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WO1990008183A1 - Procede de traitement de boissons alcoolisees par evaporation au travers d'une membrane commandee par la vapeur - Google Patents

Procede de traitement de boissons alcoolisees par evaporation au travers d'une membrane commandee par la vapeur Download PDF

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Publication number
WO1990008183A1
WO1990008183A1 PCT/US1990/000227 US9000227W WO9008183A1 WO 1990008183 A1 WO1990008183 A1 WO 1990008183A1 US 9000227 W US9000227 W US 9000227W WO 9008183 A1 WO9008183 A1 WO 9008183A1
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WO
WIPO (PCT)
Prior art keywords
membrane
ethanol
liquid
water
feed side
Prior art date
Application number
PCT/US1990/000227
Other languages
English (en)
Inventor
Eric K. Lee
Vinay J. Kalyani
Stephen L. Matson
Original Assignee
Sepracor, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/296,255 external-priority patent/US4933198A/en
Priority claimed from US07/382,615 external-priority patent/US5013436A/en
Priority claimed from US07/463,098 external-priority patent/US5013447A/en
Application filed by Sepracor, Inc. filed Critical Sepracor, Inc.
Publication of WO1990008183A1 publication Critical patent/WO1990008183A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H3/00—Methods for reducing the alcohol content of fermented solutions or alcoholic beverage to obtain low alcohol or non-alcoholic beverages
    • C12H3/04—Methods for reducing the alcohol content of fermented solutions or alcoholic beverage to obtain low alcohol or non-alcoholic beverages using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/24—Specific pressurizing or depressurizing means
    • B01D2313/243—Pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/46—Supply, recovery or discharge mechanisms of washing members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/90—Additional auxiliary systems integrated with the module or apparatus
    • B01D2313/903—Integrated control or detection device

