WO2007034213A1 - Process for encapsulation of edible oil products with whey protein and encapsulated edible oil products - Google Patents

Process for encapsulation of edible oil products with whey protein and encapsulated edible oil products Download PDF

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Publication number
WO2007034213A1
WO2007034213A1 PCT/GB2006/003546 GB2006003546W WO2007034213A1 WO 2007034213 A1 WO2007034213 A1 WO 2007034213A1 GB 2006003546 W GB2006003546 W GB 2006003546W WO 2007034213 A1 WO2007034213 A1 WO 2007034213A1
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WO
WIPO (PCT)
Prior art keywords
capsule
micro
oil
whey protein
acid
Prior art date
Application number
PCT/GB2006/003546
Other languages
French (fr)
Inventor
Nigel Slater
Original Assignee
Cambridge Applied Polymers Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0519509A external-priority patent/GB0519509D0/en
Priority claimed from GB0616102A external-priority patent/GB0616102D0/en
Application filed by Cambridge Applied Polymers Limited filed Critical Cambridge Applied Polymers Limited
Publication of WO2007034213A1 publication Critical patent/WO2007034213A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A23L33/12—Fatty acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • This invention relates to a method for encapsulation of edible oil products, encapsulated edible oil products made thereby, and use of such products in the production of finished food products.
  • the edible oils with which the invention is concerned in particular are edible oils, including but not necessarily restricted to omega-3 rich nutrient oils which are usually sourced from fish or monocellular vegetable sources such as algae and fungi.
  • omega-3 rich nutrient oils which are usually sourced from fish or monocellular vegetable sources such as algae and fungi.
  • the latter are of particular interest as they are suitable for all vegetarians.
  • Chemically omega-3 rich oils contain a high proportion of unsaturated fatty acids, having at least three unsaturated carbon-carbon bonds, and preferably five or six. Examples of such fatty acids are:-
  • Omega-3 rich oils have a value as a nutritional or dietary supplement, with however little clear guidance as to best or maximum recommended intake. Specific positive heath effects, especially in infants have been linked to the presence in diets of omega-3 oils, more specifically to the unsaturated fatty acids EPA and DHA.
  • omega-3 rich oils it is desirable for such omega-3 rich oils to be made available in a form which is suitable for addition to food products.
  • a further problem of such oil and fatty acids is that on oxidation, e.g. on exposure to the air, they have a tendency to emit an unpleasant 'fishy odour' (they are in fact the source of this smell as experienced with poorly kept fish). For this reason, it is desirable to protect the oil product from contact with air.
  • One method of doing so is encapsulation, by coating droplets of the oil with a sealant.
  • Gelatine products being of animal origin are not suitable for products intended to be available for vegetarians. It is an object of the invention to provide a process for micro-encapsulating edible oils, and edible oil products made thereby wherein the oils are kept from contact from air or other sources of oxidation, in a manner which presents no ethical or dietary problems.
  • a range of edible oils may be encapsulated in a material including a major portion of whey-protein, wherein the edible oil comprises up to 50% by weight of the total.
  • the edible oil comprises upto 25% by weight of the whey protein.
  • the invention provides an encapsulated product comprising edible oil encapsulated or micro-encapsulated in a material including a major portion of whey-protein, or an encapsulated material as produced by the method of the first aspect.
  • the invention further provides a food product when including an encapsulated product according to the invention.
  • the process may be a batch process or a continuous process.
  • the encapsulating material may be prepared first by adding whey-protein to water, preferably together with a binding material such as carboxyl methyl cellulose, the mixture is blended, and heated to de-nature the protein, then cooled.
  • the denaturing is carried out by use of a multistage heating process, the mixture being initially heated to 6O 0 C for 5 minutes, then to 7O 0 C for 10 minutes and finally to 77 0 C for 15 minutes.
  • the edible oil is chosen from the group comprising; nutritional oils, flavour oils, phytosterols, oryzanol, tocopherol, tocotrienol and polyphenol.
