WO1994027451A1 - Method for producing a natural citrus pulp thickener, stabilizer and cloud agent for beverages - Google Patents

Method for producing a natural citrus pulp thickener, stabilizer and cloud agent for beverages Download PDF

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Publication number
WO1994027451A1
WO1994027451A1 PCT/US1994/005672 US9405672W WO9427451A1 WO 1994027451 A1 WO1994027451 A1 WO 1994027451A1 US 9405672 W US9405672 W US 9405672W WO 9427451 A1 WO9427451 A1 WO 9427451A1
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WIPO (PCT)
Prior art keywords
slurry
log
insoluble solids
citrus
thickener composition
Prior art date
Application number
PCT/US1994/005672
Other languages
French (fr)
Inventor
Robert Earl Tarr
David Lee Montezinos
Paul Ralph Bunke
Donald Elmer Weik
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU69170/94A priority Critical patent/AU6917094A/en
Publication of WO1994027451A1 publication Critical patent/WO1994027451A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/62Clouding agents; Agents to improve the cloud-stability
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L19/00Products from fruits or vegetables; Preparation or treatment thereof
    • A23L19/03Products from fruits or vegetables; Preparation or treatment thereof consisting of whole pieces or fragments without mashing the original pieces
    • A23L19/07Fruit waste products, e.g. from citrus peel or seeds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/231Pectin; Derivatives thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/262Cellulose; Derivatives thereof, e.g. ethers
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/20Reducing nutritive value; Dietetic products with reduced nutritive value
    • A23L33/21Addition of substantially indigestible substances, e.g. dietary fibres
    • A23L33/22Comminuted fibrous parts of plants, e.g. bagasse or pulp

Definitions

  • This invention relates to a natural thickener, stabilizer and cloud-generating agent de ⁇ ved from citrus fruit, preferably citrus pulp, for beverages and methods for producing said natural thickener.
  • the challenge of producing beverages which are acceptable to a broad range of consumers involves making a unique product having an acceptable appearance, flavor, aroma and satisfactory mouthfeel.
  • the aroma and flavor ingredients along with the amount of pectinaceous materials, pulp and fiber in beverages affect the flavor and mouthfeel characteristics of the beverage.
  • Xanthan gum, carboxymethylcellulose and propylene glycol alginate are three of the most commonly used beverage thickeners or gums.
  • thickeners gums such as carboxymethylcellulose. It is an object of the present invention to provide a thickener which provides juice-like texture and superior stability of suspensions of juice solids or cloud oils over time, temperature and pH. It is an object of the present invention that the thickener, stabilizer and cloud generating agent be naturally derived from citrus fruits.
  • Homogenized pulp is known in the art and can be added to beverages to achieve improved mouthfeel and viscosity. It is an object of the present invention to provide a thickener which is superior to homogenized pulp in terms of its ability to increase viscosity and to maintain viscosity and appearance stability over time at refrigerated or unrefrigerated temperatures as high as about 120°F (49 °C) and at a pH of from about 3 to about 8, preferably from about 3 to about 7. In the production of dilute juice beverages, it is desired to produce the opacity or cloud usually associated with natural juices.
  • Clouding agents that are used in beverages typically contain large amounts of edible oil and fat which can cause problems with unsightly separation when they coalesce and float to the top and with off-flavors when they oxidize. It is an object of the present invention that the thickener provide cloud to the beverages in which it is used through insoluble solid materials derived from citrus fruit without objectionable oils.
  • the thickener provide both soluble and insoluble fiber which is believed to be important in lowering blood cholesterol levels and in improving the overall intestinal function. It is an object that the thickener be derived from inexpensive starting materials derived from citrus fruit, such as citrus pulp, and be produced by a relatively inexpensive method. It is an object that the thickener can be utilized in all types of beverages, e.g. milk, fruit juices, vegetable juices and soft drinks.
  • beverages e.g. milk, fruit juices, vegetable juices and soft drinks.
  • the present invention relates to a process for preparing natural thickener compositions derived from citrus fruit for beverages, to the thickener compositions derived from citrus fruit themselves and to beverages comprising the thickener compositions derived from citrus fruit.
  • the process for making a thickener composition of the present invention comprises the steps of: a) preparing a slurry of water and citrus pulp, said slurry having an insoluble solids content of from about 0.15% to about 10% on an anhydrous weight basis; b) heating said slurry to a temperature of from about 158°F (70°C) to about 356°F (180°C) for at least about 2 minutes, generally from about 2 to about 240 minutes; and thereafter c) subjecting said slurry to high shear treatment by imparting shear at a rate of from about 20,000 sec -1 to about 100,000,000 sec" ⁇ preferably by a process selected from the group consisting of homogenization at a pressure of from about 1,000 psig to about 15,000 psig and colloidal milling.
  • the preferred process for making a thickener composition of the present invention comprises the steps of: a) preparing a slurry of citrus pulp and water wherein said mixture has an insoluble solids content of from about 0.15% to about 10%, on an anhydrous weight basis; b) heating said slurry to a temperature of from about 158°F (70°C) to about 356°F (180°C) for at least about 2 minutes, generally from about 2 to about 240 minutes; and thereafter c)subjecting said slurry to a high shear treatment by homogenizing said slurry at a pressure of from about 1,000 psig to about 15,000 psig, preferably from about 3,000 psig to about 8,000 psig.
  • the invention relates to thickener compositions prepared by these methods.
  • the invention relates to beverages comprising the thickener compositions of the present invention.
  • the Figure 1 represents a graph of elastic modulus (G') values (y-axis plotted on a log scale) measured across a range of strain values (x-axis, also plotted on a log scale) for a group of four samples of insoluble solids extracted from beverages and diluted to 0.25% on an insoluble anhydrous solids basis as detailed in Example 4.
  • the solid square data points are values for insoluble solids from a formulated dilute juice beverage of essentially the same composition as that in Example 1.
  • the open square data points are values for insoluble solids from United Dairy farmers brand orange juice.
  • the solid diamond data points are values for insoluble solids from Dittmeyer's Punica brand dilute juice beverage.
  • the open diamond data points are values for insoluble solids from Tropicana Twister brand orange-peach beverage.
  • the data points for the three commercial brand samples are lower than the limit line, but the corresponding data point for the formulated beverage is above the limit line.
  • citrus pulp means citrus fruit structures which comprise juice vesicles or juice sacs of the orange or other citrus fruits, including rag membrane, albedo and peel. Optionally, these citrus fruit structures are dried and milled to produce a fiber powder.
  • citrus fruits refers to fruits produced by any of a group of often thorny trees and shrubs (citrus and related genera of the rue family) grown in warm regions for their edible fruit (such as the orange) with firm usually thick rind and pulpy flesh.
  • citrus fruits for use herein are orange, lemon, lime, grapefruit, tangerine, and mandarins.
  • Preferred citrus fruits for use are orange, grapefruit, lemon, lime and mixtures thereof.
  • sweeteners includes sugars, for example glucose, sucrose, and fructose. Sugars also include high fructose corn syrup solids, invert sugar, sugar alcohols, including sorbitol, and mixtures thereof. Artificial or high intensity sweeteners are also included in the term sweetener.
  • the flavor component of the present invention contains flavors selected from natural flavors, botanical flavors and mixtures thereof.
  • flavors refers to those flavors derived from the edible reproductive part of a seed plant, especially one having a sweet pulp associated with the seed.
  • synthetically prepared flavors made to simulate fruit flavors derived from natural sources.
  • fruit juice beverage refers to a fruit juice product which is in a single-strength, ready-to-serve, drinkable form.
  • Fruit juice beverages of the present invention can be of the "full-strength" type which typically comprise at least about 95% fruit juice.
  • Fruit juice beverages within the scope of the present invention also include extended juice products which are referred to as "nectars". These extended juice products typically comprise from about 50 to about 90% fruit juice. Preferred extended juice products comprise from about 50 to about 70% fruit juice. Also included within the scope of the present invention are dilute juice beverages which comprise from about 0.2% to about 50% fruit juice. Preferred dilute juice beverages comprise from about 1% to about 35% fruit juice.
  • fruit juice concentrate refers to a fruit juice product which, when diluted with the appropriate amount of water, forms drinkable fruit juice beverages.
  • Fruit juice concentrates within the scope of the present invention are typic-tally formulated to provide drinkable beverages when diluted with 3 to 5 parts by weight water.
  • citrus juice refers to citrus juices, noncitrus juices such as, but not limited to, apple juice, grape juice, pear juice, cherry juice, berry juice, pineapple juice, peach juice, apricot juice, plum juice, prune juice, mango juice, banana juice, and mixtures of these juices.
  • citrus juice refers to fruit juices selected from orange juice, lemon juice, lime juice, grapefruit juice, tangerine juice and mixtures thereof.
  • the term “comprising” means various components can be conjointly employed. Accordingly, the term “comprising” encompasses the more restrictive terms “consisting essentially o and “consisting of. Starting Materials
  • the thickener is derived from citrus fruit and comprises particles of cellulose and pectinaceous material. The process allows for mobilization of pectin without separating the pectin away from the cellulose.
  • the preferred starting material is citrus pulp derived from citrus fruits.
  • citrus fruits for use herein are orange, grapefruit, lemon, lime, tangerine, mandarin, and mixtures thereof.
  • the preferred citrus fruits for use are orange, grapefruit, lemon, lime and mixtures thereof.
  • the most preferred citrus fruit for use is oranges.
  • the citrus pulp can be washed or unwashed, as well as dried.
  • the most preferred source of starting material is commercially produced citrus pulp as is produced during the manufacturing of concentrated citrus juices. Examples of commercially available pulp for use herein are Valencia orange pulp and Early Mid orange pulp from Cargill, Inc. ( Box 37, Frostproof, FL 33843) and washed and dried, sugar-free citrus pulp (CitroFiber DF-50®, from Citrosuco Paulista S/A, Postal 01, Matao, 15990, Brazil).
  • an aqueous slurry is prepared.
  • the slurry is prepared by adding water to dried citrus pulp and/or wet citrus pulp. Water is added as needed to achieve the desired insoluble solids content as described herein.
  • Wet citrus pulp which can be a by-product of juice production wherein the water is that which is naturally occurring in the citrus fruit, i.e., juice, may not require the addition of water to achieve a suitable insoluble solids content.
