WO1994013159A1 - Concentration osmotique - Google Patents

Concentration osmotique Download PDF

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Publication number
WO1994013159A1
WO1994013159A1 PCT/US1993/011824 US9311824W WO9413159A1 WO 1994013159 A1 WO1994013159 A1 WO 1994013159A1 US 9311824 W US9311824 W US 9311824W WO 9413159 A1 WO9413159 A1 WO 9413159A1
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WO
WIPO (PCT)
Prior art keywords
juice
wine
chamber
osmotic concentration
osmotic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1993/011824
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English (en)
Inventor
John R. Herron
Edward G. Beaudry
Rob Mommsen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osmotek Inc
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Osmotek Inc
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Filing date
Publication date
Priority claimed from US07/986,921 external-priority patent/US5281430A/en
Application filed by Osmotek Inc filed Critical Osmotek Inc
Priority to EP94903482A priority Critical patent/EP0683631A4/fr
Priority to AU57410/94A priority patent/AU5741094A/en
Publication of WO1994013159A1 publication Critical patent/WO1994013159A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F5/00—Coffee; Coffee substitutes; Preparations thereof
    • A23F5/24—Extraction of coffee; Coffee extracts; Making instant coffee
    • A23F5/28—Drying or concentrating coffee extract
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
    • A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
    • A23L2/72—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration
    • A23L2/74—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration using membranes, e.g. osmosis, ultrafiltration
    • 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
    • B01D61/002—Forward osmosis or direct osmosis
    • B01D61/0023—Accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B01D63/084—Flat membrane modules comprising a stack of flat membranes at least one flow duct intersecting the membranes
    • B01D63/085—Flat membrane modules comprising a stack of flat membranes at least one flow duct intersecting the membranes specially adapted for two fluids in mass exchange flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/02—Forward flushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/20—By influencing the flow
    • B01D2321/2008—By influencing the flow statically
    • B01D2321/2016—Static mixers; Turbulence generators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/30—Mechanical cleaning, e.g. with brushes or scrapers