  • the nutritional oils are chosen from the group comprising; omega 3 -oils, polyunsaturated vegetable oils, rice bran oil, wheat germ oil, maize germ oil and other vegetable oils.
  • the omega-3 rich oil preferably containing a high proportion of EPA and/or DHA, which may be derived from fish, or mono-cellular fungi, but is preferably derived from mono-cellular algae is then added to the encapsulating material.
  • the mixture may be gelled by adding a gelling agent such as citric acid or other food grade acids, and is homogenised by agitation.
  • a droplet size of 60-80 microns is achieved and more preferably a droplet size of 40 microns is achieved.
  • the product of this process may then be freeze dried, and milled until free flowing.
  • the milled material may then be added to a solution of carboxyl methyl cellulose in water, stirred whilst heating, preferably at a temperature of 4O 0 C, and then left to cool.
  • a further gelling step involving the addition of a food grade acid e.g. citric acid, may follow and then the product may be cryostructured by controlled - A -
  • freeze drying which causes the carboxyl methyl cellulose to cross-link to provide insoluble micro-capsules, which are then milled until free flowing.
  • micro-capsule from this exemplified process comprises (by weight) Water 3.5 to 4.2%
  • Citric acid 28.2 to 33.5% The product may then be stored for use, and transported to a use site where it may be mixed with water to form a slurry, and sprayed onto a food product, such as a cereal to provide a coating of edible oil micro-capsules on the surface of the food product.
  • the food product is chosen from the group comprising hard cheese, cottage cheese and cream cheese, yoghurt, quark, margarine, low fat spreads, mayonnaise and salad dressings, ice cream, and baked goods.
  • the slurry may alternatively be mixed into semi-solid products such as cottage cheese and mayonnaise.
  • the process is preferably carried out in a non-reactive atmosphere, such as a nitrogen blanket, and the mixing and blending steps may be carried out in a vessel which incorporates a heating apparatus and means to establish and maintain the non- reactive atmosphere.
  • a non-reactive atmosphere such as a nitrogen blanket
  • the food grade acids that may be used are chosen from the group comprising; citric acid, tartaric acid, lactic acid and phosphoric acid.
  • the mixture is allowed to stand for a period of time, e.g. 12 hours, to allow further gelation.
  • the multiple whey protein/oil molecules are held together in particles by the carboxylic acid groups of the carboxyl methyl cellulose molecules. The hydrogen bond cross- linking of these groups, to produce micro-capsules enhances the integrity of the particles.
  • the mixture is then stirred whilst a solution of carboxyl methyl cellulose in water is added.
  • the resultant mixture is spray dried to give a free flowing powdered product, wherein the carboxyl methyl cellulose is cross-linked to provide an outer shell for the particles.
  • the microcapsule according to the second embodiment comprises by % weight on a dry basis Whey protein 51.7 to 61.3%
  • the gelling of the mixtures previously described is achieved by adding sufficient acid to lower the pH of the mixture to 3.0 at a temperature of 1O 0 C.
  • micro-capsule for the encapsulation of edible oils and processes for the preparation of said micro- capsule substantially as described herein with reference to and as illustrated by any appropriate combination of the accompanying drawings.
  • Encapsulation of edible oils results in the edible oil being adsorbed onto the hydrophobic surfaces within the whey protein particles.
  • the whey proteins protect the edible oils, particularly omega-3 oils from oxidation thus enhancing the shelf-life of the product.
  • Figure 2 is a flow-diagram illustrating the steps of one exemplified embodiment/process according to the invention
  • Figure 3 is a diagram showing initial steps of a further exemplified embodiment/process according to the invention
  • Figure 4 is a diagram showing a first series of intermediate steps of the further exemplified embodiment/process according to the invention
  • Figure 5 is a diagram showing a second series of intermediate steps of the further exemplified process according to the invention
  • Figure 6 is a diagram showing the final step of an exemplified embodiment/process according to the invention.
  • Figures 7a-7d shows schematically the various conformations adopted by whey protein oil and carboxyl methyl cellulose during the encapsulation process; and
  • Figure 8 shows schematically an expanded view of the structure of a carboxyl methyl cellulose micro-capsule encapsulating particles of whey protein and oil.