  • Wet citrus pulp as used herein can include washed citrus pulp.
  • the slurry be such that it is pumpable and pourable for the convenience of manufacture. Further, it is preferred that any large pieces be comminuted to avoid clogging of the process equipment.
  • the slurry of starting material and water is generally prepared such that the slurry has an insoluble solids content of from about 0.15% to about 10%, preferably from about 0.15% to about 5% and most preferably from about 0.2% to about 3%, on an insoluble anhydrous solids weight basis.
  • the insoluble solids content can be from about 0.1 % to about 15%, preferably from about 0.2% to
  • the slurry is subjected to a heat treatment.
  • the slurry is heated to at least about 158°F (70°C).
  • the slurry is heated to temperatures ranging from about 158°F (70°C) to about 356°F (180°C) for at least one minute and generally for from about 2 to about 240 minutes.
  • the slurry is heated to temperatures from about 158°F (70 ⁇ C) to about 248°F (120°C) and most preferably from about 176°F (80°C) to about 212°F (100°C) for from about 2 to about 240 minutes.
  • Other preferred processing temperatures and times are from about 176°F (80°C) to about 275°F (135°C) for from about 2 to about 240 minutes, more preferably from about 185°F (85°C) to about 257°F (125°C) for from about 3 to about 120 minutes and most preferably from about 212°F (100°C) to about 248°F (120°C) for from about 3 to about 15 minutes.
  • Heating times will be related to the temperature used, higher temperatures requiring less heating time.
  • treatment can be preferably from about 10 minutes to about 240 minutes, and most preferably from about 30 minutes to about 210 minutes.
  • temperatures of from about 248°F (120°C) to about 284°F (140°C) can be preferably from about 8 minutes and to about 180 minutes, and most preferably from about 10 minutes to about 120 minutes.
  • temperatures of from about 284°F (140°C) to about 356°F (180°C) treatment can be preferably from about 2 minutes to about 90 minutes and most preferably from about 5 minutes to about 60 minutes.
  • the preferred heat treatment method is to heat the pulp slurry in a kettle such as a 30 gallon Hamilton Kettle" (Hamilton Kettles, 11861 Mosteller Rd., Cincinnati, OH 45241) for laboratory purposes and for plant purposes commercially available an external heat exchanger can be used with a 3,000 gallon tank. Conventional heat exchange and tank combinations or continuous processes that provide appropriate temperatures and heating times can also be used. High Shear Treatment
  • the material is subjected to high shear treatment. Shearing may be performed immediately while still hot, or it can be accomplished hours, days or weeks later after the material has cooled or even been frozen and then thawed. Further, the heated material may be further diluted with water, if desired for ease of processing, before the high shear treatment. Dilution with water to replace any water lost during heat treatment or storage is preferred such that the solids to water content of the aqueous slurry corresponds to the ranges of from about 0.15% to about 10%, preferably from about 0.15% to about 5% and most preferably from about 0.2% to about 3% of insoluble solids on an anhydrous weight basis.
  • high shear treatment refers to methods of treatment having shear rates (calculated) of at least about 20,000 sec" 1 .
  • high shear treatment methods useful in the present invention impart shear rates of from about 20,000 sec" 1 to about 100,000,000 sec -1 .
  • Preferred high shear treatment methods impart shear rates of from about 50,000 sec" 1 to about 20,000,000 sec” 1 .
  • the most preferred high shear treatment methods impart shear rates of from about 100,000 sec" 1 to about 8,000,000 sec "1 .
  • the high shear treatment is preferably imparted to the material for a period of time sufficient to reduce said citrus pulp particles in the slurry to a particle size of from about 5 micrometers to about 500 micrometers, more preferably from about 5 micrometers to about 200 micrometers.
  • the preferred high shear treatment method is to homogenize the slurry of water and citrus pulp under high pressure.
  • High pressure homogenizers typically comprise a reciprocating plunger or piston type pump together with a homogenizing valve assembly affixed to the discharge end of the pump.
  • Suitable high pressure homogenizers useful in carrying out the high shear treatment include high pressure homogenizers manufactured by APV Gaulin Corporation of Everett, Mass. U.S. Pat. No. 4,352,573 to Pandolfe, issued Oct. 5, 1982 and U.S. Pat. No.
  • Suitable pressures for obtaining high shear rates are at least about 1000 pounds per square inch (psig), and preferably at least about 3000 psig. Typically, these pressures are in the range of from about 1000 psig to about 15,000 psig, preferably from about 3000 psig to about 8000 psig. The most preferred pressures for carrying out high pressure homogenization are in the range of from about
  • the preferred pressures are in the range of from about 3000 psig to about 15,000 psig and more preferably from about 5000 psig to about 15,000 psig.
  • High pressure homogenization can be carried out at any suitable temperature. Suitable feed temperatures for carrying out this high pressure homogenization are typically from about 32°F to about 356°F (from about 0°C to about 180°C). Preferably, the slurry is fed to the homogenizer at a temperature of from about 77°F to about 212°F (from about 25°C to about 100 ⁇ C). Following high pressure homogenization, the resulting thickener material is typically cooled, if necessary, to a temperature of below about 120°F (49 ⁇ to prevent degradation of the product viscosity. However, the thickener can be hot packed and then cooled as is normal for a hot packing process. Additionally, the thickener can be cooled and then aseptically packed.
  • the desired effects of the resulting rheology of the thickener compositions and preferably a particle size of from about 5 to about 500 micrometers can be achieved by one pass through the high pressure homogemzer. However, more than one pass of the slurry through the high pressure homogenizer may be desired to maximize the desired effects, depending upon the particular composition of the mixture and especially if lower pressures are used.
  • the slurry is passed through the high pressure homogenizer from about 1 to about 3 times.
  • the number of passes through the high pressure homogenizer is from about 1 to about 2.
  • colloidal milling of the slurry Another example of a suitable high shear treatment method is colloidal milling of the slurry.
  • the shear imparting components of a colloidal mill typically comprise a revolving rotor and a fixed stator.
  • the rotor and the stator are configured so as to fit together in working combination, e.g. a truncated cone-shaped rotor and a concave-shaped stator.
  • Suitable colloidal mills useful in carrying out the method of the present invention include those manufactured by APV Gaulin Corporation and those manufactured by Greerco Corporation of Hudson, N.H.
  • the slurry is subjected to high shear rates as the result of impact and hydraulic shear forces.
  • the turbine blades on the upper surface of the rotor create a negative pressure differential which pushes the slurry into a first shearing zone located at the small diameter end of the rotor.
  • the slurry is subjected to high impact and sudden shear, plus centrifugal force, that drives the pulp against the surface of the stator.
  • the turbine blades pass in close tolerance to the stator surface. Serrations formed in the upper surface of the rotor at the base of the turbine blades also rotate rapidly past the stator and cause further comminution of the pulp particles.
  • the slurry containing partially comminuted pulp particles flows through channels formed by the cooperation of the upper surface of the rotor and the lower surface of the stator.
  • the slurry is then subjected to extreme forces of hydraulic shear as it passes through the narrow gap (e.g., on the order of about 0.010 inches (0.25 mm)) between the rotor and the stator.
  • the slurry is finally thrown, by high centrifugal force, from the rotor against the smooth portion of the wall of the stator. This high velocity impingement provides additional size reduction of the pulp particles.
  • colloidal milling of the slurry can be carried out at temperatures suitable for high pressure homogenization. Also like high pressure homogenization, colloidal milling can be carried out by one or more passes of the mixture through the mill to achieve the desired thickener attributes.
  • the resulting thickener material can be cooled to below about 120°F (49°C) to prevent deterioration of the product viscosity. This can be done by blending it immediately into the final beverage formulation, or by cooling with appropriate heat exchangers and placing it in a storage tank. Alternatively, the product can be placed into bottles, cans, or other storage vessels at about 190°F (88°C), sealed and then cooled to produce a hot packed sterile product for later use. The product can be stored without refrigeration or aseptic packaging if appropriate food approved antimicrobial agents are added. The material may be frozen for storage, except that when thawed, additional shearing may be necessary to return the material to its original viscosity.
  • the viscous behavior of the slurry can be described in terms of a pseudoplastic fluid, in contrast to the Newtonian behavior of water or a sugar solution. If measurements are made at different velocity gradients (shear rates), the ratio of shear stress (ST) to shear rate (SR) will not be constant. The ratio is frequently called the apparent viscosity (Ua) which decreases as the shear rate is increased.
  • the shear stress is the force per unit area required to keep the fluid moving, while the shear rate is the velocity gradient perpendicular to the direction of flow.
  • the shear rate for a colloid mill (e.g. Greerco) having a 7.5 inch diameter (D) rotor operating at 3550 rpm with a 0.010 inch gap setting between the stator and rotor is defined by the equation:
  • the shear rate for a high pressure homogenizer (e.g. APV Gaulin) is -calculated from the dimensions of the valves and volumetric capacity of product at a given operating pressure. Representative valve dimensions and capacities are given in U.S. Pat. No. 4,352,573 to Pandolfe, Issued Oct. 5, 1982 and incorporated herein by reference.
  • a homogenizer operating at 4000 psig achieves 120 gallon per hour capacity through a valve having about a 0.001 inch width and about a 0.77 inch circumference.
  • the shear rate (SR) for homogenization is defined as follows:
  • Solids can be distinguished from liquids by the fact that the solids tend both to resist deformation and to return to their original state when deformed because a deforming force is stored and then used to regenerate the original shape. Liquids resist deformation by dissipating the deforming force as heat but do not recoil. The solid resistance is referred to as elasticity, while the resistance of the liquid is known as viscosity.
  • a low shear oscillatory rheology test is used.
  • the sample is moved back and forth over a very small distance, or known as the strain, (too small to cause significant change in the sample).
  • Measuring the amount of stress generated in the sample that is in phase with these oscillations provides information on the near-resting viscosity of the sample, and measuring the 90°-out-of-phase stress tells us about its elasticity.
  • a Vilastic rheometer is used. The Vilastic rheometer is supplied by Vilastic Scientific, Inc., P. O. Box 160261, Austin, TX, 78716.
  • the oscillation motor pumps the sample up and down in a small capillary, usually over a distance (strain range) of from about 0.05 to about 11 capillary diameters (the diameter is commonly 1 mm).
  • the generated stress is measured by a pressure sensor below the capillary, and the calculation of in-phase and out-of-phase components is done with an attached personal computer.