Definitions

  • the present invention relates to an osmotic concentration apparatus and osmotic concentration cell having a configuration which promotes turbulence at a first membrane surface to prevent fouling of the membrane surface.
  • the cell may also be used as a dialysis cell.
  • the present invention further relates to a method for making a low alcohol wine or other fermented beverage, a method for improving the quality of a wine beverage, a process to provide a grape juice concentrate from mid to early harvest grapes that can be used for a desert wine, and a method for improving the quality of a grape juice concentrate used for wine fermentation.
  • Osmotic concentration cells are often used to concentrate food products, such as fruit juices, by selectively removing water.
  • water diffuses from the food product to be concentrated through a semipermeable membrane into a solution having a much lower water content.
  • Osmotic concentration systems are of interest to concentrate food products without use of heat that may damage the food product, such as a fruit juice or a grape juice used in wine making. This prevents much of the quality degradation associated with evaporative processes.
  • Food products of particular interest for osmotic concentration include other fruit and vegetable juices, agricultural products such as aloe vera, and pharmaceutical and biopharmaceutical products.
  • freeze concentration can eliminate self-oxidation problems and produce a higher quality juice than evaporators.
  • RO reverse osmosis
  • DOC direct osmotic concentration
  • Freeze concentration can eliminate self-oxidation problems and produce a higher quality juice than evaporators.
  • problems associated with freeze concentration including: (1) only clarified juices can be concentrated, (2) some minor juice constituents are lost, and (3) capital costs of a commercial scale freeze concentration plant is many times that of an evaporation plant. Accordingly, the costs for freeze concentration are prohibitive, making this process not economically feasible, especially in wine making operations.
  • RO operates by squeezing water out of a juice through a semipermeable membrane (a thin polymer which has been manufactured to be porous).
  • semipermeable membranes the pore structure is small enough that small molecules, such as water, can pass through, while larger organic molecules are prevented from passing.
  • Drawbacks to RO are that the membranes foul rapidly and extremely high pressures (e.g., 3000 psi) are needed to form a juice concentrate.
  • Direct osmotic concentration has been studied less than other cold concentration processes. DOC uses semipermeable membranes.
  • DOC instead of squeezing water out with pressure, DOC uses a solution with a lower mole fraction of water to pull water out of a product.
  • This solution with a low mole fraction of water is an osmotic agent (OA).
  • OA osmotic agent
  • any water pulled from the product into the OA must be subsequently removed from the OA, preferably by evaporation, in order for the OA to be recycled. Evaporation of the OA does not effect product quality because the product itself is not heated. Since DOC requires an evaporation step, its energy requirement is similar to evaporative concentration.
  • Concentrating products containing large organic molecules and solutions with suspended solids creates severe membrane fouling problems, particularly in RO systems. Even when a product is first filtered to remove suspended solids, there is severe fouling due to deposition of films on the surfaces of the semipermeable membrane. Such films are composed of large molecules such as polypeptides, pectins and polysaccharides. Large organic molecules adhere to the surface of the membrane due to Nan der Waals attraction. After attachment, the large molecules slowly denature and unfold and then form multiple hydrogen bonding and multiple ionic interactions with the membrane. Therefore, it is desirable to induce a high degree of turbulence at the membrane surface to sweep these molecules away from the membrane surface before they adhere due to stronger bond formation.
  • Another method for concentrating juices to a high Brix level in an RO system first removes all large molecules by ultrafiltration before RO concentration. This method allows for concentration of a 60 Brix juice. However this method is relatively expensive, is difficult to maintain in view of the ultrafiltration step, and is energy intensive.
  • Osmotic potential is a measure of the tendency of water to diffuse through a membrane from a region of high water concentration to a region of lower water concentration.
  • q cRT, wherein c is the molar concentration of non-water species in a solution, R is a gas constant, and T is the absolute temperature.
  • RO systems pressure differences are large but the osmotic potential of a permeate (the solution water is pushed into) is essentially zero.
  • DOC systems pressure differences are negligible and flux depends on the difference in osmotic potential.
  • the value of the flux constant k w is determined by molecular-scale hydrodynamic resistance to flow through the membrane pores.
  • RO systems use extremely thin membranes (e.g., less than 0.01 mm thick) supported by a porous backing wherein the backing provides structural properties to the membrane to be able to withstand high applied pressure.
  • the pores in the back are much larger than pores in the membrane, hence the backing contributes little to flow resistance across the membrane.
  • DOC k w values are primarily controlled by diffusion rates. Diffusion rates are less dependent upon pore diameter than hydrodynamic flow rates. Thus, in DOC cells, the presence of a membrane backing can severely reduce flux rates. Therefore, DOC membranes and their backings, if any, must be as thin as possible.
  • Boundary layers are thin regions in the fluid next to a membrane surface where mixing with bulk fluid is ineffective.
  • An impact of boundary layers is creation of an extra region that water must diffuse through.
  • Boundary layers are often avoided by using high fluid velocity (turbulent flow if possible) to sweep away boundary layers. Therefore, it is important in this art to design a flow cell configuration to avoid dead spots in fluid flow near membranes.