Definitions

  • This invention relates to novel methods and apparatus for manipulating the ' concentration of volatile components in a liquid, in particular the ethanol content in alcoholic beverages such as wines, distilled spirits, beers, and sparkling wines etc.. by selectively removing at least one preselected member of a plurality of volatile components present in the • liquid while a substantial portion of the remaining members of the plurality of volatile components is retained in the liquid.
  • the present method and apparatus allows for the selective removal of, for example, water, ethanol, or the simultaneous removal of water and ethanol, in any desired proportion, including that which corresponds to the ethanol concentration of the original beverage.
  • VAP vapor-arbitrated pervaporation
  • the invention has general applicability to the manipulation of the concentration, by partial depletion of one or more volatile components in a given liquid while leaving the other volatile components in the liquid in an enriched, but otherwise substantially undisturbed or unadulterated, state.
  • the resultant burnt taste can be distinct, objectionable, and difficult to mask by blending with other beverage ingredients .
  • MEMBRANE DISTILLATION METHODS The technique of membrane distillation involves separating volatile components from a liquid into a gaseous extraction media through a microporous membrane. The membrane impedes passage of liquid but not vapor, and functions essentially as a phase separator which does not impart any permselectivity. As such, the degree of ethanpl reduction made possible by this technique is governed by the state of vapor-liquid equilibrium which exists in the absence of the membrane. In a variation of the membrane distillation technique, Japan Patent No.
  • Reverse osmosis is a pressure-driven membrane process usually operating at ambient or sub-ambient temperatures that has been used commercially for alcohol reduction of beverages. Alcohol removal is achieved by . simultaneous removal of ethanol and water by pressurizing the beverage against a membrane with limited ethanol/water selectivity (Bui et al., 1986, Am. J. Enol. Vitic, 37: 297, and Light et al., 1985, AIChE Symp. Ser. 250, No. 82, Recent Ad vances in Separation Techniques and Light, in U.S. Patent No. 4,617,127). To compensate for the water loss, the beverage is diluted with water prior to alcohol reduction, or water could be added to the concentrated product after * processing to replace the volume originally occupied by ethanol and water.
  • Rejection is a common measure of selectivity of a reverse osmosis membrane, defined as ( (C f -C p ) /C f ) '100%, where C f and C p are the steady-state solute concentrations in the feed and in the permeate, respectively.
  • the ethanol-impermeable membrane cited as an example in U.S. Patent No. 4,806,366, showed only a 50% ethanol rejection toward a 2 vol% ethanol feed at 50 to 60 bar applied pressure. This level of selectivity can be expected to decrease at the higher alcohol concentrations more representative of wines, i.e. 10 to 14 vol%, and likely becoming non-selective at the 40 vol% or higher alcohol concentrations found in distilled spirits .
  • Managing the interaction between the two reverse osmosis systems and matching the operating conditions to the characteristics of each membrane also add to the complexity of this process .
  • Membrane extraction in which a membrane is interposed between a solvent containing a solute to be extracted and a second, immiscible extraction solvent, prevents the solvent entrainment and emulsion formation problems inherent to conventional solvent extraction technology.
  • Kim in U.S. Patent No. 4,443,414, used a microporous membrane to extract molybdenum from solutions containing molybdenum and other mineral ions.
  • Lee et al. in U.S. Patent No. 3,956,112, described a membrane solvent extraction system for general application based upon the use of a non-porous membrane.
  • the above membrane solvent extraction systems involve the use of solvent-swollen membranes, they do not prevent the molecular diffusion of dissolved solvent into the aqueous phase. Furthermore, the membranes of the prior systems show no permselectivity for the solutes to be removed. Instead, any observed selectivity is due to the choice of the extraction solvent or to the inclusion of chelating agents in the solvent that are selective for the metal ions that are to be extracted. Finally, the organic extraction solvents employed by Ho et al. , and Lee et al.
  • Tilgner et al. in U.S. Patent No. 4,664,918, used alcohol-free fruit drinks or alcohol-reduced fermented drinks as ethanol extractants in a dialysis process. While ethanol can be removed effectively this way, the drinks used as dialyzing solution may contain components that are not part of the beverage whose alcohol content is to be reduced. Diffusion of such substances into the beverage can alter its organoleptic profile. Furthermore, water can permeate freely across the membrane because both the beverage and the dialyzing drink are aqueous. Unless the osmolality of the two phases are critically balanced, the beverage may experience a net gain or loss of its water content.
  • pervaporation is governed by the permselectivity of the membrane and not the relative volatility of the components, in contrast to evaporative or membrane distillation processes. For this reason, pervaporation can accomplish selective removal of ethanol over other volatile components if a membrane permselective toward ethanol is used.
  • a hydrophobic membrane with low water permeability is used to limit water loss. The result is significant loss of non-polar volatile components because of their solubility in, and ability to permeate across, the similarly non-polar polymer membrane.
  • a hydrophilic membrane instead of a hydrophobic membrane helps preserve those non-polar components in the feed beverage, but the consequent water loss would introduce problems similar to those with reverse osmosis, i.e., the need to exchange part or most of the native water in the beverage.
  • membrane materials with good ethanol permeability also exhibit some water permeability because of the chemical similarities between the two components; the water-barrier property of such membranes is necessarily compromised. For these reasons, beverages produced via conventional pervaporation are characterized by low quality.
  • Ethanol should be removed as selectively as possible, i.e. with minimal simultaneous removal of water.
  • Ethanol should be removed in such a way that addition of water to or removal of water from the product is avoided.
  • Alcoholic beverages are concentrated and enriched for a variety of reasons.
  • Galzy et al. in U.S. Patent No. 4,610,887, used reverse osmosis to remove water from wines and fermented juices to increase the concentratio of the beverage ingredients.
  • Membranes exhibiting good retention of ethanol and other organic compounds with molecular weights below 200 daitons were specified for this process to minimize loss of those organic compounds.
  • Bonnome in U.S. Patent No. 4,532,140, described the following two-step procedure to prepare an alcohol-enriched, flavored beverage for direct consumption o as a means of reducing the cost of transportation.
  • a portio of water and ethanol from the beverage was first removed by means of reverse osmosis or ultrafiltration to yield a flavo concentrate liquid.
  • the ethanol in the permeate stream was then isolated, by means of a second reverse osmosis stage, and returned to the concentrated flavor liquid.
  • different membranes are thus required to generate the flavor concentrate liquid and to separate ethanol from water because of the different ethanol permeation/retention properties needed at each step.
  • the beverage concentrate would eventually be reconstituted to its origina volume by adding water.
  • Fricker in European Patent No. 116,462 alcoholic beverages were concentrated by combining reverse osmosis and distillation methods. The reverse osmosis portion of this process concentrated the flavor compounds while allowing partial passage of water, ethanol, and some of the volatile flavor components from the beverage into the permeate stream.
  • Alcohol and volatile flavor components were then recovered b distilling the permeate and returned to the beverage concentrate. Again, this procedure is aimed at reducing the volume, and hence the transportation cost, of beverages such as beer, wine, cider, etc. whose principal constituent is water. Frequently, however, concentration or enrichment is performed as an intermediate step in a dealcoholization process. Dikansky et al., in French Patent 2,620,129, described a process which is typical of this approach. .An alcoholic beverage was processed by reverse osmosis to remov the water and ethanol as permeate from the other beverage components retained in a substantially reduced volume ⁇ concentrate.
  • Water and ethanol should be removed in any proportion desired, and in particular in the same proportion corresponding to that presen in the original beverage. 2) The water-alcohol mixture should be removed in such a way that most organic compound present in the beverage are retained in the beverage to the greatest extent during removal o those two components .
  • Vapor-arbitrated pervaporation is a membrane process in whic one side of a semipermeable membrane is in contact with a feed liquid containing one or more volatile substances, and the second side of the membrane is exposed either to a sweep gas stream comprising a non-condensable gas and a regulated quantity of one of the said volatile substances, or to a partial vacuum containing a regulated quantity of one of the said volatile substances. More generally, the invention can be used to adjust the concentration of one or more volatile components in a given solution to any desired level.
  • low- alcohol beverages are produced by a process involving the extraction of ethanol through a semipermeable membrane with the aid of an ethanol-recovery extraction fluid capable of absorbing permeated ethanol as it issues from the membrane while neither absorbing water from the beverage nor contributing additional water to the beverage.
  • the nature and properties of the membrane and/or extraction fluid are chosen such that substantially all of the other desirable organic constituents or congeners of the alcoholic beverage are not co-extracted simultaneously with the ethano to an excessive degree. As a result, organic constituents o the beverage are selectively retained, while the alcohol content of the beverage is selectively reduced.
  • the finished reduced-alcohol product retains the flavor of the original alcoholic beverage but has an alcohol content that is up to about 97% lower than that of the starting material.
  • the present invention in a specific embodiment, relates to a method comprising exposing one side of a membrane to a beverage and the other side of the membrane to a gas-phase extraction fluid, and equalizing the water activities in the beverage and throughout the gas-phase by adjusting the amount, pressure or temperature of the water vapor in the gas-phase extraction fluid.
  • the process of thi invention is referred to as vapor-arbitrated pervaporation.
  • the membrane used in this invention should be selectively permeable to ethanol in preference to the flavor, aroma and color components in the beverage.