  • a mixer blender apparatus comprises a vessel
  • An agitator or stirrer is provided in the form of mixer blades 15, which are mounted for rotation on the lower end of a shaft 16 which is driven by a sealed motor unit 17 on the upper wall of the vessel.
  • An electrical heating apparatus is also provided, and is shown diagrammatically as a heating element 18 disposed below the vessel 10. This of course could be an immersion heater actually extending into the vessel 10.
  • the vessel also has a water jacket 19 which can be used to cool the vessel when required.
  • the vessel may be emptied by opening a sealed lid part which includes the motor 17, and decanting the liquid product 14 from the vessel.
  • a quantity of whey-protein and carboxyl methyl cellulose, in a 10 to 1 weight ratio is added.
  • the additives are stirred into the water for 10 minutes at 2O 0 C.
  • the next step is to denature the protein.
  • an omega-3 rich oil is added to the mixture, at 1O 0 C whilst stirring for one minute.
  • the oil may for example be a proprietary supplied oil such as DHA-rich algal oil, and may be added in a proportion of 25% by weight of the whey- protein.
  • the next step is to gel the mixture. This is done by addition of solid citric acid or other food-grade acid, in quantity sufficient to achieve a pH of 3.0 at 1O 0 C.
  • the product resulting is then homogenised by rapid stirring for 1 minute to a droplet size of 60-80 microns, e.g. 40 microns. All these operations are carried out under a non-oxidising nitrogen atmosphere in the upper part 13 of the vessel.
  • the homogenised product comprising gelled micro-droplets (particles) which are also known as capsules which may also be reformed to as capsules of oil and whey, is then subjected to freeze drying for four hours, without vacuum, at - 3O 0 C, and then for 20 hours at - 3O 0 C under a reduced pressure at - 80m Torr.
  • a fresh charge of water in the vessel 10, or a second similar vessel is prepared by adding a further quantity of carboxyl methyl cellulose, whilst stirring and heating at 100 0 C for five minutes, and cooling to 4O 0 C, where it is held for five minutes before adding the product from the freeze-drying step, after milling of the latter for 1 minute at 1O 0 C.
  • the addition is carried out whilst stirring, and cooling to 4O 0 C in a nitrogen atmosphere.
  • the mixture is then gelled again by adding solid citric acid or other food grade acid to achieve a pH of 3.0 at 1O 0 C and the product thus obtained cryostructured by a controlled freeze drying procedure comprising first freeze-drying for 4 hours at - 3O 0 C under normal pressure, then 20 hours ramping at - 3O 0 C to - 1O 0 C, under - 80m Torr vacuum.
  • a controlled freeze drying procedure comprising first freeze-drying for 4 hours at - 3O 0 C under normal pressure, then 20 hours ramping at - 3O 0 C to - 1O 0 C, under - 80m Torr vacuum.
  • the product is then subjected to ageing, and milled for 1 minute at 1O 0 C, until free-flowing.
  • a food grade surfactant may be added to avoid particle agglomeration.
  • the product following cryostructing may comprise, (by weight %).
  • the product may be aged and bagged for at least 24 hours at 1O 0 C 5 and stored and/or distributed by commercial channels to the end user who uses it by adding the encapsulated oil/whey/carboxyl methyl cellulose powder to water to form a slurry, homogenising the same and possibly filtering or straining it before use.
  • One use is to spray the product as a liquid slurry onto a food product such as a flake or biscuit/mini biscuit type cereal or to fruit pieces, nuts or other food ingredients to provide a coating on at least one surface thereof of the encapsulated omega-3 rich oil, whereby this may act as a dietary supplement to add value to the food product.
  • a further embodiment of the process for producing micro-capsules according to the invention is described with reference to Figure 3. The process may be carried out using the apparatus previously disclosed and under a nitrogen atmosphere, as before.
  • a volume of de-ionised and de-aerated water (100Og) 15, in a vessel 10 is stirred (step 1) and then, a quantity of whey protein (20Og) and carboxyl methyl cellulose (2Og), in a 10 to 1 weight ratio is added (step 2).