  • the present invention was made, in part, to solve some of the problems of DOC systems for juice concentrators and dialysis systems.
  • the flavorings and aroma agents that form the bouquet and other such substances of a wine beverage include about 400 to 600 different substances, such as higher alcohols, esters, aldehydes, ketones, lactones, etc.
  • the total volume of such substances is only about 0.5% to about 1% of the wine volume.
  • many of these substances are volatile with their boiling points being below and above the boiling point for ethanol. These substances also overlap the corresponding properties of ethanol with regard to their extraction behavior.
  • Dilution of fermented beverages during alcohol removal is undesirable because, by itself, removal of alcohol decreases the sensory impact of beverage flavors. A dilution of the product further decreases product flavor.
  • U.S. Patent 4,867,997 describes a complicated high-pressure extraction process in the presence of carbon dioxide in a supercritical fluid state. Therefore, there is a need in the art to find an improved process to make a low alcohol fermented beverage (e.g., wine, beer or champagne) that retains the flavor and aroma characteristics of the original beverage.
  • the present invention was made to achieve such a goal.
  • the present invention provides an osmotic concentration cell and an osmotic concentration apparatus (comprising an array or plurality of osmotic concentration cells), wherein each cell has a first chamber with a fluid flow design with high turbulence at a first semipermeable membrane surface wherein a flow path of the first chamber has a continual change in flow direction.
  • the osmotic agent (OA) flows on the second side of the semipermeable membrane in a second chamber, preferably in a torturous path between support members, and in the same net direction as the flow and with a slightly lower pressure than the juice.
  • each osmotic concentration cell comprising an enclosed apparatus having one or two semipermeable membranes per cell, each semipermeable membrane having a first side defining a first chamber and a second side defining a second chamber.
  • the semipermeable membrane rests on support members (such as rod- shaped support members) spaced from about 1 cm to about 10 cm apart, wherein the support members are within the second chamber.
  • support members such as rod- shaped support members
  • This flow path is called “corrugated.”
  • the juice flow path is continually changing, in a "serpentine" pattern, wherein the radius of curvature of the juice flow path is from about 1.5 cm to about 4.5 cm depending upon the distance between the support members. Preferably, the radius of curvature is about 2.0 cm.
  • the osmotic concentration apparatus further comprises one or a plurality of enclosed cells having a flow inlet opening leading to the first chamber of each cell, a flow outlet communicating with the first chamber of each cell, an OA inlet and an OA outlet connected to each second chamber.
  • the second chamber of an osmotic concentration apparatus is defined by internal walls of the osmotic concentration apparatus and the second sides of the semipermeable membranes.
  • the present invention further comprises a DOC method for selectively removing water from a juice in an osmotic concentration cell or apparatus, comprising: (a) providing a juice in a continuous flow stream to a juice inlet, (b) pumping the juice at a pressure of from about 1 to about 30 psi through a first chamber and out a juice outlet, and wherein the first chamber comprises a continually changing direction flow path, wherein the radius of curvature of the continually changing direction flow path is from about 1.5 cm to about 4.5 cm., (c) providing an OA in a second chamber, wherein the second chamber is defined by the second side of a semipermeable membrane and enclosed by the cell, and wherein the OA comprises the salt components of the juice at a molar concentration at least three times and preferably at least five times greater than the undiluted juice.
  • the OA further comprises at least 50 weight
  • the present invention further comprises a method for removing water from grape juice used for wine making, comprising: (a) providing a grape juice to a juice inlet in an osmotic concentration apparatus described herein; (b) providing an OA to the OA chamber, wherein the
  • OA comprises from about 30% to about 85% by weight sugar; (c) applying greater pressure to the grape juice than to the OA to deflect the semipermeable membrane into a corrugated flow path; and (d) removing water from the grape juice.
  • Water is preferably removed from grape juice to produce a grape juice similar to a late-harvest grape juice by increasing the solids content of the grape juice, or to compensate for a short growing season to increase the solids content of the grape juice to make a stronger wine that could not otherwise be produced by nature, or to produce a dessert wine by concentrating grape juice.
  • the present invention further comprises a method for producing a low alcohol wine, comprising: (a) providing wine to a juice inlet in an osmotic concentration apparatus described herein; (b) providing an OA to the OA chamber, wherein the OA comprises from about 10% to about 30% by weight sugar; (c) applying greater pressure to the wine than to the OA to deflect the semipermeable membrane into a corrugated flow path; and (d) removing mostly alcohol from the wine.
  • the application of pressure in step (c) is accomplished with nitrogen pressurization to avoid any unnecessary shear pressure on the wine.
  • the present invention further comprises a method for strengthening wine, comprising: (a) providing wine to a juice inlet in an osmotic concentration apparatus described herein; (b) providing an OA to the OA chamber, wherein the OA comprises from about 25% to about 50% by weight sugar; (c) applying greater pressure to the wine than to the OA to deflect the semipermeable membrane into a corrugated flow path; and (d) removing approximately equal percentages of alcohol and water from the wine.