  • the gas-phase extraction fluid may consist of a non-condensable gas and water vapor above, at or near atmospheric pressure, or it may consist of a partial vacuum and water vapor.
  • the vapor may contain or have added to it, other organic or inorganic materials.
  • ethanol permeates from the beverage across the membrane into the gas-phase. Permeation of the flavor and aroma components is impeded by the membrane.
  • the presence of sufficient water vapor in the gas-phase extraction fluid to provide a water activity approximately equal to that in the beverage inhibit water transport across the membrane, independent of the ethanol/water selectivity of the membrane.
  • ethanol-enriched beverages are produced by a process involving the extraction of water through a semipermeable membrane in conjunction with a water-recovery extraction fluid capable of absorbing permeated water as it issues from the membrane while neither absorbing ethanol from the beverage nor contributing additional ethanol to the beverage.
  • the nature and properties of the membrane and/or extraction fluid are chosen such that substantially all of the other desirable organic constituents or congeners of the alcoholic beverage are not co-extracted simultaneously with the water to an excessive degree. As a result, organic constituents of the beverage are selectively retained, while the water content of the beverage is selectively reduced.
  • the finished reduced-water product thus retains the flavor of the original alcoholic beverage, indeed has an enhanced flavor thereover, but has a water content that is up to about 95% lower than that of the starting material. Also, this reduced-water product necessarily has a higher alcohol content than the original feed beverage.
  • the present invention in a specific embodiment relates to a method comprising exposing one side of a ' membrane to a beverage and the other side of the membrane to a gas-phase extraction fluid, and equalizing the ethanol activities in the beverage and throughout the gas-phase by adjusting the amount, pressure or temperature of the ethanol vapor in the gas-phase extraction fluid.
  • This related process of the present invention may also be referred to as vapor-arbitrated pervaporation.
  • the membrane used in this invention should be permeable to water selectively over the flavor and aroma components in the beverage.
  • the gas-phase extraction fluid may consist of a non-condensable gas and ethanol vapor above, at or near atmospheric pressure, or it may consist of a partial vacuum and ethanol vapor.
  • the vapo may contain, or have added to it, other organic or inorganic materials. Under the prescribed conditions, water permeates from the beverage across the membrane into the gas-phase. Permeation of the flavor and aroma components is impeded by the membrane. Furthermore, the presence of sufficient ethanol vapor in the gas-phase extraction fluid to provide an ethanol activity approximately equal to that in the beverage inhibits ethanol transport across the membrane, independent of the ethanol/water selectivity of the membrane.
  • a method which pertains to the net reduction in the volume of the beverage with no significant change in its alcohol content.
  • This process may be accomplished through the use of membranes, chosen such that they are poorly permeable to many of the desirable organic constituents or congeners of the alcoholic beverage, in conjunction with gas- phase extraction fluids capable of absorbing permeated water and permeated ethanol as they issue from the membrane.
  • gas- phase extraction fluids capable of absorbing permeated water and permeated ethanol as they issue from the membrane.
  • the concentration ratio of ethanol and water complements the inherent selectivity ratio of the membrane
  • the product then has the same level of alcohol as the original beverage, but is enriched in flavor and aroma components.
  • the gas-phase . extraction fluids may consist of a non-condensable gas, ethanol vapor, and water vapor at or near atmospheric pressure, or it may consist of a partial vacuum, ethanol vapor, and water vapor.
  • the methods of this invention offer a means to produce flavor- and aroma-enriched beverages with alcohol contents similar to those of the beverages prior to processing.
  • Yet another embodiment of the present invention involves a method of manipulating the concentration of at least one preselected member of a plurality of volatile components present in a liquid comprising:
  • Yet another embodiment of the present invention involves a method of reducing the concentration of native ethanol in an aqueous liquid comprising: (a) providing a membrane having a feed side and a permeate side opposite said feed side, said membrane being permeable to ethanol;
  • Yet another embodiment of the present invention involves a method of enriching the concentration of native ethanol in an aqueous liquid comprising: (a) providing a membrane having a feed side and permeate side opposite said feed side, said membrane being permeable to water;
  • Yet another embodiment of the present invention involves a method of reducing the volume of a liquid comprising at least two volatile solvents, which method r comprises :
  • the carrier gas is a non-condensable gas; i.e., one which does not condense to a significant degree under conditions which are sufficient to condense the volatile components of interest in said fluid mixture.
  • Yet another embodiment of the present invention involves an apparatus for manipulating the concentration of at least one preselected member of a plurality of volatile components present in a liquid comprising:
  • a membrane having a feed side and a permeate side opposite said feed side, said membrane being permeable to at least one preselected member of a plurality of volatile components present in a given liquid;
  • FIG. 1 is a schematic representation of the principles of the vapor-arbitrated pervaporation process of the present invention during which a liquid present on one side of a membrane in a liquid phase contains at least two volatile components A and B, and on the other side of membrane an extraction fluid, comprising a non-condensable gas and a controlled amount of the vapor of component B, is present such that a potential for the net transport of component A from the liquid phase to the vapor phase is obtained, while the potential for the net transport of component B from the liquid phase to the vapor phase is virtually eliminated.
  • the liquid phase may be an alcoholic beverage.
  • FIG. 2 shows a plot of the relative humidity required to prevent water transport across the membrane as a function of ethanol concentration (in volume %) in the liquid phase.
  • FIG. 3 shows a plot of ethanol saturation ratio in the vapor stream required to balance the activity of ethanol in the beverage, as a function of the concentration of ethanol (volume %) in the liquid phase.
  • FIG. 4 is a schematic representation of the basic membrane extraction alcohol reduction process, wherein an alcohol-containing beverage and an extraction fluid move, optionally but preferably in countercurrent fashion, on opposite sides of a permselective membrane, so that only ethanol permeates into the extraction fluid.
  • FIG. 5 is a schematic representation of the basic vapor-arbitrated pervaporation process for the removal of ethanol from alcoholic beverages wherein the water activity is equalized in the liquid phase and gaseous phase by addition of water vapor to the gaseous phase.
  • FIG. 6 is a schematic representation of a vapor- arbitrated pervaporation process with feed- and permeate-side water activity equalization and ethanol recovery.
  • FIG. 7 shows a schematic representation of a process whereby liquid water entering a gas-liquid contactor is vaporized and blended with a non-condensable gas. Ethanol is recovered by using a condenser.
  • FIG. 8 shows a schematic representation of a process whereby steam is mixed with the non-condensable gas in a condenser to produce a humidified exit gas stream. Ethanol is recovered with a condenser.
  • FIG. 9 shows a bench-scale apparatus for pervaporation removal of ethanol from beverages using a vapor-swept system.
  • FIG. 10 is a schematic representation of a prevaporation system with permeate removal by vacuum and permeate-side water activity control.
  • FIG. 11 illustrates the basic vapor-arbitrated pervaporation process for alcohol enrichment.
  • FIG. 12 illustrates one embodiment of the process for alcohol enrichment utilizing a vapor-swept system.
  • FIG. ' 13 illustrates a vapor-swept system incorporating means for ethanol vapor recycling.
  • FIG. 14 illustrates yet another embodiment of ' the ethanol vapor management scheme of the present invention.
  • FIG. 15 shows a schematic diagram of an alcohol enrichment process which utilizes a vacuum system.
  • FIG. 16 illustrates the basic vapor-arbitrated pervaporation process for flavor and aroma enrichment of beverages.
  • FIG. 17 illustrates a typical process scheme for the vapor-swept configuration useful for the dual vapor- arbitrated pervaporation process for flavor and aroma enrichment.
  • FIG. 18 illustrates a particular embodiment of the alcohol-enrichment aspect of the present invention.
  • the present invention pertains to the controlled manipulation of ethanol content in alcoholic beverages while simultaneously preserving the flavor and aroma contents originally present in the beverage.
  • Such manipulation includes 1) selective removal of ethanol; 2) selective removal of water; and 3) selective removal of ethanol and water at a preselected proportion.
  • These manipulations are available in a class of membrane processes referred to as vapor-arbitrated pervaporation.
  • the present invention pertains to the separation of two volatile components A and B present in a liquid phase by selectively removing one of those components, say A, through a membrane into a gas phase while substantially retaining the other component, B, in the liquid phase.
  • the liquid phase becomes partially depleted in component A.
  • the concentration of the retained component B is increased, i.e. enriched, in the liquid phase.
  • the present invention provides for equalizing the permeate-side activity of component B and the feed-side activity of component B in the liquid phase. In so doing, the driving force for diffusional transport of B is diminished, and the need for replenishing component B at the end of the process is averted.
  • R is the universal gas constant (82.06 mL-atm/°K-mol)
  • T is temperature (°K)
  • fi is the fugacity of species i
  • 0(T) is a constant.
  • the fugacity of a substance may be defined as the tendency of a substance in the liquid phase to escape into the gaseous phase and vice versa. From equation (1) , it follows that at a given temperature, the fugacity of component i in the liquid phase, fi, ⁇ should equal the fugacity of component i in the gas phase, fi,g.
  • Xi mole fraction of i in the liquid phase
  • yi mole fraction of i in the vapor phase
  • 0i fugacity of saturated liquid or vapor i
  • P total pressure
  • the activity of a substance in the gases or liquid phase is the ratio of the fugacity of the substance at a given temperature T to the fugacity of the substance in the standard state. Therefore, if the fugacity of component i in its liquid and gaseous states are equivalent, then it follows that the activities are also equivalent.
  • Vi i molar volume of liquid component i.