  • the additives are stirred into water for 10 minutes at 2O 0 C.
  • the next step is to denature the protein (step 3).
  • the oil may for example be a proprietory supplied oil such as DHA-rich algal oil, and may be added in a proportion of 25% relative to the whey-protein.
  • the next step is to gel the mixture (step 6). This is done by the addition of solid citric acid (7Og), or other food grade acid, in quantity sufficient to achieve a pH of 3.0 at 1O 0 C. In this way the carboxylic acid groups, of the carboxyl methyl cellulose are protonated. The resultant hydrogen bond cross-linking enhances the integrity of the particles.
  • the resulting product is then homogenised by rapid stirring to a droplet size of 60 - 80 ⁇ m, e.g. 40 ⁇ m (step 7).
  • the homogenised product comprises oil and whey protein held together in particles by carboxyl methyl cellulose molecules.
  • the product is then allowed to stand for 12 hours, to allow further gelation.
  • a second solution comprising 2% of carboxyl methyl cellulose (1Og) in water (500g) is prepared (step 8).
  • the second solution is heated and stirred to completely dissolve the carboxyl methyl cellulose.
  • the 2% carboxyl methyl cellulose solution is then added to an approximately equal volume of the homogenised produced comprising water (500g), whey protein (10Og), carboxyl methyl cellulose (1Og) 5 oil (25g) and citric acid (35g) (step 9).
  • the homogenised product comprising particles of oil and whey, being stirred at a temperature of 2O 0 C and the carboxyl methyl cellulose being added over a period of 5 minutes.
  • This stage of the process provides an outer shell of carboxyl methyl cellulose (CMC) which encapsulates the particles, thus, giving the final product in the form of a micro-capsule containing particles of oil and whey.
  • CMC carboxyl methyl cellulose
  • the mixture is cooled to a temperature of 10 to 2O 0 C, before spray drying using high pressure air at 170 to 19O 0 C (step 10), the outlet of the spray dryer being at a temperature of 70 - 9O 0 C.
  • the product may typically comprise by weight on a dry basis:
  • Figure 7a shows the conformation of a whey protein molecule dissolved in water. Hydrophobic regions of the whey protein molecular are internalised to minimise their interaction with the aqueous phase.
  • Figure 7b shows the conformation of a thermally denatured whey protein molecule.
  • the hydrophobic regions of the whey protein molecules are now exposed and available to associate with hydrophobic oil molecules.
  • Figure 7c shows multiple whey protein/oil molecules held together in a nano- particle by CMC molecules.
  • the pH of the aqueous phase is then lowered by the addition of citric acid, or other food grade acid, resulting in the protonation of the
  • FIG. 7d shows the second stage of the encapsulation process wherein CMC provides an outer shell for the particles.
  • Figure 8 is an expanded version of the Figure 7d enabling the structure of the micro-capsule encapsulating the particles of whey-protein and oil to be more clearly seen.
  • the structure of the capsules encapsulating the whey protein and oil, obtained by the process described herein, are believed to be the same, or at least similar in structure to those obtained by the previously described process which utilises two freeze drying steps in the production of the micro-capsules.
  • the whey protein and carboxyl methyl cellulose used in the process described herein are food grade materials.
  • capsules and microcapsules described herein could be used to manufacture larger capsules, for example capsules which are sized for consumption by humans and animals.
  • temperatures at which the various steps disclosed above are carried out may be varied by +/-15 0 C. It may be possible to remove or dispense with the use of citric acid.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
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  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Dispersion Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Edible Oils And Fats (AREA)
  • Dairy Products (AREA)

Abstract

A micro-capsule for the encapsulation of edible oil characterised in that the material used to form the capsule comprises a whey protein.

Description

PROCESS FOR ENCAPSULATION OF EDIBLE OIL PRODUCTS WITH WHEY PROTEIN AND
ENCAPSULATED EDIBLE OIL PRODUCTS
This invention relates to a method for encapsulation of edible oil products, encapsulated edible oil products made thereby, and use of such products in the production of finished food products.