  • the inventive method further comprises recycling the OA by selectively distilling off alcohol and water to restore the original weight percentage of sugar in the OA.
  • the OA further comprises at least 1 mM of an organic acid.
  • the organic acids in the OA are selected from the group consisting or malic acid, citric acid, tartaric acid, ascorbic acid, and combinations thereof.
  • Figure 1 illustrates a side view of a portion of an osmotic concentration cell.
  • the supports members are straight bars a ⁇ -anged in parallel which extend into and out of the page. In this cell, the distance between support member centers is about 2.5 cm and the height of the support members is about 2 cm.
  • the pressure difference between the juice and OA is held below 30 psi and the radius of curvature (i.e., deflection) of the membrane between the support members is about 2.0 cm.
  • the flow path is shown by the curving arrow between the membranes. Due to a continual change in flow direction, the flow path induces a high degree of turbulence.
  • the OA flows through a gap between the support members (i.e., second chamber), preferably in a direction perpendicular to the juice flow direction.
  • Figure 2 illustrates a diagram of half (bottom portion) of an inventive DOC apparatus.
  • the top portion of the apparatus (not shown) is identical except for positioning of support members, juice inlet and exit ports.
  • the apparatus shown in Figure 2 is a miniature lab scale pilot model having a top cell and a bottom cell but not having any middle cells.
  • a commercial scale apparatus would have much larger width and length and a greater number of cells (e.g. middle cells), however, the spacing between support members and operating pressures would be similar to the illustrated lab scale model.
  • FIG. 3 is a schematic diagram of the inventive direct osmotic concentration (DOC) process to concentrate a juice and remove water from the OA by a evaporation process.
  • DOC direct osmotic concentration
  • Figure 4 shows a graph of water flux rate from orange juice during a concentration process described in Example 2 herein. A least squares analysis shows that the rate of concentration was linear with time indicating that there was no significant membrane fouling that could impede performance of the apparatus.
  • Figure 5 shows a graph of flux constant versus time of concentration measuring either the tomato juice or the OA.
  • the line for flux of water into the OA is relatively linear over time, indicating that there is very little, if any, membrane fouling.
  • Figure 6 shows flux from concentrating coffee described in Example 4 herein. The Brix numbers for coffee increased linearly.
  • Figure 7 shows a stacking design to stack a plurality of modules in a relatively small area.
  • the present invention provides an osmotic concentration cell and apparatus that have a novel design for flow of a juice providing for high turbulence at a first side of a semipermeable membrane that defines a first chamber.
  • the flow path of the juice to be concentrated is called "corrugated" because there is a continual change in flow path direction. It is this corrugated flow path that provides for a high amount of turbulence at the first side of the membrane and acts to significantly prevent fouling of the membrane.
  • presence of suspended solids within the juice can further act as a abrasive agent to continually cleanse the first side of the semipermeable membrane and further prevent membrane fouling.
  • the present invention provides an osmotic concentration cell and an osmotic concentration apparatus (comprising an array or plurality of osmotic concentration cells), wherein each cell has first chamber with a fluid flow design with high turbulence at a first semipermeable membrane surface by having a flow path of the first chamber with a continual change in flow direction.
  • the osmotic agent (OA) flows on the second side of the semipermeable membrane in a second chamber with a slightly lower pressure than the juice.
  • the juice refers to any liquid that is to be concentrated by selectively removing water or another species, such as alcohol to create a concentrated juice.
  • the concentrated juice may be a low alcohol wine or a concentrated thin wine.
  • juices that are concentrated to remove water as the solvent include any fruit juice (e.g., orange, apple, red raspberry, pear, cranberry, guava, grapefruit, lemon, other citrus fruits, tropical fruits or berries), vegetable juices such as tomato or carrot juices, coffees and teas, milk and diary products and specialty juices such as aloe vera, and perfumes and flavoring agents.
  • juices may be processed to remove other solvents, such as alcohol and/or water from alcoholic beverages, such as beer or wine to create low alcohol beers or wines or premium wines from thin, low-grade wines.
  • Concentration of a juice is determined by the Brix number. Brix is a measure of percentage of dissolved solids. Therefore, selective removal of a solvent from the juice will increase the percentage of dissolved solids and the Brix number.
  • each osmotic concentration cell comprising an enclosed apparatus having one or two semipermeable membranes per cell, each semipermeable membrane having a first side defining a first chamber and a second side defining a second chamber.
  • the semipermeable membrane wraps around support members (such as rod-shaped support members) spaced from about 1 cm to about 10 cm apart, wherein the support members are within the second chamber.
  • each cell further comprises a sealing device, such as an O-ring that surrounds the semipermeable membrane to seal it and prevent leakage of liquid contents around the semipermeable membrane.
  • the apparatus and cell is made from a rigid material suitable to contact for the particular juice and OA that flows within the cell or apparatus. If food juices are being concentrated, examples of suitable rigid materials include stainless steel, polycarbonate, or other food-grade polymeric materials. The juice preferably contacts only the first surface of the semipermeable membrane and not the material that forms the walls of the cell or apparatus.
  • the semipermeable membrane is either hydrophobic for non-aqueous juices or hydrophilic for aqueous juices.
