alcohol composition has an ethyl acetate concentration of 5 ppm to 300 ppm as measured by liquid-phase gas chromatography-mass spectrometry.

11. g) removing one or more additional homologs of a homolog group comprising ethyl acetate, acetaldehyde, ethanol, isobutanol, 2-methyl-1-butanol, acetic acid, or furfural from the first purified alcoholic composition to provide a second purified alcoholic composition; 10. The method of claim 1, further comprising:

12. The pressure-controllable environment comprises: a pressure vessel defining a pressure-controllable chamber; a jacket at least partially surrounding and in thermal communication with the pressure-controllable chamber; a liquid inlet port in fluid communication with the pressure-controllable chamber; a gas outlet port in fluid communication with the pressure-controllable chamber; a vacuum pump in fluid communication with the gas outlet port; A collection tank; a liquid outlet port in fluid communication with the pressure-controllable chamber; Further comprising:

2. The method of claim 1 .

13. 13. The method of claim 12, wherein the jacket is a water jacket.

14. During b), the pressure of the pressure-controllable environment is reduced to a pressure of 42 Torr; c), wherein the pressure-controllable environment is maintained at a pressure of 42 Torr.

2. The method of claim 1 .

15. 1. A method for removing ethyl acetate from an alcoholic composition, comprising: a) establishing a partial vacuum in a pressure vessel; b) pouring a quantity of an alcoholic composition into the pressure vessel; c) at least partially preferentially removing ethyl acetate relative to acetaldehyde or ethanol from the alcoholic composition to provide a purified alcoholic composition; d) extracting the purified alcoholic composition from the pressure vessel, wherein the alcoholic composition remains liquid while in the pressure vessel; A method comprising:

16. the partial vacuum is in the range of 35 torr to 90 torr; c) is carried out at a temperature of 10 to 35 degrees Celsius for 5 to 60 seconds; 16. The method of claim 15.

17. the partial vacuum is 42 Torr; c) is performed at 22 degrees Celsius for 5 seconds; 16. The method of claim 15.

18. 1. A method for removing ethyl acetate from an alcoholic composition, comprising: a) providing a quantity of crude alcohol-water solution in a pressure and temperature controllable environment; b) reducing the pressure of the pressure and temperature controllable environment to a pressure between 80 and 20 Torr; c) maintaining the pressure of the pressure and temperature controllable environment between 80 and 20 Torr for a first predetermined period of time; d) removing ethyl acetate from the crude aqueous alcoholic solution to provide a first purified alcoholic composition; e) removing the first purified alcohol composition from the pressure and temperature controllable environment; Equipped with the first purified alcohol composition has the same composition as the crude alcohol-water solution, except that the first purified alcohol composition contains less ethyl acetate than the crude alcohol-water solution; During c), the temperature in the pressure and temperature controllable environment is controlled so that only ethyl acetate is removed from the crude aqueous alcohol solution. A method characterized by:

19. 20. The method of claim 18, wherein during step c), the pressure in the pressure and temperature controllable environment is maintained between 20 Torr and 55 Torr and the temperature in the pressure and temperature controllable environment is maintained at 22 degrees Celsius.

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