  • G' storage
  • G loss
  • viscous moduli also referred to as elastic and viscous moduli
  • the thickener compositions of the present invention are paniculate material similar in size and microscopic appearance to background pulp and other homogenized pulps. It can, therefore, be readily screened to remove sensible pulp and extracted from a beverage by centrifugation. Repeated washings with 70°F(21°C) water can reduce gums, sugars and emulsion droplet concentrations to insignificant levels (less than about 0.2°Brix), leaving a pulp residue suitable for insoluble anhydrous solids determination. This insoluble solids residue can then be diluted to the appropriate 0.25% level for a Vilastic run and tested to determine if it falls within the region determined to be occupied by a functional thickener composition of the present invention.
  • a suspension of sheared particles of thermally treated citrus material comprising cellulose and pectinaceous material prepared by our process can be identified by its rheological characteristics in combination with its microscopic mo ⁇ hology using the following procedure.
  • the thickener of the present invention is obtained, at least in part, from the cell walls of plants. These cell walls are fragmented in processing, but retain identifiable mo ⁇ hology. Light microscopic identification of citrus cell wall fragments should be performed by a person skilled in the art who has knowledge of the appearance of the cell walls of the source plant material. These fragments can be identified as being derived from cell walls using one or more of the brightfield, interference or phase contrast forms of microscopy, along with polarized light microscopy.
  • Analyzer® (Vilastic Scientific, Inc.) equipped with a 1 mm capillary with a temperature-controlled jacket is used to determine the dynamic oscillatory rheology of beverage products, including those containing finely fragmented plant cell wall pieces.
  • the viscometer is equilibrated at 52°F (11.1°C), and the sample is run at 1.592 sec "1 .
  • a strain sweep is run including the range of strains between 0.3 and 3.
  • Samples containing the present compositions will exhibit an elastic modulus (G') in this standardized test such that, for the entire range of strains between 0.3 and 3, log(G') > ((-0.69897) x log(strain)) -
  • step 5 If the elastic modulus values determined in step 5 above are such that, for the range of strains between 0.3 and 3, log(G') > ((-0.69897) x log(strain)) - 0.96754, the presence of the present compositions can be verified by repeating step 5, except with the rheometer equilibrated at
  • samples containing at least 0.25% insoluble solids of the thickener of this invention can be heated to a temperature of about
  • the thickener compositions of the present invention can be used as thickeners and/or stabilizers and/or clouding agents in any beverage.
  • Preferred ranges are from about 0.05% to about 2%, more preferably from about 0.1 % to about 1% and most preferably from about 0.1 % to about 0.5% of the beverage on an anhydrous weight basis is the thickener composition.
  • the invention relates to beverages comprising the thickener of the present invention.
  • a fruit juice concentrate of the present invention can comprise from about 0.2% to about 8%, by anhydrous weight, of a citrus fruit derived thickener composition of the present invention.
  • Another preferred fruit juice concentrate of the present invention comprises: a) from about 0.2% to
  • the thickener compositions of the present invention can be dried.
  • water soluble, inert substances such as sweeteners and maltodextrins may be added, if necessary, to achieve, °Brix to insoluble anhydrous solids ratio of from about 1: 1 to about 10: 1, preferably from about 2:1 to about 10:1 and most preferably from abut 3:1 to 10:1.
  • the purpose of these water soluble inert materials is to aid in the drying of the thickener and rehydration of the dried material, as is commonly practiced in the spray drying of instant coffee.
  • the preferred water soluble inert materials for addition are sweeteners like glucose, sucrose, fructose, high fructose com syrup solids, invert sugar, sugar alcohols and mixtures thereof.
  • the most preferred sweetener for use is sucrose.
  • sweeteners may not be necessary. If the addition of sweeteners is necessary to achieve the appropriate °Brix to insoluble solids ratio, the addition can be in the form of adding dry sweeteners with agitation to the slurry, by adding a slurry of sweeteners and water to the slurry or in any other conventional method typical for adding sweeteners during beverage processing.
  • the slurry is dried to a moisture content of from about 1 % to about 15%, preferably from about 4% to about 9%, water. This can be done by any of the conventional means, such as spray drying, vacuum oven drying, drum drying, or freeze drying.
  • the preferred method of drying is by spray drying by using commercially available spray dryers such as those made by Niro Atomizer (9165 Rumsey Rd., Columbia, MD 21045).
  • the process of the present invention can comprise the additional steps of: a)adding a sweetener such that said slurry has a °Brix to insoluble solids ratio of from about 1: 1 to about 10:1, preferably from about 2:1 to about 10:1 and most preferably from about 3:1 to about 10:1; and b)drying said slurry to a moisture content of from about 1% to about 15% preferably from abut 4% to about 9%, water.
  • the material is cooled to about 80°F (27°C) over the course of about one hour. It is then subjected to high shear treatment by homogenization by passing it through a Gaulin M-3® homogenizer (APV Gaulin, Inc., 500 Research Drive, Wilmington, MA 01887) at about 4000 psig, using two separate passes.
  • Gaulin M-3® homogenizer AMV Gaulin, Inc., 500 Research Drive, Wilmington, MA 01887
  • the resulting thickener slurry provides good clouding properties. Take 1 part of the resulting slurry and dilute with 9 parts water making 10% water solution having turbidity of 807 NTLPs as measured on a Model DRT 100B Turbidimeter (HF Instruments, Ft. Meyers, FL).
  • the beverage has a viscosity of about 15.2 cp at about 7.3 sec" 1 of shear as measured in a UL Adapter® on a Brookfield LVDV- ⁇ l® viscometer (Brookfield Engineering Lab, Inc., 240 Cushing St., Stoughton, MA 02072).
  • EXAMPLE 2 Sixty pounds of commercial Valencia citrus pulp (Cargill, Inc., Box 37, Frostproof, FL 33843) containing about 5% insoluble solids on an anhydrous weight basis is added to about 120 pounds of water producing a slurry of about 1.25% insoluble solids on an anhydrous weight basis. The slurry is stirred and heated at about 190°F (88°C) for a period of about 1 hour in a 30 gallon Hamilton Kettle (Hamilton Kettles, 11861 Mosteller Rd., Cincinnati, OH 45241). The material is cooled to about 80°F (27°C) over the course of about one hour.
  • EXAMPLE 3 Five grams of washed and dried, sugar-free citrus pulp (CitroFiber DF-50®, from Citrosuco Paulista S/A, Postal 01, Matao, 15990, Brazil) is added to about 1000 grams of water and comminuted using a food processor for sufficient time to produce a slu ⁇ y which easily passes through the homogenization equipment. It is then heated to about 205°F
  • the slurry is subjected to high shear treatment by homogenization using two passes through a model M-110T MicroFluidizer®
  • the resulting slurry has a viscosity of about 27 cp at about 7.3 sec" 1 .
  • Tropicana Twister brand orange-peach beverage (a beverage thickened with pulp and pectinaceous material);
  • Dittmeyer's Punica a dilute juice beverage thickened with homogenized citrus pulp
  • AU samples are strained through a 50-mesh screen to remove large particles. They are then tested for steady shear viscosity using a Brookfield Model LVDV-IQ® Programmable Rheometer equipped with a ULA Adapter and a temperature-controlled jacket. The viscometer is equilibrated at 52°F (11.1°C), and the samples run at about 7.3 sec" 1 using the standard operating procedures detailed in the manuals for this instrument.
  • the measured viscosities of these samples are about 10.5 cp for the United Dairy farmers orange juice, about 2.4 cp for the United Dairy farmers orange drink, about 3.7 cp for the Tropicana Twister orange-peach beverage, about 2.5 cp for Dittmeyer's Punica, about 4.0 cp for Awake, and about 19.4 cp for the formulated dilute juice beverage containing the thickener material of the present invention described herein.
  • the viscosities of some of these beverages are less than about 3 cp, as a scientific exercise, all examples are examined further.
  • the four remaining samples are centrifuged using a Beckman J2-21® operating at about 39°F(4°C) equipped with a type JA-10® rotor running at about 7000 ⁇ m for about 30 minutes, the supematants discarded, and the pellets resuspended in ambient temperature (70°F(21°C)) water three times. Then the washed samples are centrifuged once more and decanted to obtain pellets of insoluble solids.
  • the dynamic rheology of the four samples containing about 0.25% insoluble solids is determined using a Vilastic V-E System Viscoelastic Analyzer® (Vilastic Scientific, Inc.) equipped with a 1 mm capillary with a temperature-controlled jacket. The rheometer is equilibrated at 52°F (ll.TC), and the samples run at 1.592 Hz. Using the standard operating procedures detailed in the manuals for this instrument, a strain sweep including the range of strains between 0.3 and 3 are run on each sample.
  • the G' values for the formulated dilute juice beverage containing the thickener material of the present invention described herein are above those values ( Figure 1).

Abstract

The present invention relates to a process for preparing natural thickeners derived from citrus fruit for beverages, to the thickeners themselves and to beverages comprising the thickeners. The process for making the thickener compositions comprises the steps of: (a) preparing a slurry of water and citrus pulp, said slurry having an insoluble solids content of from about 0.15 % to about 10 % on an anhydrous weight basis; (b) heating said slurry to a temperature of from about 158 °F (70 °C) to about 356 °F (180 °C) for at least about 2 minutes, generally from about 2 to about 240 minutes; and thereafter (c) subjecting said slurry to high shear treatment by imparting shear at a rate of from about 20,000 sec-1 to about 100,000,000 sec-1, preferably by a process selected from the group consisting of homogenization at a pressure of from about 1,000 psig to about 15,000 psig and colloidal milling.

Description

Method for Producing a Natural Citrus Pulp Thickener, Stabilizer and Cloud Agent for Beverages
TECHNICAL FIELP
This invention relates to a natural thickener, stabilizer and cloud-generating agent deπved from citrus fruit, preferably citrus pulp, for beverages and methods for producing said natural thickener.
BACKGROUND OF THE INVENTION Fruit juice beverage consumption continues to increase in part because of technological change in juice processing and concentration methods. Flash pasteurization, improved thermal concentrating, freeze concentrating, blending, freezing, and drying or crystallization all contributed to this growth by providing better quality, better tasting and higher purity juice products which are more convenient to use. The current health awareness of consumers has also contributed to the consumption of fruit juices, dilute juice beverages and other natural beverages.