  • hydrophilic membranes include membranes composed of cellulose acetate, cellulose triacetate, polysulfones, other polymeric hydrophilic materials, and composite membranes formed from combinations of the foregoing materials.
  • the juice flow path is continually changing, in a serpentine pattern, wherein the radius of curvature of the juice flow path is from about 1.5 cm to about 4.5 cm depending upon the distance between the support members.
  • the radius of curvature is about 2.0 cm.
  • appropriate pressure differences between the first and second chambers is from about 1 to about 30 psi.
  • the osmotic concentration apparatus further comprises one or a plurality of enclosed cells having a flow inlet opening leading to the first chamber of each cell, a flow outlet communicating with the first chamber of each cell, an OA inlet and an OA outlet connected to each second chamber.
  • the second chamber of an osmotic concentration apparatus is defined by internal walls of the osmotic concentration apparatus and the second sides of the semipermeable membranes.
  • the apparatus is composed of a plurality of stackable module cells.
  • the top and bottom cells comprise the outer walls of the apparatus and one or a plurality of middle cells comprise the middle modules.
  • the middle modules, or cells have no outer walls, but instead have a frame support holding the parallel support members.
  • the semipermeable membranes are placed inside the rows of support members and sealed into place with an appropriate sealing device, such as an O-ring or with an adhesive agent.
  • the semipermeable membranes can be replaced when the modular apparatus is disassembled into its component modules.
  • Each module can be stacked to reduce total area of the apparatus. An example of one stacking arrangement of three modules is shown in Figure 7.
  • the apparatus can be operated in a horizontal, inclined, or preferably, in a vertical orientation.
  • the advantage of vertical orientation is easier removal of bubbles as well as easier assembly and maintenance.
  • the support members are arranged in parallel to support formation of a "corrugated" flow path with each first chamber when greater pressure is applied to the first chamber to deflect the semipermeable membrane into the second chamber.
  • the support members can be any shape so long as there is a rounded surface contacting the second side of the semipermeable membrane. Examples of appropriate shapes are rods, rounded cones or boxes with at least one rounded face.
  • a novel feature of the inventive osmotic concentrator cell is controlled deflection of the semipermeable membrane between support members to provide a flow path with continually changing direction and a high amount of turbulence on the first side of the membrane. This provides for an osmotic concentration cell that can concentrate liquids with gel forming dissolved solids, such as aloe vera or orange juice with pulp that could not otherwise be concentrated in DOC or RO systems.
  • FIG. 1 A diagram of a section of a cell is provided in Figure 1.
  • the product being concentrated flows along the first side of a semipermeable membrane that is deflected between two sets of support members by virtue of a higher pressure in the first chamber than in the second chamber. Due to the offset positioning of each set of parallel support members, a corrugated flow pattern is formed in the first chamber.
  • the continuous direction changes for the flow produces a high amount of turbulence at the first side of the semipermeable membrane, the side most prone to fouling.
  • a sheer fabric support can be used as a backing on the second side of the membrane. This support can be either attached to the frame or fused with the membrane.
  • the inventive design also reduces membrane stress and susceptibility to bursting. This is important because thin membranes are preferred for DOC systems.
  • resistance of a membrane to pressure induced bursting is inversely related to the membrane radius of curvature. Therefore a deflection to form a radius of curvature from about 1 to about 4 cm, and preferably from about 2 to about 3 cm, allows the inventive osmotic concentrator cell and apparatus to use extremely thin membranes.
  • the design of the osmotic concentration cells allows for construction of an osmotic concentration apparatus in a plate and frame type structure.
  • a plate and frame structure allow for the use of relatively inexpensive sheet semipermeable membranes and allows for rapid instillation and replacement of membranes.
  • Such a design is shown in Figure 7.
  • a diagram of the flow paths of an osmotic concentration apparatus is shown in Figure 2.
  • the OA flows in second chambers in a torturous path between support members in the same net direction as the flow.
  • membrane seals to prevent leakage between the flow chambers and the OA chambers are made by compressing ends of membranes between gaskets (i.e., O-rings) mounted to boxes in the OA chambers.
  • the osmotic agent is designed to osmotically pull the selected solvent (usually water for fruit or vegetable juices or ethanol for beer or wine) from the juice into the OA.
  • the osmotic pressure is initially greater for solutes (e.g., salts, sugars, glycols, and organic volatile agents such as flavors or perfume ingredients) in the OA.
  • solutes e.g., salts, sugars, glycols, and organic volatile agents such as flavors or perfume ingredients
  • the composition of the OA depends upon the particular juice to be concentrated and what are the solutes in solution in the juice.
  • the OA for fruit or vegetable juices can comprise sugars, such as high fructose corn syrup. The question of whether the sugars from the OA migrate into the concentrated juice was investigated by monitoring the stable carbon isotope ratios in the juice and the OA.
  • the ratios of the OA sugar and juice sugar naturally differ to a great extent. It was found that the ratios did not change during the inventive juice concentrating process. Therefore, sugars did not cross the membrane.
  • flavoring agents include organic acids such as malic, citric and tartaric acids.