  • the activity coefficient, Yi can be obtained from experimental measurements of partial pressures of component i over a mixture of volatile liquid components. If Xi and P are fixed, then yi, the mole fraction of component i in the gas stream required to balance its chemical potential in the liquid (or to have zero component i transport across the membrane) can be found from Equation (6) .
  • Equation (6) For the manipulation of ethanol concentration in alcoholic beverages, two working relationships can be developed. To achieve alcohol reduction, it is necessary to equalize water activities on both sides of the membrane.
  • the relationship between the relative humidity in the gas-phase and the mole fraction of water in the beverage at a given temperature is:
  • Relative humidity (%) (y w P/P WfSa t) x 100. (7)
  • a saturation ratio term may be defined as the ratio of ethanol partial pressure to the vapor pressure of ethanol at that temperature:
  • Equations (7) and (8) indicate water and ethanol respectively.
  • the partial pressures of water and ethanol at various temperatures and compositions are shown in Table I. From these experimental data and the equations supra, the relative humidity required for operating vapor-arbitrated pervaporation in the alcohol reduction mode without water loss has been calculated as a function of beverage alcohol content as shown in Figure 2. For example, the relative humidity required to prevent water transport across the membrane from a 40 vol% alcohol beverage is about 85% at ambient temperature and pressure. Similarly, the relative ethanol pressure required for operating vapor-arbitrated pervaporation in the alcohol enrichment mode without ethanol loss is shown in Figure 3. Beverage ethanol contents are shown in these figures in vol%, the common units employed in the labeling of alcoholic beverages.
  • P w and P e are in units of mm Hg.
  • FIG. 4 5.1 ALCOHOL REDUCTION Removal of ethanol by extraction in general is illustrated in Figure 4.
  • a semipermeable membrane is interposed at the interface between the alcoholic beverage that is to be processed and an appropriate gaseous extraction fluid.
  • Certain desirable organic components or congeners of the beverage are unable to pass through the permselective membrane and into the extraction fluid; additionally, the extraction fluid itself may exhibit a degree of selectivity for the preferential volatilization of ethanol over the other, desirable organic components. In this manner. preferential removal of ethanol over other desirable organic solutes in the beverage is realized.
  • a second aspect of the invention is its ability to selectively remove ethanol in preference to water.
  • a distinguishing feature of this invention is that the membrane need not be selectively permeable to ethanol over water. Indeed, the overall process can exhibit remarkable ethanol removal selectivity, even when water would normally be capable of freely permeating the membrane along with ethanol. This performance results from the characteristics of the extraction fluid.
  • the extraction fluid is chosen such that it does not absorb permeated water from the wine or other alcoholic beverage being treated, nor does the extraction fluid donate water to the alcoholic beverage.
  • the present invention provides a method for producing from a first alcoholic beverage a second beverage of reduced alcoholic content comprising the steps: providing a membrane which is alcohol permeable; feeding a first alcoholic beverage across a feed side of said membrane; feeding a gas-phase extraction fluid across a permeate side of said membrane, said extraction fluid being alcohol absorbing, but substantially not water absorbing and said extraction fluid comprising water vapor in an amount sufficient to minimize the diffusion of water from said first alcoholic beverage to said permeate side of said membrane by balancing the activity of water on said feed side of said membrane so as to evaporate into said gas-phase extraction fluid the portion of the alcohol initially present in said first alcoholic beverage which has crossed to the permeate side of said membrane, thereby forming from said first alcoholic beverage a second beverage having reduced alcoholic content; and withdrawing said gas-phase extraction fluid containing water vapor and alcohol from said permeate side of said membrane, whereby said second beverage having reduced alcoholic content is produced on said feed side of said membrane.
  • the features of the process are depicted conceptually in Figure 5.
  • the use of a membrane that is more permeable to ethanol than to the congeners ensures that most of the congeners will be retained in the beverage during ⁇ ethanol removal.
  • the gas-phase extraction fluid may be maintained in the gas-phase using either a non-condensable gas (e.g. air or nitrogen) or vacuum applied from a vacuum pump.
  • the gas-phase. extraction fluid further comprises water vapor to balance the water activities on the permeate and feed sides of the membrane, as will be discussed infra.
  • the gas-phase extraction fluid may also comprise organic or inorganic components so as to prevent the permeation of such components present in the beverage across the membrane. These components may be naturally in the extraction fluid or they may be added selectively hereto.
  • the present invention is primarily intended for ethanol removal from beverages, the process concept described herein can be applied generically to the selective removal of one or more volatile components from aqueous solutions while retaining other dissolved volatile and non-volatile components.
  • Commercially available alcoholic beverages which include but are not limited to beer, wine, and distilled spirits, have an initial ethanol content of from about 5 to about 75 volume %.
  • the relative humidity should be maintained at about 60 to about 95% at about 5°C to about 75°C.
  • the relative humidity should be maintained at about 95% to about 100% at about • 5°C to about 75°C. If the alcoholic beverage is a wine with an initial ethanol content from about 9 to about 13% volume, the relative humidity should be maintained at about 85 to 95% at about 5° to about 75°C. If the alcoholic beverage is a brandy with an initial ethanol content from about 35 to abou 55 volume %, the relative humidity should be maintained at about 80 to 90 % at about 20° to about 75°C.
  • the alcoholic beverage is a distilled spirit with an initial ethanol content from about 50 to about 70 volume %
  • thej» relative humidity should be maintained at about 75 to about 85% at about 20°C to about 75°C. In some cases, processing temperatures below about 20°C or above about 75°C may be desirable. The same principle of relative humidity adjustment applies generally at those other temperatures.
  • the alcoholic beverage may be processed at or nea atmospheric pressure.
  • a slightly higher pressure may also be applied such that the carbon dioxide dissolved in those beverages is preserved during alcohol reduction treatment.
  • the principle of vapor- arbitrated pervaporation remains generally applicable at those other pressures.
  • a variety of process schemes are possible for equalizing feed- and permeate-side water activities in vapor arbitrated pervaporation.
  • the invention also relates to an apparatus for
  • the present invention is primarily intended for ethanol removal from beverages, the concept described herein can be applied generically to the selective removal of one or more volatile components from aqueous solutions while retaining other dissolved components.
  • a preferred vapor-swept pervaporation system embodying the water activity management concept is shown conceptually in Figure 6.
  • a membrane unit comprises two flo compartments, one on each side of the membrane 15.
  • Beverage 10 is fed to compartment A of the membrane unit, a gas-phas extraction fluid 31 comprising a mixture of non-condensable gas (such as air or nitrogen) and water vapor is fed to the other compartment B as a sweep stream.
  • a feed subsystem regulates the delivery rate and the temperature of the beverage; it also replenishes the latent heat of evaporation lost from the feed stream during ethanol pervaporation.
  • a humidification subsystem is used to regulate the temperature, relative humidity (and thus water activity) , and flow rate o the sweep stream.
  • An alcohol recovery subsystem 39 separates the water and ethanol 40 from the non-condensable gas 37 in the gas-phase extraction fluid that emerges 32. Provided that the sweep stream flow rate is sufficiently hig to prevent excess ethanol accumulation on the permeate side of the membrane, the pervaporation and purging actions will continue to sustain ethanol reduction. Another function of the sweep stream is to help supply part of the latent heat o ethanol evaporation.
  • FIG. 7 Another preferred embodiment of the humidification su b system is shown in Figure 7.
  • the beverage 10 is circulated via a pump 11 to compartment A of the membrane unit containing membrane 15.
  • the beverage emerges with a reduced alcoholic content 16.
  • Liquid water 25 is vaporized with the non-condensable gas 20 in a gas/liquid contactor 22 (e.g. a spray tower, packed column, etc.). Excess water may be removed yia an outlet 24.
  • the temperature T s inside the contactor 22 (approximately equal to that of the incoming water) is set to produce a water loading of the gas which, upon heating with a process heater 29 to the operating temperature T of the resulting gas-phase extraction fluid 31 will give exactly the desired relative humidity.
  • the proces heater may be for example a steam or electrical heater, a heat exchanger, or some other heat source operated at a temperature sufficiently high to give the desired relative humidity.
  • the gas-phase extraction fluid that emerges from compartment B of the membrane unit, comprising non- condensable gas, water vapor, ethanol vapor, and other volatile organic components (e.g. congeners) 32 may be coole with a condenser 35 and the liquified ethanol solution 40 ma be collected.
  • the non-condensable gas, stripped of water an ethanol vapors, can be vented 37 via a valve 36 or recycled 38 to the humidification system. Recycling is desirable in some cases.
  • nitrogen may be used as the non- condensable gas for the purpose of minimizing oxidation of the beverage; but disposal of the gas after a single pass through the membrane unit would be uneconomical. Another reason for recycling is to allow certain permeated congeners to accumulate in the gas stream so as to deter further loss of those congeners from the beverage.
  • the temperature and flow rate of the incoming non-condensable ga stream may be adjusted so that the gas does not become saturated with water vapor in the liquid-gas contactor, rather, the exiting gas stream would have the required temperature and relative humidity with no further heating or cooling.
  • FIG 8. As in Figure 7, the beverage 10 is circulated vi a pump 11 to compartment A of the membrane unit containing membrane 15. The beverage emerges with a reduced alcoholic content 16. Steam 21 is mixed with the non-condensable gas 20 in a condenser 23 to produce a water-saturated gas-phase extraction fluid at a temperature Ts. Excess water condense from the steam 24 is removed from the condenser 23. Again, the gas-phase extraction fluid is heated to a preselected operating temperature with a process heater 29 to produce a gas-phase extraction fluid having the desired relative humidity. Alternatively, direct injection of steam at a precisely controlled rate into a pre-conditioned air stream is an even more preferable means of generating the desired humidified air sweep stream in a single step.