The edible oils with which the invention is concerned in particular are edible oils, including but not necessarily restricted to omega-3 rich nutrient oils which are usually sourced from fish or monocellular vegetable sources such as algae and fungi. The latter are of particular interest as they are suitable for all vegetarians.
Chemically omega-3 rich oils contain a high proportion of unsaturated fatty acids, having at least three unsaturated carbon-carbon bonds, and preferably five or six. Examples of such fatty acids are:-
Figure imgf000002_0001
DHA and EPA are the most commonly encountered.
Omega-3 rich oils have a value as a nutritional or dietary supplement, with however little clear guidance as to best or maximum recommended intake. Specific positive heath effects, especially in infants have been linked to the presence in diets of omega-3 oils, more specifically to the unsaturated fatty acids EPA and DHA.
It is desirable for such omega-3 rich oils to be made available in a form which is suitable for addition to food products.
A further problem of such oil and fatty acids, is that on oxidation, e.g. on exposure to the air, they have a tendency to emit an unpleasant 'fishy odour' (they are in fact the source of this smell as experienced with poorly kept fish). For this reason, it is desirable to protect the oil product from contact with air. One method of doing so is encapsulation, by coating droplets of the oil with a sealant. One method is described in US 4,182,778 which disclosed micro encapsulation of a nutrient in a matrix comprising ethyl cellulose with a propylene glycol mono-ester and acetylated monoglyceride, while in WO 96/20612 it is suggested to encapsulate food or flavour particles using fish gelatine.
Gelatine products, being of animal origin are not suitable for products intended to be available for vegetarians. It is an object of the invention to provide a process for micro-encapsulating edible oils, and edible oil products made thereby wherein the oils are kept from contact from air or other sources of oxidation, in a manner which presents no ethical or dietary problems.
In accordance with a first aspect of the invention, a range of edible oils may be encapsulated in a material including a major portion of whey-protein, wherein the edible oil comprises up to 50% by weight of the total.
Preferably the edible oil comprises upto 25% by weight of the whey protein.
From another aspect, the invention provides an encapsulated product comprising edible oil encapsulated or micro-encapsulated in a material including a major portion of whey-protein, or an encapsulated material as produced by the method of the first aspect.
The invention further provides a food product when including an encapsulated product according to the invention.
The process may be a batch process or a continuous process. In an exemplified process, the encapsulating material may be prepared first by adding whey-protein to water, preferably together with a binding material such as carboxyl methyl cellulose, the mixture is blended, and heated to de-nature the protein, then cooled. Preferably, the denaturing is carried out by use of a multistage heating process, the mixture being initially heated to 6O0C for 5 minutes, then to 7O0C for 10 minutes and finally to 770C for 15 minutes.
Preferably the edible oil is chosen from the group comprising; nutritional oils, flavour oils, phytosterols, oryzanol, tocopherol, tocotrienol and polyphenol.
More preferably the nutritional oils are chosen from the group comprising; omega 3 -oils, polyunsaturated vegetable oils, rice bran oil, wheat germ oil, maize germ oil and other vegetable oils.
The omega-3 rich oil, preferably containing a high proportion of EPA and/or DHA, which may be derived from fish, or mono-cellular fungi, but is preferably derived from mono-cellular algae is then added to the encapsulating material. The mixture may be gelled by adding a gelling agent such as citric acid or other food grade acids, and is homogenised by agitation. Preferably a droplet size of 60-80 microns is achieved and more preferably a droplet size of 40 microns is achieved.
The product of this process may then be freeze dried, and milled until free flowing. The milled material may then be added to a solution of carboxyl methyl cellulose in water, stirred whilst heating, preferably at a temperature of 4O0C, and then left to cool. A further gelling step, involving the addition of a food grade acid e.g. citric acid, may follow and then the product may be cryostructured by controlled - A -
freeze drying, which causes the carboxyl methyl cellulose to cross-link to provide insoluble micro-capsules, which are then milled until free flowing.