The challenge of producing beverages which are acceptable to a broad range of consumers involves making a unique product having an acceptable appearance, flavor, aroma and satisfactory mouthfeel. The aroma and flavor ingredients along with the amount of pectinaceous materials, pulp and fiber in beverages affect the flavor and mouthfeel characteristics of the beverage.
The standard way to achieve acceptable mouthfeel and appearance is to add thickeners, particularly in dilute juice beverages to achieve a juice-like texture. Xanthan gum, carboxymethylcellulose and propylene glycol alginate are three of the most commonly used beverage thickeners or gums.
In view of the consumers preference for all natural beverages, a need has arisen for a natural replacement for thickeners gums such as carboxymethylcellulose. It is an object of the present invention to provide a thickener which provides juice-like texture and superior stability of suspensions of juice solids or cloud oils over time, temperature and pH. It is an object of the present invention that the thickener, stabilizer and cloud generating agent be naturally derived from citrus fruits.
Homogenized pulp is known in the art and can be added to beverages to achieve improved mouthfeel and viscosity. It is an object of the present invention to provide a thickener which is superior to homogenized pulp in terms of its ability to increase viscosity and to maintain viscosity and appearance stability over time at refrigerated or unrefrigerated temperatures as high as about 120°F (49 °C) and at a pH of from about 3 to about 8, preferably from about 3 to about 7. In the production of dilute juice beverages, it is desired to produce the opacity or cloud usually associated with natural juices. Clouding agents that are used in beverages typically contain large amounts of edible oil and fat which can cause problems with unsightly separation when they coalesce and float to the top and with off-flavors when they oxidize. It is an object of the present invention that the thickener provide cloud to the beverages in which it is used through insoluble solid materials derived from citrus fruit without objectionable oils.
It is a further object that the thickener provide both soluble and insoluble fiber which is believed to be important in lowering blood cholesterol levels and in improving the overall intestinal function. It is an object that the thickener be derived from inexpensive starting materials derived from citrus fruit, such as citrus pulp, and be produced by a relatively inexpensive method. It is an object that the thickener can be utilized in all types of beverages, e.g. milk, fruit juices, vegetable juices and soft drinks.
These and other objects of this invention will become apparent by the following description of the invention.
All percentages and ratios herein are by weight unless otherwise indicated.
SUMMARY OF THE INVENTION
The present invention relates to a process for preparing natural thickener compositions derived from citrus fruit for beverages, to the thickener compositions derived from citrus fruit themselves and to beverages comprising the thickener compositions derived from citrus fruit.
The process for making a thickener composition of the present invention comprises the steps of: a) preparing a slurry of water and citrus pulp, said slurry having an insoluble solids content of from about 0.15% to about 10% on an anhydrous weight basis; b) heating said slurry to a temperature of from about 158°F (70°C) to about 356°F (180°C) for at least about 2 minutes, generally from about 2 to about 240 minutes; and thereafter c) subjecting said slurry to high shear treatment by imparting shear at a rate of from about 20,000 sec-1 to about 100,000,000 sec" ^preferably by a process selected from the group consisting of homogenization at a pressure of from about 1,000 psig to about 15,000 psig and colloidal milling. The preferred process for making a thickener composition of the present invention comprises the steps of: a) preparing a slurry of citrus pulp and water wherein said mixture has an insoluble solids content of from about 0.15% to about 10%, on an anhydrous weight basis; b) heating said slurry to a temperature of from about 158°F (70°C) to about 356°F (180°C) for at least about 2 minutes, generally from about 2 to about 240 minutes; and thereafter c)subjecting said slurry to a high shear treatment by homogenizing said slurry at a pressure of from about 1,000 psig to about 15,000 psig, preferably from about 3,000 psig to about 8,000 psig. The invention relates to thickener compositions prepared by these methods. Particularly, the invention relates to a thickener composition derived from citrus fruit, preferably citrus pulp, comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said thickener has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3.
Further, the invention relates to beverages comprising the thickener compositions of the present invention. Such beverages comprise from about 0.15% to about 2%, on anhydrous weight basis of insoluble solids, of a thickener composition derived from citrus fruit, preferably citrus pulp, comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of the thickener compositions has an elastic modulus (C) at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3. BRIEF DESCRIPTION OF THE DRAWING
The Figure 1 represents a graph of elastic modulus (G') values (y-axis plotted on a log scale) measured across a range of strain values (x-axis, also plotted on a log scale) for a group of four samples of insoluble solids extracted from beverages and diluted to 0.25% on an insoluble anhydrous solids basis as detailed in Example 4. The solid square data points are values for insoluble solids from a formulated dilute juice beverage of essentially the same composition as that in Example 1. The open square data points are values for insoluble solids from United Dairy Farmers brand orange juice. The solid diamond data points are values for insoluble solids from Dittmeyer's Punica brand dilute juice beverage. The open diamond data points are values for insoluble solids from Tropicana Twister brand orange-peach beverage. Also, a limit line representing modulus values delineated by equation : log(G,)=((-0.69897) x log(strain))-0.96754 is drawn for the range of strains from 0.3 to 3 (with solid triangles at the ends). In this graph, it can be seen that for any given strain value between 0.3 and 3, the data points for the three commercial brand samples are lower than the limit line, but the corresponding data point for the formulated beverage is above the limit line.
DF AI -ED DESCRIPTION OF THE INVENTION As used herein, the term "citrus pulp" means citrus fruit structures which comprise juice vesicles or juice sacs of the orange or other citrus fruits, including rag membrane, albedo and peel. Optionally, these citrus fruit structures are dried and milled to produce a fiber powder.
As used herein "citrus fruits" refers to fruits produced by any of a group of often thorny trees and shrubs (citrus and related genera of the rue family) grown in warm regions for their edible fruit (such as the orange) with firm usually thick rind and pulpy flesh. Examples of citrus fruits for use herein are orange, lemon, lime, grapefruit, tangerine, and mandarins. Preferred citrus fruits for use are orange, grapefruit, lemon, lime and mixtures thereof. As used herein, the term "sweeteners" includes sugars, for example glucose, sucrose, and fructose. Sugars also include high fructose corn syrup solids, invert sugar, sugar alcohols, including sorbitol, and mixtures thereof. Artificial or high intensity sweeteners are also included in the term sweetener.
The flavor component of the present invention contains flavors selected from natural flavors, botanical flavors and mixtures thereof. As used herein, the term "fruit flavors" refers to those flavors derived from the edible reproductive part of a seed plant, especially one having a sweet pulp associated with the seed. Also included within the term "fruit flavor" are synthetically prepared flavors made to simulate fruit flavors derived from natural sources. As used herein, the term "fruit juice beverage" refers to a fruit juice product which is in a single-strength, ready-to-serve, drinkable form. Fruit juice beverages of the present invention can be of the "full-strength" type which typically comprise at least about 95% fruit juice.
Fruit juice beverages within the scope of the present invention also include extended juice products which are referred to as "nectars". These extended juice products typically comprise from about 50 to about 90% fruit juice. Preferred extended juice products comprise from about 50 to about 70% fruit juice. Also included within the scope of the present invention are dilute juice beverages which comprise from about 0.2% to about 50% fruit juice. Preferred dilute juice beverages comprise from about 1% to about 35% fruit juice.
As used herein, the term "fruit juice concentrate" refers to a fruit juice product which, when diluted with the appropriate amount of water, forms drinkable fruit juice beverages. Fruit juice concentrates within the scope of the present invention are typic-tally formulated to provide drinkable beverages when diluted with 3 to 5 parts by weight water.
As used herein, the term "fruit juice" refers to citrus juices, noncitrus juices such as, but not limited to, apple juice, grape juice, pear juice, cherry juice, berry juice, pineapple juice, peach juice, apricot juice, plum juice, prune juice, mango juice, banana juice, and mixtures of these juices.
As used herein, the term "citrus juice:" refers to fruit juices selected from orange juice, lemon juice, lime juice, grapefruit juice, tangerine juice and mixtures thereof. As used herein, the term "comprising" means various components can be conjointly employed. Accordingly, the term "comprising" encompasses the more restrictive terms "consisting essentially o and "consisting of. Starting Materials
The thickener is derived from citrus fruit and comprises particles of cellulose and pectinaceous material. The process allows for mobilization of pectin without separating the pectin away from the cellulose.
The preferred starting material is citrus pulp derived from citrus fruits.
Examples of citrus fruits for use herein are orange, grapefruit, lemon, lime, tangerine, mandarin, and mixtures thereof. The preferred citrus fruits for use are orange, grapefruit, lemon, lime and mixtures thereof. The most preferred citrus fruit for use is oranges.
The citrus pulp can be washed or unwashed, as well as dried. The most preferred source of starting material is commercially produced citrus pulp as is produced during the manufacturing of concentrated citrus juices. Examples of commercially available pulp for use herein are Valencia orange pulp and Early Mid orange pulp from Cargill, Inc. ( Box 37, Frostproof, FL 33843) and washed and dried, sugar-free citrus pulp (CitroFiber DF-50®, from Citrosuco Paulista S/A, Postal 01, Matao, 15990, Brazil).
Once a starting material has been selected, an aqueous slurry is prepared. The slurry is prepared by adding water to dried citrus pulp and/or wet citrus pulp. Water is added as needed to achieve the desired insoluble solids content as described herein. Wet citrus pulp, which can be a by-product of juice production wherein the water is that which is naturally occurring in the citrus fruit, i.e., juice, may not require the addition of water to achieve a suitable insoluble solids content. Wet citrus pulp as used herein can include washed citrus pulp.
It is preferred that the slurry be such that it is pumpable and pourable for the convenience of manufacture. Further, it is preferred that any large pieces be comminuted to avoid clogging of the process equipment. The slurry of starting material and water is generally prepared such that the slurry has an insoluble solids content of from about 0.15% to about 10%, preferably from about 0.15% to about 5% and most preferably from about 0.2% to about 3%, on an insoluble anhydrous solids weight basis. For commercial production, the insoluble solids content can be from about 0.1 % to about 15%, preferably from about 0.2% to
10% and most preferably from about 2% to about 10%.