  • the condenser 23 in this case would function as an optional mixing chamber for air and steam and the reheater 29 would be used as a tri heater or trim cooler for optional final adjustment of vapor stream temperature.
  • the gas-phas extraction fluid that emerges 32 from compartment B of the membrane may be cooled with a condenser 35 and the liquified ethanol solution 40 may be collected.
  • the non-condensable gas may be vented 37 via a valve 36 or recycled 38 to the humidification system.
  • the alcoholic beverage 10 is circulated with a pump 11 t compartment A of the membrane unit containing membrane 15.
  • process heater 12 may be used to maintain the feed stream at an operating temperature T.
  • a flowmeter 13 may be used to monitor the flow rate of the beverage stream.
  • the gas-phase extraction fluid 31, supplied to compartment B of the membrane unit, may be produced by pumping air 20 through a separate column 22 where it contacts water 25 heated with process heater 27 at a temperature T s to reach saturation.
  • flowmeter 21 may be used to monitor the flow rate of the a .20.
  • a pump 26 may be used to control the flow rate of the water. Excess water may be removed via an outlet 24.
  • the saturated gas phase extraction fluid 28 may then be reheat with a process heater 29 to the operating temperature T to attain a relative humidity governed by the temperature rise (T-T s ) .
  • T s may be determined from a given T and the requir relative humidity by using the procedure described in Secti 5.1, Table I and Figure 2. Equalizing the temperature of t feed and sweep streams, although optional, may help maintai a uniform relative humidity along.the permeate side of the membrane by reducing transmembrane heat transfer beyond tha associated with pervaporation of ethanol.
  • the apparatus ma be equipped with an automatic humidity control system that monitors the relative humidity of the gas-phase extraction fluid 31 at the entrance to the membrane module, and adjust the saturation temperature T s to compensate for deviations from the relative humidity set point.
  • the gas-phase extraction fluid 32 exiting from the membrane module is se to a condenser 35 where water and the pervaporated ethanol are liquified and collected.
  • a thin-film composite membran comprising an interfacially crosslinked polyurea membrane supported by an asymmetric, microporous polysulfone substra is preferred. Such a membrane is described further in Section 5.5, infra.
  • a pervaporation system embodying the water-activi equalization concept but which uses vacuum to remove the permeate is depicted in Figure 11.
  • Beverage 10 is fed into compartment A of the membrane unit containing membrane 15 a pump 11 to produce a beverage of reduced alcoholic conten 16.
  • the inlet to the permeate side of the membrane unit is connected to a water reservoir 25 equipped with a heater 27
  • Compartment B of the membrane unit is connected, sequentiall to a back-pressure regulator 34, a condenser 35, and a 5 vacuum pump 41.
  • This arrangement is used to regulate water vapor supply to the gas-phase extraction fluid 31 entering the permeate side of the membrane while continuously removin the pervaporated ethanol from the emerging gas-phase extraction fluid 32.
  • the water vapor is supplied at a partial pressure lower than its vapor pressure at that temperature. This ste is accomplished by adjusting the back-pressure regulator 34 to open whenever the permeate-side pressure is in excess of the target partial pressure. Ethanol and water vapors
  • a CQHQL ENRICHMENT Alcohol-enriched beverages whose organoleptic • 20 quality significantly surpasses those attainable by present means can be produced by the process described herein. Enrichment of ethanol through selective removal of water is accomplished by placing the beverage, the membrane, and the vapor-phase extraction fluid in a spatial arrangement shown
  • the driving force for diffusional ethanol transport is nullified according to the mathematical relationships shown in Section 5, supra, and preferential removal of water over ethanol results.
  • the use of a membrane that is more permeable to water than to the congeners ensures that most of the congeners will be retained in the beverage during ethanol enrichment.
  • the present invention provides a method for producing from a first alcoholic beverage a second beverage of increased alcoholic content comprising: providing a membrane which is water permeable; feeding a first alcoholic beverage across a feed side of said membrane; feeding a gas-phase extraction fluid across a permeate side of said membrane, said extraction fluid being water absorbing, but substantially not ethanol absorbing and said extraction fluid comprising ethanol vapor in an amount sufficient to minimize the diffusion of ethanol from said first alcoholic beverage to said permeate side of said membrane by balancing the activity of ethanol on said feed side of said membrane so as to evaporate into said gas-phase extraction fluid the portion of the water initially present in said first alcoholic beverage which has crossed to the permeate side of said membrane, thereby forming from said first alcoholic beverage a second beverage having increased alcoholic content; and withdrawing said gas-phase extraction fluid containing ethanol vapor and water from said permeate side o i said membrane, whereby said second beverage having increased alcoholic content is produced on said feed side of said membrane.
  • the gas-phase extraction fluid may be maintained i the gas-phase using either a non-condensable gas (e.g. air o nitrogen) or vacuum applied from a vacuum pump.
  • the gas- phase extraction fluid further comprises ethanol vapor to balance the ethanol activities on the permeate and feed side of the membrane, as will be discussed infra.
  • the gas-phase extraction fluid may also comprise organic or inorganic components so as to prevent the permeation of such components present in the beverage across the membrane. These components may be naturally in the extraction fluid or they may be added selectively hereto.
  • the present invention is primarily intended for water removal from beverages and the ethanol enrichment .thereof, the process concept described herein can be applie generically to the selective removal of one or more volatil components from aqueous solutions while retaining other ⁇ , dissolved components.
  • the invention also relates to an apparatus for producing from a first alcoholic beverage a second beverage of increased alcoholic content comprising a membrane which is water permeable; means for feeding a first alcoholic beverage acro a feed side of said membrane; and means for providing a gas-phase extraction fluid a permeate side of said membrane; means for regulating the partial pressure of ethanol in the said gas-phase extraction fluid on said permeate side of said membrane; and whereby water diffuses from the first beverage through the membrane into said gas-phase extraction fluid to produce said second beverage on said feed side of said membrane having increased alcohol content and a gas-phase extraction fluid comprising ethanol vapor and water vapor on said permeate side of said membrane.
  • Particular embodiments of the technology are described infra. In all cases relatively polar, hydrophilic membranes with good water/congener selectivity are assumed to be used.
  • the present invention is primarily intended for ethanol enrichment in beverages, the concept described herein can be applied generally to the selective enrichment of one or more volatile components in solutions while retaining other dissolved volatile or non-volatile components.
  • VAPOR-SWEPT SYSTEMS A preferred vapor-swept pervaporation system embodying the ethanol activity management concept s shown conceptually in Figure 12.
  • a membrane unit comprises two flow compartments, one on each side of the membrane 15'.
  • Beverage 10 is fed to compartment A of the membrane unit, a gas-phase extraction fluid 31' comprising a mixture of non- condensable gas (such as air or nitrogen) and ethanol vapor is fed to the other compartment B as a sweep stream.
  • a feed subsystem regulates the delivery rate and the temperature of the beverage; it also replenishes the latent heat of evaporation lost from the feed stream during water pervaporation.
  • a sweep gas conditioning subsystem is used to • regulate the -temperature, ethanol content (and thus ethanol activity), and flow rate of the sweep stream.
  • the beverage emerges with an increased alcoholic content 16' .
  • An alcohol recovery subsystem 39 separates the water and ethanol 40' from the non-condensable gas 37 in the gas-phase extraction fluid that emerges 32' .
  • the sweep stream flow* rate is sufficiently high to prevent excess water accumulation on the permeate side of the membrane, the pervaporation and purging actions will continue to sustain water removal, and hence ethanol enrichment.
  • Another function of the sweep stream is to help supply part of the latent heat of evaporation for water.
  • a source of ethanol is required to supply the permeate side of the membrane continually for the ethanol enrichment mode of vapor-arbitrated pervaporation to function. Because the cost of ethanol is much higher than that of water, and for environmental protection reasons, it is desirable to reuse the ethanol vapor in the gas-phase sweep stream.
  • a particularly preferred embodiment of the proce incorporates the ethanol vapor recycle scheme shown in Figu ' 13.
  • the beverage 10 is circulated via a pump to compartme A of the membrane unit containing membrane 15' .
  • the bever emerges with a reduced water content 16' .
  • a recirculation blower 51 feeds a sweep stream of non-condensable gas t ro compartment B of the membrane unit.
  • ethanol is supplied from an external source 52 through a valve 53 and mixing valve 55 into the gas-phase sweep stream until the concentration required to substantially equalize the ethano activities on both sides of the membrane is reached.
  • the external ethanol supply is stopped, while the gas phase sweep stream continues to be recirculated through compartment B of the membrane unit.
  • the ethanol vapor 57 passes through the heat exchanger 58 where it preheats the condensed liquid to be distilled, and is blend into the recirculating gas-phase sweep stream through mixin valve 55.
  • the gas stream 38' emerging from the condenser 5 is re-heated by heat exchanging with the water stream 37' from the still, and then combined with the ethanol vapor 57 for recirculation to compartment B of the membrane unit afte temperature adjustment with heat exchanger 60.
  • the condenser may be operated at a temperature that is sufficiently low to condense most of the water from the sweep stream while leaving a substantial . amount of ethanol in.the vapor state. Clean separation of small quantities of ethanol from water is readily accomplished with a still with minimal fractionation capabilities. As a result, little ethanol is lost in the r effluent water stream 37' . It also means that most of the ethanol is recycled without going through energy-intensive phase changes.
  • the gas-phase sweep stream emerging the membrane unit may contain a very small amount of ethanol.
  • the condenser 56 it may be possible to rely on the condenser 56 alone to separate water from the ethanol to be recycled without further distillation. This would be particularly desirable if the ethanol/water condensate has utility without further purification, such as in the manufacturing of certain beverages.