Preferably the micro-capsule from this exemplified process comprises (by weight) Water 3.5 to 4.2%
Whey Protein 40 .3 to 47.8%
Carboxy methyl cellulose 8.0 to 9.5%
Oil 5 to 20%
Citric acid 28.2 to 33.5% The product may then be stored for use, and transported to a use site where it may be mixed with water to form a slurry, and sprayed onto a food product, such as a cereal to provide a coating of edible oil micro-capsules on the surface of the food product.
Preferably the food product is chosen from the group comprising hard cheese, cottage cheese and cream cheese, yoghurt, quark, margarine, low fat spreads, mayonnaise and salad dressings, ice cream, and baked goods.
The slurry may alternatively be mixed into semi-solid products such as cottage cheese and mayonnaise.
The process is preferably carried out in a non-reactive atmosphere, such as a nitrogen blanket, and the mixing and blending steps may be carried out in a vessel which incorporates a heating apparatus and means to establish and maintain the non- reactive atmosphere.
The food grade acids that may be used are chosen from the group comprising; citric acid, tartaric acid, lactic acid and phosphoric acid. In an alternative embodiment of the exemplified process according to the present invention, once the mixture has been processed to the point where it has been initially gelled and homogenised, as previously described, the mixture is allowed to stand for a period of time, e.g. 12 hours, to allow further gelation. At this point the multiple whey protein/oil molecules are held together in particles by the carboxylic acid groups of the carboxyl methyl cellulose molecules. The hydrogen bond cross- linking of these groups, to produce micro-capsules enhances the integrity of the particles.
The mixture is then stirred whilst a solution of carboxyl methyl cellulose in water is added. The resultant mixture is spray dried to give a free flowing powdered product, wherein the carboxyl methyl cellulose is cross-linked to provide an outer shell for the particles.
Preferably the microcapsule according to the second embodiment comprises by % weight on a dry basis Whey protein 51.7 to 61.3%
Carboxyl methyl cellulose 10.3 to 12.2%
Oil 5 to 20%
Citric acid 18 to 21.4%
The product of this presently exemplified process may be used in the same way as the product of the previously described embodiment/process.
Preferably the gelling of the mixtures previously described is achieved by adding sufficient acid to lower the pH of the mixture to 3.0 at a temperature of 1O0C.
Included within the scope of the invention there is provided a micro-capsule for the encapsulation of edible oils and processes for the preparation of said micro- capsule substantially as described herein with reference to and as illustrated by any appropriate combination of the accompanying drawings.
Encapsulation of edible oils, by use of the process disclosed herein, results in the edible oil being adsorbed onto the hydrophobic surfaces within the whey protein particles. In this way the whey proteins protect the edible oils, particularly omega-3 oils from oxidation thus enhancing the shelf-life of the product.
When the encapsulated edible oil is ingested it passes through the stomach to the lower intestine, wherein the whey protein is digested to release the oil. In this way the problems associated with reflux offish oils, for instance, are avoided. Preferred embodiments according to the invention will now be described by way of example, with reference to the accompanying drawings, wherein: - Figure 1 is a diagram showing a mixing and blending apparatus used in several stages of the process;
Figure 2 is a flow-diagram illustrating the steps of one exemplified embodiment/process according to the invention;
Figure 3 is a diagram showing initial steps of a further exemplified embodiment/process according to the invention; Figure 4 is a diagram showing a first series of intermediate steps of the further exemplified embodiment/process according to the invention; Figure 5 is a diagram showing a second series of intermediate steps of the further exemplified process according to the invention;
Figure 6 is a diagram showing the final step of an exemplified embodiment/process according to the invention; Figures 7a-7d shows schematically the various conformations adopted by whey protein oil and carboxyl methyl cellulose during the encapsulation process; and
Figure 8 shows schematically an expanded view of the structure of a carboxyl methyl cellulose micro-capsule encapsulating particles of whey protein and oil.