Heat Treatment
The use of heat to pasteurize citrus pulp produced during the manufacture of citrus juices is well known. The difference between that practice and this invention is that this invention requires substantially more heating than is required to pasteurize the pulp. Without intending to be bound by theory, it is believed that the heat treatment step of this invention allows for the hydration and softening of the pectinaceous material in the pulp which subsequently allows significantly higher viscosities and stabilities to be produced in the shearing step than is possible from conventionally pasteurized or unheated pulps.
After preparing the slurry of water and citrus pulp, the slurry is subjected to a heat treatment. The slurry is heated to at least about 158°F (70°C). Generally the slurry is heated to temperatures ranging from about 158°F (70°C) to about 356°F (180°C) for at least one minute and generally for from about 2 to about 240 minutes. Preferably the slurry is heated to temperatures from about 158°F (70βC) to about 248°F (120°C) and most preferably from about 176°F (80°C) to about 212°F (100°C) for from about 2 to about 240 minutes.
Other preferred processing temperatures and times are from about 176°F (80°C) to about 275°F (135°C) for from about 2 to about 240 minutes, more preferably from about 185°F (85°C) to about 257°F (125°C) for from about 3 to about 120 minutes and most preferably from about 212°F (100°C) to about 248°F (120°C) for from about 3 to about 15 minutes.
Heating times will be related to the temperature used, higher temperatures requiring less heating time. For the preferred temperatures of from about 158 °F (70°C) to about 248°F (120°C), treatment can be preferably from about 10 minutes to about 240 minutes, and most preferably from about 30 minutes to about 210 minutes. For temperatures of from about 248°F (120°C) to about 284°F (140°C), treatment can be preferably from about 8 minutes and to about 180 minutes, and most preferably from about 10 minutes to about 120 minutes. For temperatures of from about 284°F (140°C) to about 356°F (180°C), treatment can be preferably from about 2 minutes to about 90 minutes and most preferably from about 5 minutes to about 60 minutes.
The preferred heat treatment method is to heat the pulp slurry in a kettle such as a 30 gallon Hamilton Kettle" (Hamilton Kettles, 11861 Mosteller Rd., Cincinnati, OH 45241) for laboratory purposes and for plant purposes commercially available an external heat exchanger can be used with a 3,000 gallon tank. Conventional heat exchange and tank combinations or continuous processes that provide appropriate temperatures and heating times can also be used. High Shear Treatment
After the specified amount of heating, the material is subjected to high shear treatment. Shearing may be performed immediately while still hot, or it can be accomplished hours, days or weeks later after the material has cooled or even been frozen and then thawed. Further, the heated material may be further diluted with water, if desired for ease of processing, before the high shear treatment. Dilution with water to replace any water lost during heat treatment or storage is preferred such that the solids to water content of the aqueous slurry corresponds to the ranges of from about 0.15% to about 10%, preferably from about 0.15% to about 5% and most preferably from about 0.2% to about 3% of insoluble solids on an anhydrous weight basis. Not wishing to be bound by theory, it is believed that the high shear treatment methods according to the present invention act on the citrus pulp by shredding and disintegrating the pulp particles causing a mobilization of the hydrated, softened pectinaceous material in the primary cell walls. Generally, high shear treatment refers to methods of treatment having shear rates (calculated) of at least about 20,000 sec"1. Typically, high shear treatment methods useful in the present invention impart shear rates of from about 20,000 sec"1 to about 100,000,000 sec-1. Preferred high shear treatment methods impart shear rates of from about 50,000 sec"1 to about 20,000,000 sec"1. The most preferred high shear treatment methods impart shear rates of from about 100,000 sec"1 to about 8,000,000 sec"1. The high shear treatment is preferably imparted to the material for a period of time sufficient to reduce said citrus pulp particles in the slurry to a particle size of from about 5 micrometers to about 500 micrometers, more preferably from about 5 micrometers to about 200 micrometers.
The preferred high shear treatment method is to homogenize the slurry of water and citrus pulp under high pressure. High pressure homogenizers typically comprise a reciprocating plunger or piston type pump together with a homogenizing valve assembly affixed to the discharge end of the pump. Suitable high pressure homogenizers useful in carrying out the high shear treatment include high pressure homogenizers manufactured by APV Gaulin Corporation of Everett, Mass. U.S. Pat. No. 4,352,573 to Pandolfe, issued Oct. 5, 1982 and U.S. Pat. No. 4,383,769 to Pandolfe, issued May 17, 1983, herein incorporated by reference, describe suitable high pressure homogenizers made by APV Gaulin as, for example, the Gaulin M-3 homogenizer (APV Gaulin, Inc., 500 Research Drive, Wilmington, MA 01887).
During high pressure homogenization, the slurry is subjected to high shear rates as the result of cavitation and turbulence effects. These effects are created by the slurry entering the homogenizing valve assembly from the pump section of the homogenizer at high pressure and low velocity. Suitable pressures for obtaining high shear rates are at least about 1000 pounds per square inch (psig), and preferably at least about 3000 psig. Typically, these pressures are in the range of from about 1000 psig to about 15,000 psig, preferably from about 3000 psig to about 8000 psig. The most preferred pressures for carrying out high pressure homogenization are in the range of from about
3000 psig to about 6000 psig. For commercial production, the preferred pressures are in the range of from about 3000 psig to about 15,000 psig and more preferably from about 5000 psig to about 15,000 psig.
As the slurry enters the space between the valve and the seat, its velocity is dramatically increased. There is also a corresponding decrease in pressure which causes vapor bubbles to form in the slurry. As the slurry flows through the valve seat area, its velocity is again decreased and the pressure is again increased, resulting in an implosion of the bubbles. Bubble formation and implosion causes the cavitation effects. The intense energy release and turbulence associated with cavitation causes the disruption and disintegration of the pulp particles.
High pressure homogenization can be carried out at any suitable temperature. Suitable feed temperatures for carrying out this high pressure homogenization are typically from about 32°F to about 356°F (from about 0°C to about 180°C). Preferably, the slurry is fed to the homogenizer at a temperature of from about 77°F to about 212°F (from about 25°C to about 100βC). Following high pressure homogenization, the resulting thickener material is typically cooled, if necessary, to a temperature of below about 120°F (49β to prevent degradation of the product viscosity. However, the thickener can be hot packed and then cooled as is normal for a hot packing process. Additionally, the thickener can be cooled and then aseptically packed.
Depending upon the particular pressure selected for high pressure homogenization, and the flow rate of the slurry through the homogenizer, the desired effects of the resulting rheology of the thickener compositions and preferably a particle size of from about 5 to about 500 micrometers can be achieved by one pass through the high pressure homogemzer. However, more than one pass of the slurry through the high pressure homogenizer may be desired to maximize the desired effects, depending upon the particular composition of the mixture and especially if lower pressures are used. Typically, the slurry is passed through the high pressure homogenizer from about 1 to about 3 times. Preferably, the number of passes through the high pressure homogenizer is from about 1 to about 2.
While high pressure homogenization is the preferred way for carrying out high shear treatment according to the method of the present invention, other high shear treatment methods which achieve the shear rates defined above may also be used.
Another example of a suitable high shear treatment method is colloidal milling of the slurry. The shear imparting components of a colloidal mill typically comprise a revolving rotor and a fixed stator. The rotor and the stator are configured so as to fit together in working combination, e.g. a truncated cone-shaped rotor and a concave-shaped stator. Suitable colloidal mills useful in carrying out the method of the present invention include those manufactured by APV Gaulin Corporation and those manufactured by Greerco Corporation of Hudson, N.H. During colloid milling, the slurry is subjected to high shear rates as the result of impact and hydraulic shear forces. As the rotor of the colloidal mill turns, the turbine blades on the upper surface of the rotor create a negative pressure differential which pushes the slurry into a first shearing zone located at the small diameter end of the rotor. The slurry is subjected to high impact and sudden shear, plus centrifugal force, that drives the pulp against the surface of the stator. As the slurry enters the second shearing zone of the colloidal mill, the turbine blades pass in close tolerance to the stator surface. Serrations formed in the upper surface of the rotor at the base of the turbine blades also rotate rapidly past the stator and cause further comminution of the pulp particles. With increasing velocity, the slurry containing partially comminuted pulp particles flows through channels formed by the cooperation of the upper surface of the rotor and the lower surface of the stator. The slurry is then subjected to extreme forces of hydraulic shear as it passes through the narrow gap (e.g., on the order of about 0.010 inches (0.25 mm)) between the rotor and the stator. The slurry is finally thrown, by high centrifugal force, from the rotor against the smooth portion of the wall of the stator. This high velocity impingement provides additional size reduction of the pulp particles.
In terms of processing conditions, colloidal milling of the slurry can be carried out at temperatures suitable for high pressure homogenization. Also like high pressure homogenization, colloidal milling can be carried out by one or more passes of the mixture through the mill to achieve the desired thickener attributes.
After the high shear treatment, the resulting thickener material can be cooled to below about 120°F (49°C) to prevent deterioration of the product viscosity. This can be done by blending it immediately into the final beverage formulation, or by cooling with appropriate heat exchangers and placing it in a storage tank. Alternatively, the product can be placed into bottles, cans, or other storage vessels at about 190°F (88°C), sealed and then cooled to produce a hot packed sterile product for later use. The product can be stored without refrigeration or aseptic packaging if appropriate food approved antimicrobial agents are added. The material may be frozen for storage, except that when thawed, additional shearing may be necessary to return the material to its original viscosity.
Calculation of Shear Rate The viscous behavior of the slurry can be described in terms of a pseudoplastic fluid, in contrast to the Newtonian behavior of water or a sugar solution. If measurements are made at different velocity gradients (shear rates), the ratio of shear stress (ST) to shear rate (SR) will not be constant. The ratio is frequently called the apparent viscosity (Ua) which decreases as the shear rate is increased. The shear stress is the force per unit area required to keep the fluid moving, while the shear rate is the velocity gradient perpendicular to the direction of flow.
The behavior of pseudoplastic fluids can be described by the equation:
ST = K x SRn or the equation: Ua = ST/SR = K x SR ""1 where K and n are the fluid consistency and shear index constants, respectively. These equations are described in further detail in Perry's Chemical Engineering Handbook, 4th Edition, pp. 5-13 and pp. 5-35 to 5-38.