  • FIG. 14 An alternative embodiment of the ethanol vapor management scheme is illustrated in Figure 14.
  • the gas-phase sweep stream 32* emerging from compartment B of the membrane unit is passed through a first compartment C of a second membrane unit 61 where it contacts one side of a membrane which has the properties of being ethanol-absorbing but wat non-absorbing. Most of the ethanol in the gas phase preferentially partitions into that membrane, leaving water vapor, trace quantities of ethanol vapor, and the non- condensable gas in stream 63.
  • This stream may be vented 64 if air is used as the non-condensable gas or, if another no condensable gas is employed, recirculated after removing th water 65 by condensation using condenser 66.
  • the non-condensable gas 68 is preferred because it obviates capital and operating costs associated with condensing wate from a humid sweep stream.
  • the partially dehydrated non-condensable sweep gas 69 is passed, preferab countercurrently, .through compartment D of the second membrane unit 61 where it contacts the second side of membrane 88 and receives the ethanol that had been stripped from stream 32' .
  • a feed/recirculation blower 67 sends the ethanol-laden stream 69', which reaches a steady-state concentration needed to equalize ethanol activity across membrane 15', back to compartment B of the alcohol enrichme membrane unit after passing through heat exchanger 60 where the temperature is brought to the desired level.
  • membranes of the first type may be 1) an immobilized liquid membrane where the extractant is held as a continuous phase in the pores of a microporous membrane; or 2) a polymeric membrane that has a high solubility for, and is hence swolle by, the extractant liquid with the result that the selective properties of the liquid extractant dominates the overall selectivity of the membrane.
  • the liquid extractant used for this purpose should be low in toxicity (preferably falling within the GRAS, or Generally Recognized As Safe, classification of the U.S.
  • Some example extractants are silicone oils (which comprise polydimethylsiloxanes of certain structures and molecular weight ranges) , branched fatty alcohols in the C3.2 to C24 range (e.g. isostearyl alcohol, hexadecyl alcohol, eicosyl alcohol, etc.), and branched hydrocarbons containing up to about 24 carbon atoms that remain fluid at ambient temperatures.
  • Membranes of the second type include non-porous polymeric membranes that are relatively hydrophobic and which exhibits low permeability toward water, i.e. they should be good water barriers.
  • the absolute ethanol/water permselectivity of the membrane is not particularly stringent in this application because further separation of ethanol vapor from liquid water is performed downstream by selective condensation (66 in Figure 14) .
  • Candidate membrane materials meeting these criteria comprise certain silicone elastomers, polyolefins, and fluoropolymers. * Further variations of ethanol vapor management schemes are conceivable, including reversible absorption and stripping with selective ethanol extractants in classical gas/liquid contacting unit operations, as will be apparent to those skilled in the art.
  • a pervaporation system embodying the ethanol activity equalization concept but which uses vacuum to remove the permeate is depicted in Figure 15.
  • the beverage 10 is fed into compartment A of the membrane unit containing the membrane 15' via a pump to produce a beverage of reduced water content and enriched ethanol content 16* .
  • the outle from compartment B of the membrane unit is connected to a liquid ring pump 70, which generates a partial vacuum to a the evaporative removal of water that has permeated across the membrane from the beverage, and condenses, by compression, part of that permeate stream 32' which compri a mixture of water and ethanol vapors.
  • this condensate may be distilled at 59 to remo the residual ethanol, which may be added to the recycled ethanol vapor stream emerging from the liquid ring pump.
  • T obtain an ethanol activity less than unity, the ethanol vap is returned to the permeate side of the membrane at a parti pressure lower than its vapor pressure. This step is accomplished by adjusting the pressure control valve 53 to open and to supply a measured amount of ethanol vapor into compartment B of the membrane uni .
  • vapo arbitrated pervaporation processes are operated such that water and ethanol are removed at a given proportion until t required volume reduction, and optional changes in alcohol content, are reached.
  • the effective driving force of each component may be controlled independently in vapor- arbitrated pervaporation, whereby the relative transport rates of the components can be manipulated to differ substantially from those expected on the basis of membrane selectivities alone.
  • the inherent selectivity of .the membrane is complemented by active arbitration of the " driving force for permeation of the volatile components to be retained or removed from a feed liquid.
  • alcoholic beverages typically contain both water-soluble components and ethanol-soluble components in their natural state, and large changes in ethanol concentration may cause one or more of the components to precipitate or phase separate before the ' overall degree .of concentration or volume reduction is reached.
  • instabilities may be immediately evident, or they may be manifest in the form of reduced product stability during storage, transportation, and/or exposure to changing environmental conditions, especially temperature swings.
  • These varied objectives can be accomplished with vapor-arbitrated pervaporation by adjusting the concentrations of ethanol and water in the gaseous sweep stream so that the concentration ratio of these components in the vapor phase complements the inherent selectivity ratio of the membrane to cause simultaneous removal of water and ethanol from the beverage in the desired ratio. This concept is illustrated in Figure 16.
  • the concentration ratio of these components in the vapor phase should be adjusted so that water and ethanol are removed in exactly the same proportion as that present in the beverage phase.
  • the product then has the same alcohol level as the original beverage, but is enriched in flavor and aroma components.
  • a partial vacuum may be used to drive the permeation of the volatile component.
  • Supplying measured concentrations of the component to be retained into the partial vacuum on the permeate side of the membrane again serves to oppose diffusional transport of that component from the beverage.
  • this state often indicates a lack of sufficient selectivity.
  • conventional membrane processes may be staged, sometimes involving recycling. Even then, it is seldom feasible to obtain every possible ratio of cosolvents in the final product. It is an important advantage of the present invention that a significant degree of control hitherto not achievable can be exerted over the final composition of the product liquid.
  • a further advantage of vapor-arbitrated pervaporation is related to the presence of a gas phase on the permeate side of the membrane. Even if they may not be completely retained by the membrane, nonvolatile components such as sugars, tannins etc. remain in the beverage because they cannot evaporate into the gas phase. This situation differs from that in reverse osmosis where the simultaneous removal of ethanol and water can lead to losses of volatile and nonvolatile components alike due to flow coupling, and where the liquid phase permeate is receptive to those components because of their inherent solubility in ethanol/water mixtures.
  • VAPOR-SWEPT SYSTEMS A particularly preferred embodiment of the vapor- arbitrated pervaporation process for flavor and aroma enrichment via volume reduction of ethanol and water is show in Figure 17. Similar to the operation of the alcohol enrichment system described in Figure 13, the present embodiment incorporates reclamation of the ethanol vapor circulating in the vapor phase. In addition, a provision ha been made to supply water vapor 73 into the gas-phase sweep stream at measured rates through valve 72. Means for generating suitable sources ' of water vapor have been described in Section 5.1, supra. The desired degree of vapo arbitration for ethanol and water is achieved by adjusting the rate of addition of those vapors.
  • a vapor-arbitrated pervaporation system embodying the concept of simultaneous vapor arbitration for water and for ethanol are similar to those illustrated in Figures 10 and 15. This system creates a partial vacuum to provide the driving force for permeation in a manner similarly to that "" * depicted previously.
  • the vapor returned to the membrane unit should be relatively water-rich and ethanol-poor to encourage ethanol removal.
  • This process may be accomplished by combining part of the ethanol vapor stream obtained at the condensation step with water vapor generated by re- evaporation of part of the condensed water (or with a regulated supply of fresh steam) such that the resultant ethanol concentration in the recirculating vapor provides more impedance to water removal than to ethanol removal. T portion of the ethanol vapor that is not reused may be sent to a separate reclamation step.
  • the vapor returned to the membrane unit should be relatively ethanol-rich and water-poor to encourage water removal. This process may be accomplished b decreasing the amount of re-evaporated water vapor or steam to be mixed with the ethanol vapor.
  • the sweep stream emerging from the membrane unit is cooled to a temperature sufficiently low to liquify most of the water and ethanol. Part of this liquid is discharged, but part of it is reheated to process temperature, evaporated and recirculated to the permeate sid of the membrane for vapor arbitration purposes.
  • vapor-arbitrated pervaporation can be universally applied to controlling the loss of volatile components from liquids.
  • an appropriate amount -of the same volatile component one wishes to preserve in the feed liquid into the permeate side of the membrane, transmembrane diffusion of that component can be attenuated to the point that retention can be considered essentially perfect.
  • ethyl acetate is a congener responsible for the characteristic bouquet of certain alcoholic beverages. It is highly volatile, relatively small in molecular size, and exhibits moderate solubility in many polymers, and can therefore permeate readily through a variety of membranes.
  • ethyl acetate vapor may be blended in the form of a vaporized additive at a measured rate into the sweep gas stream during vapor-arbitrated pervaporation.
  • a low vapor-phase concentration usually suffices to halt any loss from the feed side because the ester is present only in trace quantities in most beverages. In this way, the quality of the beverage can be preserved better than has previously been possible with other processing methods.
  • This general approach of using vaporized additives in vapor-arbitrated pervaporation may therefore be considered an effective means of compensating for imperfect selectivity, a goal not attainable with conventional membrane processes.