Referring initially to Figure 1, a mixer blender apparatus comprises a vessel
10, with an inlet 11 for addition of fluent materials, controlled by a gas-tight one way valve, and a gas inlet 12 connected to a source of inert or non-oxidising gas such as nitrogen, to maintain a non-oxidising atmosphere in a volume 13 above a body of liquid 14 in the vessel 10.
An agitator or stirrer is provided in the form of mixer blades 15, which are mounted for rotation on the lower end of a shaft 16 which is driven by a sealed motor unit 17 on the upper wall of the vessel. An electrical heating apparatus is also provided, and is shown diagrammatically as a heating element 18 disposed below the vessel 10. This of course could be an immersion heater actually extending into the vessel 10. The vessel also has a water jacket 19 which can be used to cool the vessel when required.
All liquid and solid phase additives are introduced through the inlet 11. The vessel may be emptied by opening a sealed lid part which includes the motor 17, and decanting the liquid product 14 from the vessel.
Such apparatus is well known in the art, and is briefly described only to give an understanding of how many steps of the process are carried out. Referring now to the flow diagram of Figure 2, an exemplified process according to the invention will now be described by way of example.
Firstly, to a volume of de-ionised and de-aerated water 14, in a vessel 10, a quantity of whey-protein and carboxyl methyl cellulose, in a 10 to 1 weight ratio is added. The additives are stirred into the water for 10 minutes at 2O0C. The next step is to denature the protein.
This is carried out by means of a multi-stage heating process, being heated to
6O0C for five minutes, for a further ten minutes to 7O0C and then for 15 minutes to
770C, whilst being agitated by the stirrer 15. Following this, the mixture is cooled to 1O0C, over 35 minutes using water at 50C in the water jacket 19, whilst continuing stirring.
After cooling, an omega-3 rich oil, is added to the mixture, at 1O0C whilst stirring for one minute. The oil may for example be a proprietary supplied oil such as DHA-rich algal oil, and may be added in a proportion of 25% by weight of the whey- protein.
The next step is to gel the mixture. This is done by addition of solid citric acid or other food-grade acid, in quantity sufficient to achieve a pH of 3.0 at 1O0C. The product resulting is then homogenised by rapid stirring for 1 minute to a droplet size of 60-80 microns, e.g. 40 microns. All these operations are carried out under a non-oxidising nitrogen atmosphere in the upper part 13 of the vessel.
The homogenised product, comprising gelled micro-droplets (particles) which are also known as capsules which may also be reformed to as capsules of oil and whey, is then subjected to freeze drying for four hours, without vacuum, at - 3O0C, and then for 20 hours at - 3O0C under a reduced pressure at - 80m Torr.
In the next stage, a fresh charge of water in the vessel 10, or a second similar vessel is prepared by adding a further quantity of carboxyl methyl cellulose, whilst stirring and heating at 1000C for five minutes, and cooling to 4O0C, where it is held for five minutes before adding the product from the freeze-drying step, after milling of the latter for 1 minute at 1O0C.
The addition is carried out whilst stirring, and cooling to 4O0C in a nitrogen atmosphere. The mixture is then gelled again by adding solid citric acid or other food grade acid to achieve a pH of 3.0 at 1O0C and the product thus obtained cryostructured by a controlled freeze drying procedure comprising first freeze-drying for 4 hours at - 3O0C under normal pressure, then 20 hours ramping at - 3O0C to - 1O0C, under - 80m Torr vacuum. As a result of this, the carboxyl methyl cellulose cross-links to create insoluble micro-capsules.
The product is then subjected to ageing, and milled for 1 minute at 1O0C, until free-flowing. Optionally, a food grade surfactant may be added to avoid particle agglomeration.
By way of example, the product following cryostructing may comprise, (by weight %).