The shear rate for a colloid mill (e.g. Greerco) having a 7.5 inch diameter (D) rotor operating at 3550 rpm with a 0.010 inch gap setting between the stator and rotor is defined by the equation:
SR = Velocity Gradient/Distance Gradient = Tip Speed/Gap where the Tip Speed is defined by the equation:
Tip Speed = 3.1416 x D x rpm. Substitution of the numerical values given above yields a calculated shear rate of 139408.5 sec'1.
The shear rate for a high pressure homogenizer (e.g. APV Gaulin) is -calculated from the dimensions of the valves and volumetric capacity of product at a given operating pressure. Representative valve dimensions and capacities are given in U.S. Pat. No. 4,352,573 to Pandolfe, Issued Oct. 5, 1982 and incorporated herein by reference. A homogenizer operating at 4000 psig achieves 120 gallon per hour capacity through a valve having about a 0.001 inch width and about a 0.77 inch circumference. The shear rate (SR) for homogenization is defined as follows:
SR = Velocity Gradient/Distance Gradient = Bulk Velocity/Gap where the Bulk Velocity is calculated from the volumetric flow rate (Q), valve gap (G) and circumference of the valve seat (L) according to the following equation:
Bulk Velocity = Q/(G x L).
Using the numerical values given above in these equations yields a shear rate of 10,000,000 sec"1.
Thickener Product
Relevant Rheological Principles. It is generally understood that solids can be distinguished from liquids by the fact that the solids tend both to resist deformation and to return to their original state when deformed because a deforming force is stored and then used to regenerate the original shape. Liquids resist deformation by dissipating the deforming force as heat but do not recoil. The solid resistance is referred to as elasticity, while the resistance of the liquid is known as viscosity.
In reality, few food or beverage materials are readily classified as either solid or liquid. Most exhibit some combination of elasticity and viscosity. This combination of behaviors is commonly seen in steady shear tests (like those conducted using a Brookfield viscometer) where it causes shear stress vs. shear rate plots to curve. Various mathematical curve fitting schemes can be used to quantify these plots, but none clearly differentiates the elastic component of a sample's rheology from the viscous component. Since the unique properties of the thickener composition produced by the process of the present invention are most clearly seen by its elastic behavior, this lack of differentiation is a problem.
To make it possible to distinguish the elastic and viscous properties of a sample, a low shear oscillatory rheology test is used. In this type of test the sample is moved back and forth over a very small distance, or known as the strain, (too small to cause significant change in the sample). Measuring the amount of stress generated in the sample that is in phase with these oscillations provides information on the near-resting viscosity of the sample, and measuring the 90°-out-of-phase stress tells us about its elasticity. A Vilastic rheometer is used. The Vilastic rheometer is supplied by Vilastic Scientific, Inc., P. O. Box 160261, Austin, TX, 78716.
In the Vilastic rheometer, the oscillation motor pumps the sample up and down in a small capillary, usually over a distance (strain range) of from about 0.05 to about 11 capillary diameters (the diameter is commonly 1 mm). The generated stress is measured by a pressure sensor below the capillary, and the calculation of in-phase and out-of-phase components is done with an attached personal computer.
Typically used is the common convention of generating storage (G') and loss (G") modulus values (also referred to as elastic and viscous moduli) in units of dynes per square centimeter, either examining them directly or as a ratio (G7G') plotted against strain. Because the test is sensitive to the frequency of oscillation, temperature and sample concentration, these parameters must be fixed. For the rheology values used herein the frequency is set at 1.592 sec"1, the temperature at 52°F (11.1° , and the concentration at 0.25% of thickener composition on an insoluble anhydrous solids weight basis, unless otherwise specified. The mode is a strain sweep and the strain range examined is about 0.05 to about 11 (using a 1 mm diameter jacketed capillary).
Accordingly, a 0.25% insoluble solids (on an anhydrous weight basis) aqueous slurry of the thickener compositions of the present invention exhibits an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3. A 0.25% insoluble solids aqueous slurry of preferred thickener compositions of the present invention have an elastic modulus (G') at or above the values delineated by the equation: log(G') =
((-0.69897) x log(strain)) - 0.71226. A 0.25% insoluble solids aqueous slurry of most preferred thickener compositions of the present invention have an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.66901) x log(strain)) -
0.50471. Generally the upper limit of the elastic modulus (G1) for a 0.25% insoluble solids aqueous slurry of thickener compositions of the present invention are limited only by processing constraints or the palatability of beverages containing this natural thickener. For example, thickener compositions with an elastic modulus (G') above
1000 dynes/cm-^ would have a texture similar to catsup.
Testing for the Thickener Compositions in a Product Matrix.
The thickener compositions of the present invention are paniculate material similar in size and microscopic appearance to background pulp and other homogenized pulps. It can, therefore, be readily screened to remove sensible pulp and extracted from a beverage by centrifugation. Repeated washings with 70°F(21°C) water can reduce gums, sugars and emulsion droplet concentrations to insignificant levels (less than about 0.2°Brix), leaving a pulp residue suitable for insoluble anhydrous solids determination. This insoluble solids residue can then be diluted to the appropriate 0.25% level for a Vilastic run and tested to determine if it falls within the region determined to be occupied by a functional thickener composition of the present invention.
A suspension of sheared particles of thermally treated citrus material comprising cellulose and pectinaceous material prepared by our process can be identified by its rheological characteristics in combination with its microscopic moφhology using the following procedure.
1. Strain sample through a 20-mesh screen if necessary to remove very large particles, then strain sample through a 50-mesh screen to remove remaining large particles. 2. Determine the sample's steady shear viscosity using a Brookfield Rheoset
Viscometer, or a Brookfield Model LVDV-iπ® Programmable Rheometer equipped with a ULA Adapter® and a temperature-controlled jacket. Equilibrate the viscometer to 52°F (11.1°C), and run the sample at 7.3 sec"1 using the standard operating procedures detailed in the manuals for the instrument. A viscosity of at least about 3 centipoise will be detected if the thickener composition of the present invention is present at a sufficient concentration to provide a benefit. 3. Determine the sample's microscopic moφhology using light microscopy.
The thickener of the present invention is obtained, at least in part, from the cell walls of plants. These cell walls are fragmented in processing, but retain identifiable moφhology. Light microscopic identification of citrus cell wall fragments should be performed by a person skilled in the art who has knowledge of the appearance of the cell walls of the source plant material. These fragments can be identified as being derived from cell walls using one or more of the brightfield, interference or phase contrast forms of microscopy, along with polarized light microscopy.
4. Centrifuge the sample to obtain a pellet of insoluble solids. The cell wall fragments that embody the present compositions are insoluble in water. They can, therefore, be centrifuged from a dilute solution, such as a beverage, using a centrifuge. A Beckman J2-21® operating at about 39°F (4°C) equipped with a type JA-10® rotor running at about 7000 rpm for about 30 minutes will concentrate the present compositions as part of a pellet. By resuspending this pellet in water and centrifuging about three times, the product can be freed of soluble contaminants. This pellet can be checked using the same microscopic methods applied in step 3. If the pellet is multi-layered, only that portion which contains plant cell wall fragments should be retained for further processing. A sample of the washed pellet can be dried to determine its percentage content of insoluble anhydrous solids, and some or all of the pellet can then be diluted proportionally to obtain a suspension with an insoluble anhydrous solids content of 0.25%.
5. Determine the dynamic rheology of the sample containing 0.25% insoluble anhydrous solids. The Vilastic V-E System Viscoelastic
Analyzer® (Vilastic Scientific, Inc.) equipped with a 1 mm capillary with a temperature-controlled jacket is used to determine the dynamic oscillatory rheology of beverage products, including those containing finely fragmented plant cell wall pieces. The viscometer is equilibrated at 52°F (11.1°C), and the sample is run at 1.592 sec"1. Using the standard operating procedures detailed in the manuals for this instrument, a strain sweep is run including the range of strains between 0.3 and 3. Samples containing the present compositions will exhibit an elastic modulus (G') in this standardized test such that, for the entire range of strains between 0.3 and 3, log(G') > ((-0.69897) x log(strain)) -
0.96754.
6. If the elastic modulus values determined in step 5 above are such that, for the range of strains between 0.3 and 3, log(G') > ((-0.69897) x log(strain)) - 0.96754, the presence of the present compositions can be verified by repeating step 5, except with the rheometer equilibrated at
113°F (45°C). Samples containing the present compositions will continue to exhibit an elastic modulus (G*) such that, for the entire range of strains between 0.3 and 3, log(G') ≥ ((-0.69897) x log(strain)) -
0.96754. Further, samples containing at least 0.25% insoluble solids of the thickener of this invention can be heated to a temperature of about
190°F (88°C) for up to about one hour, cooled, and then retested as in step 5, and the thickener will continue to exhibit an elastic modulus (G') such that, for the entire range of strains between 0.3 and 3, log(G') ≥ ((-
0.69897) x log(strain)) - 0.96754.
Uses
The thickener compositions of the present invention can be used as thickeners and/or stabilizers and/or clouding agents in any beverage. Typically from about 0.15% to about 2% preferably from about 0.2% to about 1 % of the beverage on an anhydrous weight basis is the thickener composition. Preferred ranges are from about 0.05% to about 2%, more preferably from about 0.1 % to about 1% and most preferably from about 0.1 % to about 0.5% of the beverage on an anhydrous weight basis is the thickener composition. Further, the invention relates to beverages comprising the thickener of the present invention. Such beverages comprise: a) from about 0.15% to about 2%, by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids (on an anhydrous weight basis) aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754, preferably log (G*)=((-0.69897)x log(strain))-0.71226 and most preferably log(G')=((- 0.66901)xlog (strain))-0.50471, for the entire range of strains from 0.3 to 3.
Generally, a single-strength fruit juice beverage of the present invention comprises: a) from about 0.15% to about 2%, by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G*) at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754, preferably log (G*)=((-0.69897)x log(strain))-
0.71226 and most preferably log(G')=((-0.66901)xlog (strain))-0.50471, for the entire range of strains from 0.3 to 3; b) at least about 5%, preferably at least about 10%, and more preferably at least about 20%, fruit juice; and c) from 0% to about 30%, preferably from 0% to about 25% and most preferably from about 0% to about 20% added sweetener solids. A preferred dilute juice beverage of the present invention comprises: a) from about 0.05% to about 2% by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G1) at or above the values delineated by the equation: log(G')=((-0.69897)x log(strain)) - 0.96754, preferably log(G')=((-0.69897)x log (strain))- 0.71226 and most preferably log(G')=((-0.66901)x log (strain)) - 0.50471, for the entire range of strains from 0.3 to 3; b) from about 0.2% to about 50%, more preferably from about 1 % to about 35%, fruit juice.