  • the membranes used in the alcohol removal methods of the present invention must have a high ethanol/congener selectivity when ethanol is removed by extraction with gas- phase extraction fluids. Specifically, the membranes should be highly permeable to ethanol and be permselective between ethanol and other organic components of the beverage. Similarly, the membranes used in the alcohol enrichment methods of the present invention must have a high water/congener selectivity when water is removed by extraction with gas-phase extraction fluids. Specifically, the membranes should be highly permeable to water and be permselective between water and other organic components of the beverage.
  • a given membrane suited for the purpose of alcohol reduction will also function properly r for alcohol enrichment because its permeabilities toward ethanol and water are likely to be quite high compared to its permeabilities toward other beverage components.
  • the ethanol/water selectivity of the membrane is of secondary importance during vapor-arbitrated pervaporation.
  • membranes have potential applicability in this invention, and the choice will be influenced by economic considerations, the ethanol compatibility of the membrane, and its availability in high-surface-area configurations.
  • membranes constructed of crosslinked or uncrosslinked polymeric materials or more loosely organized elastomeric materials are suitable.
  • Membranes that are now used for reverse osmosis (RO) are good candidates for use in this invention, because RO applications entail high transmembrane water fluxes of polar permeants (e.g., water).
  • RO reverse osmosis
  • Membranes which exhibit ethanol and/or water fluxes adequate for the present invention should be thin, nonporous, and may be derived from polymers that are crosslinked or un ⁇ crosslinked, glassy or rubbery, and water—swollen to various degrees.
  • r ethanol fluxes ranging from about 0.04 to 0.09 mL/cm 2 -hr have been observed with a thin-film-composite crosslinked polyurea membrane, depending on the ethanol concentration in the feed beverage.
  • Related permeation tests conducted in our laboratory comparing various membrane types showed the relative ethanol fluxes listed in Table II.
  • membranes of varied compositions and structures contain numerous references to membranes of varied compositions and structures.
  • membranes that are relatively hydrophilic i.e. exhibiting higher permeabilities to water and ethanol than to higher alcohols
  • fluxes comparable to those mentioned supra should be suitable from a production standpoint.
  • Table III shows the ethanol/congener selectivity of a hydrophilic, crosslinked polyurea membrane in terms of congener/ethanol permeability ratios. Clearly, ethanol permeated more rapidly across the membrane than did the higher alcohols and other congeners (with the exception of methanol — a desirable attribute because of the relatively high toxicity of that alcohol) .
  • membrane types may be useful for the selective removal of ethanol from alcoholic beverages including, but not limited to, various aliphatic and aromatic polyamides, polyureas, polyetherureas, polyimides, polyoxazolines, polyetheramino- triazine, regenerated cellulose, cellulose acetate, cellulose triacetate, crosslinked polyvinyl alcohol, polyacrylonitrile and its copolymers (these polymers being particularly resistant to ethanol swelling), polybenzimidazole, and polybenzimidazolone, hydrophilic crosslinked vinyl polymers and copolymers, and ion-exchange membranes with various counterions. Any membrane geometry is potentially applicable.
  • a hollow-fiber module with high membrane area-to-module volume ratio is used.
  • the flow of alcoholic beverage may be directed through the lumen of the hollow fibers and the gas-phase extraction fluid along the exterior shell of the fibers, or vice versa.
  • the preferred configuration will depend on the pressure capability, wettability, and porosity of the fibers, as well as on the hydrodynamic and mass transfer characteristics of the modules containing them.
  • the preferred operating pressures of the process depend on the specific embodiment. With humidified non-condensable gas as the sweep stream, the preferred gas stream pressure would be at 1 atm, or fractionally above 1 atm consistent with membrane module and piping pressure drops.
  • the beverage stream will similarly be held at or about 1 atm to minimize the transmembrane pressure. Where vacuum operation is the preferred method of removing the pervaporated ethanol, then the permeate side of the membrane will be maintained at subatmospheric pressures.
  • Examples of the practice of the invention are as follows. Examples 1-5 describe the removal of ethanol by the special pervaporation process of this invention. Examples 6— 8 describe- the enrichment of. ethanol, and Example 9 describes the controlled removal of water and ethanol such that there is a net decrease in the volume but not a significant change in ethanol concentration of the feed.
  • An alcohol reduction apparatus shown schematically in Figure 9 comprises a membrane module, a feed beverage recirculation subsystem, an air supply subsystem with adjustable flow rate, temperature, and relative humidity, and an ethanol recovery subsystem.
  • the membrane module is of a plate-and-frame modular construction that allows circulation on both sides of the membrane unit and contains 1700 cm of effective membrane area.
  • the alcohol-reduced beverage is obtained using su b stantially the same procedure as described in Section 5.1.1, a b ove, for the operation of the apparatus shown in Figure 9.
  • Feed Wine Robot Mondavi 1985 Cabernet Red Table W ine
  • the gas-phase extraction fluid a humidified air sweep stream
  • Two wine samples are generated under conditions which are summarized in Table IV, infra.
  • the alcohol-reduced samples retain virtually all of the flavor and bouquet of the original wine. More ethanol is 63
  • Whiskies are alcoholic distillates from fermente mash of grain, stored in oak containers for maturation. T examples are disclosed to illustrate the application of th present process to removing ethanol from whiskies. An alcohol reduction apparatus similar to that described in
  • Examples 1 and 2 is equipped with a plate-and-frame membran
  • Feed whisky (Early Times ) is obtained directly from the barrel nominally at 130 proof, i.e. 65 vol% ethanol. Whisky and humidified air are supplied to the membrane as described in the preceding Section. Ethanol in the sweep air stream is recovered in a condenser. The experimental conditions and . results are shown in Table V infra.
  • Both alcohol-reduced whisky samples exhibit the taste and aroma character of the original material, but at substantially higher intensity.
  • the product whiskies also show a deeper amber color compared with the feed. This result is due to the very good retention properties of the membrane and the concentration effect associated with the approximately one-third decrease in feed volume after processing.
  • the high rates of ethanol removal observed are attributable to the high alcohol concentration in whisky.
  • the relative humidity required to balance water activities on the feed and permeate sides of the membrane is about 80%, substantially lower than that needed for processing wines . This result is consistent with the fact that whiskies contai less water than do wines and hence have lower water activities.
  • the ratio of ethanol flux to water flux is abou 13 in Example 3, and about 32 in Example 4.
  • Water lost from ' the whisky represents about 1 to 2 percent of the feed volume. This observation means that almost all of the water in the feed beverage is preserved. Feed whisky flow rates above about 300 mL/min have little effect on the performance of the system.
  • the ethanol recovered as condensate is quite high in concentration and carries with it a high value as a marketable commodity.
  • EXAMPLE NO. 5 A brandy is a distilled spirit derived from wine o fermented fruit juice. This example illustrates the alcohol reduction of a cognac (a brandy produced in the Cognac region in France) .
  • An alcohol reduction apparatus similar to that described in Examples 1 and 2 is equipped with a plate-and- frame membrane stack containing 1020 cm 2 of effective membran area.
  • Feed brandy (Remy Martin VSOP available commercially which contains about 40 vol% ethanol) and humidified air are supplied to the membrane as described in the preceding examples.
  • Ethanol in the gas-phase extraction fluid is recovered in a condenser. Experimental conditions and results are shown in Table VI, infra.
  • Water activity balance is essentially perfect in this example. Water flux is only 1.4 % of the ethanol flux, indicating that the membrane process is almost perfectly selective with respect to ethanol/water selection. The organoleptic quality of the low-alcohol brandy is very close to that of the original. Also, 93 % of the two amyl-alcohols is retained. These results indicate that the membrane exhibits a very high ethanol/congener selectivity.
  • An apparatus shown schematically in Figure 18 comprises a membrane module, a feed beverage recirculation subsystem, an air supply subsystem with adjustable flow rate and temperature, and an ethanol vapor supply subsystem comprising a metering pump and a heated vaporization/mixing chamber.
  • the membrane unit is of a plate-and-frame modular
  • a beverage or alcohol-containing solution is fed into one side of the membrane module at a given flow rate an temperature.
  • Liquid ethanol or ethanol/water azeotrope (95% ethanol) is fed by the metering pump into the mixing chamber heated to approximately 80° to 90°C, where all of the liquid is vaporized. Air is pumped through the mixing chamber and blends with the ethanol vapor to a predetermined ethanol concentration. This sweep stream is brought to operating temperature in a heat exchanger and delivered to the permeate side of the membrane module.
  • an ethanol-water mixture containing about 20 vol% ethanol and trace amounts of amyl alcohol (as a model congener) is circulated on the feed side of the membrane, and an air stream containing between 2.3 and 2.6% ethanol vapor is passed along the permeate side of the membrane.
  • Two samples are produced under conditions summarized in Table VII, infra. These product liquids contain reduced amounts of water but most of the ethanol and amy alcohol in the original mixture .
  • the water flux is over a hundred fold higher than the ethanol flux, and little ethanol is lost from the original liquid mixture; these results indicate that vapor arbitration with respect to ethanol performs as expected.
  • concentration of the amyl alcohol in the feed There is also a marked increase in the concentration of the amyl alcohol in the feed.
  • a beverage or flavor extract can be partially depleted of its water content to enhance its enthanol and congener content effectively.
  • Ethanol/water mixture temp (°C) Ethanol/water flow rate (L/min) Sweep stream temperature (°C) Sweep stream flow rate (L/min) 95% ethanol input rate (mL/min)
  • An alcohol-enriched sake sample is generated by increasing its ethanol concentration from about 20 to 25 vol % under conditions shown in Table VIII.
  • the membrane and apparatus employed are similar to those described in Example 6. Using the method of ethanol vapor arbitration, about 20 % of the water present in the original beverage is removed, but only 0.5% of the ethanol is lost. The resultant sake is 5 noticeably enriched in taste.
  • This example illustrates the fact that the same preselected membrane can be used' for alcohol reduction or alcohol enrichment simply by manipulating sweep stream conditions.