  • the OA should contain less than about 75 weight % sugar.
  • the OA should be recycled by evaporating the selected solvent removed from the juice.
  • the OA only is heated, thus allowing cold concentration of a juice to prevent breakdown of any heat sensitive components in a juice.
  • the result of the Inventive DOC process using the inventive cell or apparatus is a higher quality concentrated juice that retains its flavor characteristics better that a similar juice concentrated by an evaporative process. Further, the high turbulence at the first side of the semipermeable membrane prevents membrane fouling and leads to longer lasting membranes with more infrequent membrane changes to provide a more cost effective and higher quality juice concentration process.
  • the present invention further comprises a DOC method for removing a selected solvent from a juice in an osmotic concentration cell or apparatus, comprising: (a) providing a juice in a continuous flow stream to a juice inlet, (b) pumping the juice at a pressure of from about 1 to about 30 psi through a first chamber and out a juice outlet, wherein the first chamber comprises a continually changing direction flow path, wherein the radius of curvature of the continually changing direction flow path is from about 1.5 cm to about 4.5 cm., (c) providing an OA in a second chamber, wherein the second chamber is defined by the second side of a semipermeable membrane and enclosed by the cell, and wherein the OA comprises the salt components of the juice at a molar concentration at least three times and preferably at least five times greater than the undiluted juice.
  • the OA further comprises at least 50 weight % of a sugar, wherein the sugar is selected from the group consisting of sucrose, fructose, maltose, glucose, and
  • the present invention further provides a process for improving the quality of a fruit juice used to make a wine, comprising: (a) providing a thin, low grade fruit juice composition to a juice inlet in an osmotic concentration apparatus described herein; (b) providing an OA to the OA chamber, wherein the OA comprises from about 50% to about 75% by weight sugar; (c) applying greater pressure to the fruit juice than to the OA to deflect the semipermeable membrane into a corrugated flow path; (d) removing water from the fruit juice; and (e) collecting an improved fruit juice product.
  • the inventive method further comprises recycling the OA by selectively distilling off water to restore the original weight percentage of sugar in the OA.
  • the OA further comprises at least 1 mM of an organic acid.
  • the organic acids in the OA are selected from the group consisting or malic acid, citric acid, tartaric acid, and combinations thereof.
  • the present invention further provides a process to make a grape juice that can be used for a desert wine by concentrating the grape juice to about 36 to about 40 degree Brix from a grape juice from "fully ripe" grapes (i.e., approximately 23 degrees Brix) by a process comprising: (a) providing a grape juice composition from fully ripe grapes to a juice inlet in an osmotic concentration apparatus described herein; (b) providing an OA to the OA chamber, wherein the OA comprises from about 50% to about 75% by weight sugar; (c) applying greater pressure to the grape juice than to the OA to deflect the semipermeable membrane into a corrugated flow path; (d) removing water from the grape juice; and (e) collecting an concentrated grape juice product that can be used to make a desert wine.
  • the inventive method further comprises recycling the OA by selectively distilling off water to restore the original weight percentage of sugar in the OA.
  • the OA further comprises at least 1 mM of an organic acid.
  • the organic acids in the OA are selected from the group consisting or malic acid, citric acid, tartaric acid, and combinations thereof.
  • a fermented beverage i.e., wine, beer or champagne
  • sugar i.e., from about 30% to about 85%
  • Lower sugar concentrations i.e., from about 3% to about 20%
  • a beverage/wine can be strengthened without changing the percentage alcohol content by using an intermediate (15-50% brix) concentration OA that removes water and alcohol at rates proportional to their concentrations in the beverage.
  • the inventive methods are based upon the discovery that it is not necessary to provide an OA consisting of an alcohol-free beverage or a fruit juice. Instead, the OA need only comprise sugar and water with the amount of sugar controlling the relative rates of water and alcohol removal. It is further important, when working with a delicate beverage such as a wine, to avoid shearing the beverage. Therefore, the apparatus is preferably pressurized by applying an inert gas (i.e., nitrogen) or at least a gas that avoids oxidation of the beverage, on the juice/wine side of the outlet to maintain the beverage in an inert atmosphere throughout the concentration procedure.
  • an inert gas i.e., nitrogen
  • One surprising feature of the inventive apparatus is an ability to concentrate a thin, low grade wine into a wine of much higher quality by removing both alcohol and water from the beverage.
  • the inventive method using the inventive apparatus can improve wine quality by upgrading lower grade wines (by virtue of a thin body and concentration of favoring agents) into a higher quality wine. This feature is a great significance to the wine industry.
  • EXAMPLE 1 This example illustrates the construction of a pilot scale prototype of the inventive DOC apparatus comprising one cell consisting of a top module and a bottom module that was made for conducting the following experiments to concentrate different juices. Additionally, middle modules to create a plurality of cells in an apparatus was made to increase the efficiency of the apparatus by creating additional first chambers to increase the throughput of the DOC apparatus.
  • the top module and bottom module are mirror image components (except for offset placement of the support members, i.e., rods) in a rectangular shape.
  • the pilot model was made of polycarbonate in a 28 cm by 100 cm rectangular dimension. Each component is 2.5 cm thick and the interior space houses the parallel rod-shaped support members, also made of polycarbonate affixed by solvent fusing.