A fruit juice concentrate of the present invention can comprise from about 0.2% to about 8%, by anhydrous weight, of a citrus fruit derived thickener composition of the present invention.
Generally, a preferred fruit juice concentrate of the present invention comprises: a) from about 0.60% to about 8%, by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 , preferably log (G')=((-0.69897)x log(strain))- 0.71226 and most preferably log(G')=((-0.66901)xlog (strain))-0.50471, for the entire range of strains from 0.3 to 3; and b) at least about 45% fruit juice; preferably at least about 65% and most preferably at least about 95%. Another preferred fruit juice concentrate of the present invention comprises: a) from about 0.2% to about 8%, by anhydrous weight, of a citrus fruit derived thickener composition of the present invention; and b) at least about 0.7% fruit juice.
For storage and transport convenience, the thickener compositions of the present invention can be dried. After high shear treatment, water soluble, inert substances, such as sweeteners and maltodextrins may be added, if necessary, to achieve, °Brix to insoluble anhydrous solids ratio of from about 1: 1 to about 10: 1, preferably from about 2:1 to about 10:1 and most preferably from abut 3:1 to 10:1. Without intending to be bound by theory, the purpose of these water soluble inert materials is to aid in the drying of the thickener and rehydration of the dried material, as is commonly practiced in the spray drying of instant coffee. The preferred water soluble inert materials for addition are sweeteners like glucose, sucrose, fructose, high fructose com syrup solids, invert sugar, sugar alcohols and mixtures thereof. The most preferred sweetener for use is sucrose.
The addition of sweeteners to achieve the appropriate °Brix to insoluble anhydrous solids ratio may not be necessary. If the addition of sweeteners is necessary to achieve the appropriate °Brix to insoluble solids ratio, the addition can be in the form of adding dry sweeteners with agitation to the slurry, by adding a slurry of sweeteners and water to the slurry or in any other conventional method typical for adding sweeteners during beverage processing. After the appropriate "Brix to insoluble solids ratio is achieved, the slurry is dried to a moisture content of from about 1 % to about 15%, preferably from about 4% to about 9%, water. This can be done by any of the conventional means, such as spray drying, vacuum oven drying, drum drying, or freeze drying. The preferred method of drying is by spray drying by using commercially available spray dryers such as those made by Niro Atomizer (9165 Rumsey Rd., Columbia, MD 21045).
Thus the process of the present invention can comprise the additional steps of: a)adding a sweetener such that said slurry has a °Brix to insoluble solids ratio of from about 1: 1 to about 10:1, preferably from about 2:1 to about 10:1 and most preferably from about 3:1 to about 10:1; and b)drying said slurry to a moisture content of from about 1% to about 15% preferably from abut 4% to about 9%, water. EXAMPLES
The following non-limiting examples illustrate the citrus fruit derived thickener compositions of the present invention. EXAMPLE 1
One hundred twenty pounds of commercial Valencia orange pulp (Cargill, Inc.,
Box 37, Frostproof, FL 33843) containing about 5% insoluble solids on an anhydrous weight basis is added to 120 pounds of water producing a sluπy comprising about 2.5% anhydrous weight insoluble solids. The slurry is stirred and heated at about 190 F (88°C) for a period of about 1 hour in a 30 gallon Hamilton Kettle® (Hamilton Kettles, 11861
Mosteller Rd., Cincinnati, OH 45241). The material is cooled to about 80°F (27°C) over the course of about one hour. It is then subjected to high shear treatment by homogenization by passing it through a Gaulin M-3® homogenizer (APV Gaulin, Inc., 500 Research Drive, Wilmington, MA 01887) at about 4000 psig, using two separate passes. The resulting thickener slurry provides good clouding properties. Take 1 part of the resulting slurry and dilute with 9 parts water making 10% water solution having turbidity of 807 NTLPs as measured on a Model DRT 100B Turbidimeter (HF Instruments, Ft. Meyers, FL). It is added at about a 10% level to a dilute juice beverage mixture comprising about 5% orange juice, about 12% added sweetener solids, about 0.02% orange flavor oil and about 82.98% added water. The result is a pleasingly thick juice-textured beverage with a natural cloud appearance in which the cloud and background pulp do not noticeably settle after several days. The beverage has a viscosity of about 15.2 cp at about 7.3 sec"1 of shear as measured in a UL Adapter® on a Brookfield LVDV-ϋl® viscometer (Brookfield Engineering Lab, Inc., 240 Cushing St., Stoughton, MA 02072).
EXAMPLE 2 Sixty pounds of commercial Valencia citrus pulp (Cargill, Inc., Box 37, Frostproof, FL 33843) containing about 5% insoluble solids on an anhydrous weight basis is added to about 120 pounds of water producing a slurry of about 1.25% insoluble solids on an anhydrous weight basis. The slurry is stirred and heated at about 190°F (88°C) for a period of about 1 hour in a 30 gallon Hamilton Kettle (Hamilton Kettles, 11861 Mosteller Rd., Cincinnati, OH 45241). The material is cooled to about 80°F (27°C) over the course of about one hour. It is then subjected to high shear treatment by homogenization by passing it through a Gaulin® M-3 homogenizer (APV Gaulin, Inc. , 500 Research Drive, Wilmington, MA 01887) at about 6000 psig, using one pass with an about 3000 psig pressure drop across each of two valves. The material is added at about a 20% level to a dilute juice beverage mixture comprising about 5% orange juice, about 12% added sweetener solids, about 0.02% orange flavor oil and about 72.98% added water. The result was a pleasingly thick juice-textured beverage with a natural cloud appearance in which the cloud and background pulp did not noticeably settle after several days.
EXAMPLE 3 Five grams of washed and dried, sugar-free citrus pulp (CitroFiber DF-50®, from Citrosuco Paulista S/A, Postal 01, Matao, 15990, Brazil) is added to about 1000 grams of water and comminuted using a food processor for sufficient time to produce a sluπy which easily passes through the homogenization equipment. It is then heated to about 205°F
(96°C) for about one hour. The slurry is subjected to high shear treatment by homogenization using two passes through a model M-110T MicroFluidizer®
(MicroFluidics, Coφ., 90 Oak St., Newton, MA 02164) at a pressure of about 6000 psig.
The resulting slurry has a viscosity of about 27 cp at about 7.3 sec"1 .
EXA PLE 4
Four hundred gram aliquots of the following beverages are analyzed for the presence of the thickener compositions of the present invention:
1) United Dairy Farmers brand orange juice (100% juice from concentrate);
2) United Dairy Farmers brand orange drink (a dilute juice beverage thickened with gums);
3) Tropicana Twister brand orange-peach beverage (a beverage thickened with pulp and pectinaceous material);
4) Dittmeyer's Punica (a dilute juice beverage thickened with homogenized citrus pulp);
5) Awake by Erly Juice, Inc. (a dilute juice beverage thickened with gums); and 6) A formulated dilute juice beverage of Example 1.
AU samples are strained through a 50-mesh screen to remove large particles. They are then tested for steady shear viscosity using a Brookfield Model LVDV-IQ® Programmable Rheometer equipped with a ULA Adapter and a temperature-controlled jacket. The viscometer is equilibrated at 52°F (11.1°C), and the samples run at about 7.3 sec"1 using the standard operating procedures detailed in the manuals for this instrument.
The measured viscosities of these samples are about 10.5 cp for the United Dairy Farmers orange juice, about 2.4 cp for the United Dairy Farmers orange drink, about 3.7 cp for the Tropicana Twister orange-peach beverage, about 2.5 cp for Dittmeyer's Punica, about 4.0 cp for Awake, and about 19.4 cp for the formulated dilute juice beverage containing the thickener material of the present invention described herein. Although the viscosities of some of these beverages are less than about 3 cp, as a scientific exercise, all examples are examined further.
Microscopic examination reveals the presence of small particles which can be characterized moφhologically as components of citrus materials in the United Dairy Farmers orange juice, the Tropicana Twister orange-peach beverage, Dittmeyer's Punica, and the formulated dilute juice beverage containing the thickener material of the present invention described herein. No particles from citrus materials are found in the other two samples, so no further analysis is needed.
The four remaining samples are centrifuged using a Beckman J2-21® operating at about 39°F(4°C) equipped with a type JA-10® rotor running at about 7000 φm for about 30 minutes, the supematants discarded, and the pellets resuspended in ambient temperature (70°F(21°C)) water three times. Then the washed samples are centrifuged once more and decanted to obtain pellets of insoluble solids.
Microscopic examination indicates that all four insoluble solids samples contain small particles which can be characterized moφhologically as components of citrus materials, so a portion of each is dried to obtain a percentage dry weight value. Then another portion of each is resuspended in water to a final concentration of 0.25% on an anhydrous weight basis.
The dynamic rheology of the four samples containing about 0.25% insoluble solids is determined using a Vilastic V-E System Viscoelastic Analyzer® (Vilastic Scientific, Inc.) equipped with a 1 mm capillary with a temperature-controlled jacket. The rheometer is equilibrated at 52°F (ll.TC), and the samples run at 1.592 Hz. Using the standard operating procedures detailed in the manuals for this instrument, a strain sweep including the range of strains between 0.3 and 3 are run on each sample. The elastic modulus (G') values for the three commercial products tested fall below the values defined by the equation log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains between 0.3 and 3. The G' values for the formulated dilute juice beverage containing the thickener material of the present invention described herein are above those values (Figure 1).

Claims

WHAT IS CLAIMED IS:
1. A process for preparing a thickener composition suitable for use in beverage products characterized in that the process comprises the steps of: a) preparing a slurry of water and citrus pulp, said slurry having an insoluble solids content of from 0.15% to 10%, preferably from 0.15% to 5%, on an anhydrous weight basis; b) heating said slurry to a temperature of from 158°F (70°C) to 356°F (180°C), preferably from 176°F (80°C) to 212°F (100°C), for at least 2 minutes; and thereafter c) subjecting said slurry to high shear treatment by imparting shear at a rate of at least 20,000 sec"1, preferably from 20,000 sec"1 to 100,000,000 sec"1 and more preferably from 50,000 sec"1 to 20,000 sec"1, preferably by homogenization.