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Abstract

Procédé et appareil s'appliquant d'une manière générale à la manipulation de la concentration, apprauvrissement partiel ou enrichissement, d'un ou de plusieurs composants volatils dans un liquide donné telle que la concentration d'éthanol dans des boissons alcoolisées tout en laissant les autres composants volatils dans le liquide dans un état sensiblement non altéré ou non adultéré.
PCT/US1990/000227 1989-01-12 1990-01-11 Procede de traitement de boissons alcoolisees par evaporation au travers d'une membrane commandee par la vapeur WO1990008183A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US296,255 1989-01-12
US07/296,255 US4933198A (en) 1985-10-11 1989-01-12 Production of low-ethanol beverage by membrane extraction
US382,615 1989-07-19
US07/382,615 US5013436A (en) 1989-01-12 1989-07-19 Production of low-ethanol beverage by membrane extraction
US07/463,098 US5013447A (en) 1989-07-19 1990-01-10 Process of treating alcoholic beverages by vapor-arbitrated pervaporation
US463,098 1990-01-10

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WO1990008183A1 true WO1990008183A1 (fr) 1990-07-26

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AU (1) AU5102490A (fr)
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WO (1) WO1990008183A1 (fr)

Cited By (8)

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Publication number Priority date Publication date Assignee Title
DE3940520A1 (de) * 1989-12-07 1991-06-20 Fraunhofer Ges Forschung Verfahren zur selektiven an- oder abreicherung fluechtiger bestandteile eines fluidgemisches
EP0657205A3 (fr) * 1993-12-09 1996-03-27 Bend Res Inc Pervaporation à l'aide d'un balayage condensable à contre-courant.
ES2121562A1 (es) * 1997-05-14 1998-11-16 Consejo Superior Investigacion Procedimiento de obtencion de concentrados para elaboracion de sangrias y bebidas aromatizadas de vino.
WO2000043112A1 (fr) * 1999-01-21 2000-07-27 Membrane Extraction Technology Limited Procede d'extraction de membranes
WO2017073704A1 (fr) * 2015-10-28 2017-05-04 サントリーホールディングス株式会社 Boisson au goût d'alcool
ITUA20161859A1 (it) * 2016-03-21 2017-09-21 Francesco Iappelli Bevande da frutta fermentata a tasso alcolico definito.
WO2018204329A1 (fr) * 2017-05-01 2018-11-08 Lost Spirits Technology Llc Méthode de maturation rapide des spiritueux distillés faisant appel à des procédés à pression négative
WO2018217410A1 (fr) * 2017-05-01 2018-11-29 Lost Spirits Technology Llc Méthode pour la maturation rapide d'eaux-de-vie distillées à l'aide de procédés lumineux, thermique et à pression négative

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US4681767A (en) * 1984-04-06 1987-07-21 Henkell & Co. Method for decreasing the alcohol content of alcohol-containing beverages, particularly wine and sparkling wine
US4781837A (en) * 1984-11-21 1988-11-01 Limitinstant Limited Method of performing osmetic distillation
US4804554A (en) * 1986-01-09 1989-02-14 Norbert Barth Process for the production of fermented drinks with reduced alcohol content
US4816407A (en) * 1985-10-11 1989-03-28 Sepracor Inc. Production of low-ethanol beverages by membrane extraction
US4888189A (en) * 1987-08-17 1989-12-19 Ariel Vineyards, Inc. Simultaneous double reverse osmosis process for production of low and non-alcoholic beverages

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Publication number Priority date Publication date Assignee Title
US4681767A (en) * 1984-04-06 1987-07-21 Henkell & Co. Method for decreasing the alcohol content of alcohol-containing beverages, particularly wine and sparkling wine
US4781837A (en) * 1984-11-21 1988-11-01 Limitinstant Limited Method of performing osmetic distillation
US4816407A (en) * 1985-10-11 1989-03-28 Sepracor Inc. Production of low-ethanol beverages by membrane extraction
US4804554A (en) * 1986-01-09 1989-02-14 Norbert Barth Process for the production of fermented drinks with reduced alcohol content
US4888189A (en) * 1987-08-17 1989-12-19 Ariel Vineyards, Inc. Simultaneous double reverse osmosis process for production of low and non-alcoholic beverages

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3940520A1 (de) * 1989-12-07 1991-06-20 Fraunhofer Ges Forschung Verfahren zur selektiven an- oder abreicherung fluechtiger bestandteile eines fluidgemisches
EP0657205A3 (fr) * 1993-12-09 1996-03-27 Bend Res Inc Pervaporation à l'aide d'un balayage condensable à contre-courant.
ES2121562A1 (es) * 1997-05-14 1998-11-16 Consejo Superior Investigacion Procedimiento de obtencion de concentrados para elaboracion de sangrias y bebidas aromatizadas de vino.
WO1998051775A3 (fr) * 1997-05-14 1999-02-18 Consejo Superior Investigacion Procede d'obtention de concentres pour l'elaboration de sangrias et boissons aromatisees a base de vin
WO2000043112A1 (fr) * 1999-01-21 2000-07-27 Membrane Extraction Technology Limited Procede d'extraction de membranes
WO2017073704A1 (fr) * 2015-10-28 2017-05-04 サントリーホールディングス株式会社 Boisson au goût d'alcool
JPWO2017073704A1 (ja) * 2015-10-28 2018-07-26 サントリーホールディングス株式会社 アルコールテイスト飲料
AU2016346552B2 (en) * 2015-10-28 2021-02-04 Suntory Holdings Limited Alcohol-tasting beverage
ITUA20161859A1 (it) * 2016-03-21 2017-09-21 Francesco Iappelli Bevande da frutta fermentata a tasso alcolico definito.
WO2018204329A1 (fr) * 2017-05-01 2018-11-08 Lost Spirits Technology Llc Méthode de maturation rapide des spiritueux distillés faisant appel à des procédés à pression négative
WO2018217410A1 (fr) * 2017-05-01 2018-11-29 Lost Spirits Technology Llc Méthode pour la maturation rapide d'eaux-de-vie distillées à l'aide de procédés lumineux, thermique et à pression négative

Also Published As

Publication number Publication date
NZ232088A (en) 1991-08-27
AU5102490A (en) 1990-08-13

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