  • the support membranes were placed 2.5 cm apart. The interior space is rectangular-shaped and encircled by an O-ring to help seal the membrane.
  • a cellulose triacetate semipermeable membrane having a 100 molecular weight cutoff was placed on each interior, rectangular space such that it slightly overlaps the interior space and is sealed together to form the first chamber when the top and bottom modules are joined to form a DOC cell having one first chamber and two second chambers.
  • a middle module was made comprising a polycarbonate rectangular frame of the same dimensions as the top and bottom modules.
  • the interior space of the middle module comprises a row of parallel support members having curved surfaces extending from either side of the middle module.
  • the support members were placed 2.5 cm apart.
  • a sealing means i.e., O-rings
  • Two semipermeable membranes are placed on either side of the interior space of the middle module when the apparatus is assembled.
  • the result is a stackable apparatus with a top, bottom and middle modules having two first chambers and three second chambers. Additional middle modules will increase the number of first chambers and second chambers by one.
  • the clear plastic (polycarbonate) cells allows for visualization of juice and OA flows and determination if there are difficulties with bubbles and the like.
  • the entire apparatus can be moved to a temperature-controlled room, such as a cold room to help to preserve the juice from heat degradation or microbial contamination.
  • the apparatus can be jacketed to control temperatures within the apparatus by pumping an appropriate temperature liquid through the jacket.
  • This example illustrates concentration of an orange juice using the inventive pilot scale apparatus described in Example 1. Approximately 6 liters of fresh orange juice, Brix 12.6, was obtained. Approximately 6 gallons of OA was prepared with 100% PEG (polyethylene glycol) MW 300. The module had a length of 61 inches, 100 molecular weight cutoff triacetate membrane, and 90 mm membrane thickness.
  • PEG polyethylene glycol
  • Figure 4 shows a graph of flux time versus Brix of the orange juice.
  • the orange juice was concentrated to about 50 Brix by transferring water from the orange juice to the OA.
  • the rate of concentration was about linear with time indicating that there was not a significant membrane fouling problem that could impede performance of the apparatus.
  • the Brix of the OA decreased correspondingly. Accordingly, orange juice with a high suspended solids content due to a high content of pulp, can be significantly concentrated in the inventive apparatus to almost five times more concentrated without fouling the membrane surface.
  • Conventional DOC or RO processes would have experience significant membrane fouling with a high suspended solids content orange juice that could not have economically produced high quality orange juice concentrate.
  • This example illustrates concentration of a tomato juice using the inventive pilot scale apparatus described in Example 1.
  • Approximately 2.3 gallons of tomato juice, Brix 6.0 was obtained from Nestle.
  • Figure 5 shows a graph of a flux constant versus time of concentration measuring either the juice or the O A. This graph shows that the flux of water into the OA is relatively linear over time, indicating that there is very little, if any, membrane fouling.
  • This example illustrates concentration of coffee as a step in the production of instant coffee or liquid coffee concentrates.
  • Successive coffee batches have been concentrated from 5 Brix to between 56 and 63 Brix using 60-70 Brix HFCS (high fructose corn syrup - 55% fructose, 42% glucose, 3% sucrose) as the OA.
  • HFCS high fructose corn syrup - 55% fructose, 42% glucose, 3% sucrose
  • This example illustrates concentration of a raspberry juice using a HFCS OA.
  • C13 levels in the sugars in the raspberry juice and the OA are shown in Table 2. These data show that no detectable amount of sugar passed from the OA into the juice.
  • Table 2 below provides stable carbon isotope data of red raspberry juice and concentrates and the OA before and after processing.
  • This example illustrates the results of wine making experiments to produce a low alcohol wine.
  • the resulting juice was diluted with water, prior to fermentation, to reduce the Brix level to 11 degrees.
  • the potential alcohol content of the wine after fermentation of the diluted juice would now be about 6.2%. All of the pomace (pressed skins and seeds) was re-slurried with part of the diluted juice to the original volume of 10 gallons.
  • the alcohol content of the wine made from the undiluted red wine must was 12.6%, and 6.0% from the diluted must.
  • the 12.6% alcohol wine was, for all practical purposes, a normal, high quality dry, red table wine.
  • the 6.0% alcohol wine had good color and good aroma, but the fruit flavor of the wine was dilute and had a thinner feel in the mouth than the higher alcohol wine.
  • OA high fructose corn syrup
  • This example illustrates the results of wine making experiments to improve the quality of a low grade wine.
  • the OA was HFCS of between 50 and 70 Brix.
  • the original wine (not subject to DOC) had an alcohol content of
  • This example illustrates the results of wine making experiments to concentrate grape juice to make a desert wine without waiting for late harvest grapes.
  • the resulting concentrated juice was diluted slightly to 37 degrees Brix with untreated
  • the unconcentrated juice had a potential alcohol content, after vinification, of 14.9% and little or no potential as a sweet, high alcohol, desert wine.
  • the concentrated juice had a potential alcohol content, after vinification, of 20.4%.
  • alcohol levels above 15% are toxic to wine yeast, so the concentrated juice had the potential for vinification into a desert wine of 15 to 16% alcohol with a residual sugar level of 8% to 10%.
  • one advantage of the present invention is an ability to use normal harvest grape juice to make a high quality desert wine.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Non-Alcoholic Beverages (AREA)