2. A process according to Claim 1 wherein said high shear treatment reduces the particles of said citrus pulp to a particle size of from 5 micrometers to 500 micrometers.
3. A process according to Claim 1 wherein said slurry is subjected to high shear treatment to the extent that a 0.25%, on an anhydrous weight basis, of insoluble solids aqueous slurry exhibits an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3.
4. A process according to Claim 1 comprising the additional steps of: a) adding a sweetener such that said slurry has a °Brix to insoluble solids ratio of from 1:1 to 10:1; and b) drying said slurry to a moisture content of from 1% to 15% water.
5. A thickener composition derived from citrus fruits characterized in that it is produced by the process of Claim 1.
6. A process for preparing a thickener composition suitable for use in beverage products characterized in that the process comprises the steps of: a) preparing a slurry of citrus pulp and water wherein said slurry has an insoluble solids content of from 0.15% to 10%, preferably from 0.15% to 5%, on an anhydrous weight basis; b) heating said slurry to a temperature of from 158°F (70°C) to 35<5°F (180°C), preferably from 176°F (80°C) to 212°F (100°C), for at least 2 minutes; and thereafter c) subjecting the slurry to a high shear treatment by homogenizing said slurry at a pressure of from 1000 to 10,000, preferably from 3000 to 6000, pounds per square inch.
7. A process according to Claim 8 comprising the additional steps of: a) adding a sweetener such that said slurry has a °Brix to insoluble solids ratio of from 1:1 to 10:1; and b) drying said slurry to a moisture content of from 1% to 15% water.
8. A thickener composition derived from citrus fruits characterized in that it is produced by the process of Claim 6.
9. A thickener composition derived from citrus fruits characterized in that it is produced by the process of Claim 6 wherein said slurry is homogenized to the extent that a 0.25% insoluble solids aqueous slurry of the resulting slurry exhibits an elastic modulus (G1) at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3.
10. A thickener composition characterized in that it is derived from citrus fruits comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3.
11. A thickener composition derived from citrus fruits according to Claim 10 wherein the elastic modulus (G1) is at or above the values delineated by the equation: log(G') = ((-0.69897) x log (strain)) - 0.71226 for the entire range of strains from 0.3 to 3.
12. A thickener composition derived from citrus fruits according to Claim 11 wherein the elastic modulus is at or above the values delineated by the equation: log(G') = ((-0.66901) x log (strain)) - 0.50471 for the entire range of strains from 0.3 to 3.
13. A beverage characterized in that it comprises from 0.15% to 2%, on an anhydrous weight basis, of insoluble solids of a thickener composition derived from citrus fruits wherein a 0.25% insoluble solids aqueous slurry of said thickener composition has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.66901) x log (strain)) - 0.50471 for the entire range of strains from 0.3 to 3.
14. A fruit juice concentrate characterized in that it comprises: a)from about 0.60% to about 8%, by anhydrous weight, of a thickener composition derived from citrus fruits comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G1) at or above the values delineated by the equation: log (G')=((- 0.69897)x log(strain))-0.96754 for the entire range of strains from 0.3 to 3; and b) at least about 45% fruit juice.
15. A process for preparing a thickener composition suitable for use in beverage product, characterized in that the process comprises the steps of: a)preparing a slurry of water and citrus pulp, said slurry having an insoluble solids content of from 0.1% to 15%, preferably from 2% to 10%, on an anhydrous weight basis; b)heating said slurry to a temperature of at least 158°F (70°C) for at least 1 minute, preferably from 158°F (70°C) to 356°F (180°C) for at least one minute; more preferably from 176°F (80°C) to 275°F (135°C) for at least 2 to 240 minutes; and most preferably from 185°F (85°C) to 257°F (125°C) for from 3 to about 120 minutes, and thereafter c)subjecting said slurry to high shear treatment by homogenizing at a pressure of at least 1000 pounds per square inch, preferably at least 3,000 psig and more preferably from 3000 psig to about 15,000 psig.
16. A thickener composition derived from citrus pulp characterized in that it is produced by the process of Claim 20.
17. A process according to Claim 15 characterized in that it is comprises the additional steps of: a)adding a sweetener such that said slurry has a °Brix to insoluble solids ratio of from 1: 1 to 10:1; and b)drying said slurry to a moisture content of from 1% to 15% water.
18. A thickener composition produced by the process of Claim 15 wherein said slurry is homogenized to the extent that a 0.25% insoluble solids aqueous slurry of the resulting slurry exhibits an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log( strain)) - 0.96754 for the entire range of strains from 0.3 to 3.
19. A beverage, comprising from 0.05% to 2%, on an anhydrous weight basis, of insoluble solids of a thickener composition derived from citrus &uit wherein a 0.25% insoluble solids aqueous slurry of said thickener composition has an elastic modulus (G1) at or above the values delineated by the equation: log(G') = ((-0.66901) x log (strain)) - 0.50471 for the entire range of strains from 0.3 to 3.
20. A fruit juice concentrate characterized in that it comprises: a)from 0.2% to 8%, by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material wherein a 0.25% insoluble solids aqueous slurry of said cellulose and pectinaceous material has an elastic modulus (G') at or above the values delineated by the equation : log (G')=((-0.69897)x log(strain))-0.96754 for the entire range of strains from 0.3 to 3; and b)at least about 0.7% fruit juice.
21. A beverage comprising : a)from 0.05% to 2%, by anhydrous weight, of a thickener composition derived from citrus fruit comprising cellulose and pectinaceous material has an elastic modulus (G') at or above the values delineated by the equation: log(G') = ((-0.69897) x log(strain)) - 0.96754 for the entire range of strains from 0.3 to 3; and b)from 0.2% to 50% fruit juice.
PCT/US1994/005672 1993-05-28 1994-05-20 Method for producing a natural citrus pulp thickener, stabilizer and cloud agent for beverages WO1994027451A1 (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2311024A (en) * 1996-03-15 1997-09-17 Systems Bio Ind Depolymerised pectins
WO1998026675A2 (en) * 1996-12-19 1998-06-25 The Coca-Cola Company Stabilizer system and method for lessening the separation of solids in juice-containing products
WO1998028991A2 (en) * 1996-12-11 1998-07-09 Gist-Brocades B.V. Cloudy fruit juices and methods for making same
US7335389B2 (en) 2002-06-12 2008-02-26 The Coca-Cola Company Beverages containing plant sterols
ES2329862A1 (en) * 2008-02-22 2009-12-01 Consejo Superior De Investigtaciones Cientificas Procedure to obtain a prebiotic product of high content in fiber soluble, said product and its applications (Machine-translation by Google Translate, not legally binding)
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US20140356463A1 (en) * 2012-01-20 2014-12-04 Cargill, Incorporated Process for obtaining citrus fiber from citrus peel
EP2330928B1 (en) 2008-08-29 2016-02-24 Tropicana Products, Inc. Naturally sweetened juice beverage products
WO2017019752A1 (en) * 2015-07-30 2017-02-02 Cargill, Incorporated Dry citrus fibers and uses thereof
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US20180155869A1 (en) * 2010-07-30 2018-06-07 Cargill, Incorporated Process for modifying the properties of citrus pulp
US20180155454A1 (en) * 2010-07-30 2018-06-07 Cargill, Incorporated Process for obtaining citrus fiber from citrus pulp
US20180153199A1 (en) * 2014-07-15 2018-06-07 Cargill, Incorporated Process for obtaining citrus fiber from citrus peel
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US10334870B2 (en) 2010-10-07 2019-07-02 Tropicana Products, Inc. Processing of whole fruits and vegetables, processing of side-stream ingredients of fruits and vegetables, and use of the processed fruits and vegetables in beverage and food products
US10667546B2 (en) 2013-02-15 2020-06-02 Pepsico, Inc. Preparation and incorporation of co-products into beverages to enhance nutrition and sensory attributes
WO2020157102A1 (en) 2019-02-01 2020-08-06 Societe Des Produits Nestle S.A. Syrup binder system for preparing food, and preparation process and use thereof
WO2021250150A1 (en) 2020-06-10 2021-12-16 Herbstreith & Fox Gmbh & Co. Kg Pektin-Fabriken Activatable, pectin-containing citrus fiber
WO2021250152A1 (en) 2020-06-10 2021-12-16 Herbstreith & Fox Gmbh & Co. Kg Pektin-Fabriken Activated, pectin-containing citrus fiber
WO2022029152A1 (en) 2020-08-05 2022-02-10 Herbstreith & Fox Gmbh & Co. Kg Pektin-Fabriken Activatable, deesterified fruit fiber
WO2022029131A1 (en) 2020-08-05 2022-02-10 Herbstreith & Fox Gmbh & Co. Kg Pektin-Fabriken Activatable, deesterified pectin-converted fruit fiber

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292046A2 (en) * 1987-05-18 1988-11-23 The Procter & Gamble Company Low viscosity evaporative orange juice concentrates having less cooked off-flavor
EP0337526A1 (en) * 1988-03-31 1989-10-18 The Procter & Gamble Company Low viscosity orange juice concentrates useful for high Brix products having lower pseudoplasticity and greater dispersibility
WO1990004333A1 (en) * 1988-09-05 1990-05-03 Institut National De La Recherche Agronomique (Inra) Process for treating products rich in plant cell walls, in particular rich in pectins, said pectins, the extraction residues from the process, their use and compositions containing them
EP0485030A1 (en) * 1990-11-06 1992-05-13 The Procter & Gamble Company Fruit juice plus citrus fiber from pulp
US5260086A (en) * 1992-05-15 1993-11-09 The Procter & Gamble Company Fresh-like storage-stable pulp and improved juice product and process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292046A2 (en) * 1987-05-18 1988-11-23 The Procter & Gamble Company Low viscosity evaporative orange juice concentrates having less cooked off-flavor
EP0337526A1 (en) * 1988-03-31 1989-10-18 The Procter & Gamble Company Low viscosity orange juice concentrates useful for high Brix products having lower pseudoplasticity and greater dispersibility
WO1990004333A1 (en) * 1988-09-05 1990-05-03 Institut National De La Recherche Agronomique (Inra) Process for treating products rich in plant cell walls, in particular rich in pectins, said pectins, the extraction residues from the process, their use and compositions containing them
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Publication number Priority date Publication date Assignee Title
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