Abstract

L'invention concerne une cellule de concentration osmotique dont la chambre d'écoulement définie par une membrane semi-perméable présente une voie d'écoulement changeant constamment afin de créer une région à forte turbulence dans ladite membrane. Une forte turbulence au niveau d'une interface membranaire semi-perméable permet de réduire sensiblement l'encrassement de la membrane pendant la concentration osmotique et d'utiliser une cellule de concentration à des fins multiples telles que, par exemple, la production de vin à faible teneur en alcool, la concentration d'un vin sans corps en vin de qualité, d'un jus de raison de qualité médiocre en jus de raison de meilleure qualité afin d'obtenir par fermentation un vin de qualité supérieure, de divers jus de fruit ou de légume ainsi que de diverses boissons telles que le thé ou le café.
PCT/US1993/011824 1992-12-08 1993-12-06 Concentration osmotique Ceased WO1994013159A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94903482A EP0683631A4 (fr) 1992-12-08 1993-12-06 Concentration osmotique.
AU57410/94A AU5741094A (en) 1992-12-08 1993-12-06 Osmotic concentration

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/986,921 US5281430A (en) 1992-12-08 1992-12-08 Osmotic concentration apparatus and method for direct osmotic concentration of fruit juices
US07/986,921 1992-12-08
US11327993A 1993-08-27 1993-08-27
US08/113,279 1993-08-27

Publications (1)

Publication Number Publication Date
WO1994013159A1 true WO1994013159A1 (fr) 1994-06-23

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Cited By (6)

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WO1998000225A1 (fr) * 1996-06-28 1998-01-08 Krebs & Co. Ag Procede de pervaporation et module de mise en oeuvre dudit procede
EP0893065A3 (fr) * 1997-07-25 1999-05-26 Kraft Foods, Inc. Extrait de café aromatisé liquide à haute concentration et café liquide ainsi obtenu
WO2016038433A1 (fr) * 2014-09-12 2016-03-17 Kraft Foods R & D, Inc. Fabrication de produits pour boisson solubles
CN110290854A (zh) * 2016-12-23 2019-09-27 波里费拉公司 通过正向渗透除去醇溶液的组分和相关系统
US11571660B2 (en) 2015-06-24 2023-02-07 Porifera, Inc. Methods of dewatering of alcoholic solutions via forward osmosis and related systems
US11759751B2 (en) 2012-12-21 2023-09-19 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers

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US3052546A (en) * 1961-06-16 1962-09-04 Vie Del Grape Products Company Concentrated de-alcoholized wine product
US4581236A (en) * 1979-06-15 1986-04-08 Akzo N.V. Process and apparatus for reduction of alcohol by dialysis in fermented beverages
US4664918A (en) * 1980-03-14 1987-05-12 Akzo Nv Process for reducing alcohol in fermented beverages by means of dialysis
US4988525A (en) * 1987-08-28 1991-01-29 Bucher-Guyer Ag Maschinenfabrik Process for selective removal of volatile substances from liquids, as well as unit and device for carrying out the process
US4942045A (en) * 1988-10-06 1990-07-17 Chateau Yaldara Pty. Ltd. Grape juice concentrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998000225A1 (fr) * 1996-06-28 1998-01-08 Krebs & Co. Ag Procede de pervaporation et module de mise en oeuvre dudit procede
EP0893065A3 (fr) * 1997-07-25 1999-05-26 Kraft Foods, Inc. Extrait de café aromatisé liquide à haute concentration et café liquide ainsi obtenu
US11759751B2 (en) 2012-12-21 2023-09-19 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
WO2016038433A1 (fr) * 2014-09-12 2016-03-17 Kraft Foods R & D, Inc. Fabrication de produits pour boisson solubles
US11571660B2 (en) 2015-06-24 2023-02-07 Porifera, Inc. Methods of dewatering of alcoholic solutions via forward osmosis and related systems
CN110290854A (zh) * 2016-12-23 2019-09-27 波里费拉公司 通过正向渗透除去醇溶液的组分和相关系统
EP3559197A4 (fr) * 2016-12-23 2020-09-16 Porifera, Inc. Élimination de composants de solutions alcooliques par osmose directe et systèmes associés
US11541352B2 (en) 2016-12-23 2023-01-03 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems
US12390767B2 (en) 2016-12-23 2025-08-19 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems

Also Published As

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EP0683631A1 (fr) 1995-11-29
AU5741094A (en) 1994-07-04
EP0683631A4 (fr) 1996-09-04

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