Water (de-ionised, de-aerated) 3.9%
Whey protein 44.7%
Carboxyl methyl cellulose 8.9%
DHA-rich oil 11.2% Citric acid 31.3%
Following this the product may be aged and bagged for at least 24 hours at 1O0C5 and stored and/or distributed by commercial channels to the end user who uses it by adding the encapsulated oil/whey/carboxyl methyl cellulose powder to water to form a slurry, homogenising the same and possibly filtering or straining it before use. One use is to spray the product as a liquid slurry onto a food product such as a flake or biscuit/mini biscuit type cereal or to fruit pieces, nuts or other food ingredients to provide a coating on at least one surface thereof of the encapsulated omega-3 rich oil, whereby this may act as a dietary supplement to add value to the food product. A further embodiment of the process for producing micro-capsules according to the invention is described with reference to Figure 3. The process may be carried out using the apparatus previously disclosed and under a nitrogen atmosphere, as before.
A volume of de-ionised and de-aerated water (100Og) 15, in a vessel 10 is stirred (step 1) and then, a quantity of whey protein (20Og) and carboxyl methyl cellulose (2Og), in a 10 to 1 weight ratio is added (step 2). The additives are stirred into water for 10 minutes at 2O0C. The next step is to denature the protein (step 3).
This is carried out by means of a multi-stage heating process. The mixture being heated to 6O0C for 5 minutes, for a further 10 minutes to 7O0C and then for 15 minutes to 770C, whilst being agitated by the stirrer 15. Following this, the mixture is cooled to 1O0C over 35 minutes using water at 50C in the water jacket 19, whilst continuing stirring (step 4). All of the operations of the present process, other than a spray drying step, described later, are carried out under a non-oxidising atmosphere in the upper part 13 of the vessel e.g. under nitrogen. Referring now to Figure 4, after cooling, an edible oil (5Og), is added to the mixture, at 1O0C whilst stirring for 1 minute (step 5). The oil may for example be a proprietory supplied oil such as DHA-rich algal oil, and may be added in a proportion of 25% relative to the whey-protein. The next step is to gel the mixture (step 6). This is done by the addition of solid citric acid (7Og), or other food grade acid, in quantity sufficient to achieve a pH of 3.0 at 1O0C. In this way the carboxylic acid groups, of the carboxyl methyl cellulose are protonated. The resultant hydrogen bond cross-linking enhances the integrity of the particles. The resulting product is then homogenised by rapid stirring to a droplet size of 60 - 80 μm, e.g. 40μm (step 7). The homogenised product, comprises oil and whey protein held together in particles by carboxyl methyl cellulose molecules. The product is then allowed to stand for 12 hours, to allow further gelation.
Referring now to Figure 5, a second solution comprising 2% of carboxyl methyl cellulose (1Og) in water (500g) is prepared (step 8). The second solution is heated and stirred to completely dissolve the carboxyl methyl cellulose.
The 2% carboxyl methyl cellulose solution is then added to an approximately equal volume of the homogenised produced comprising water (500g), whey protein (10Og), carboxyl methyl cellulose (1Og)5 oil (25g) and citric acid (35g) (step 9). The homogenised product comprising particles of oil and whey, being stirred at a temperature of 2O0C and the carboxyl methyl cellulose being added over a period of 5 minutes. This stage of the process provides an outer shell of carboxyl methyl cellulose (CMC) which encapsulates the particles, thus, giving the final product in the form of a micro-capsule containing particles of oil and whey. Referring now to Figure 6, the mixture is cooled to a temperature of 10 to 2O0C, before spray drying using high pressure air at 170 to 19O0C (step 10), the outlet of the spray dryer being at a temperature of 70 - 9O0C. This gives the product as free flowing powdered micro-capsules. By way of example, the product may typically comprise by weight on a dry basis:
Whey protein lOOg (55.6%)
Carboxyl methyl cellulose 2Og (11.1%)
Oil 25g (13.9%) Citric acid 35g (19.4%)
Reference is now made to Figures 7a to 7d which show schematically the process by which edible oils are encapsulated according to the present invention.
Figure 7a shows the conformation of a whey protein molecule dissolved in water. Hydrophobic regions of the whey protein molecular are internalised to minimise their interaction with the aqueous phase.
Figure 7b shows the conformation of a thermally denatured whey protein molecule. The hydrophobic regions of the whey protein molecules are now exposed and available to associate with hydrophobic oil molecules.
Figure 7c shows multiple whey protein/oil molecules held together in a nano- particle by CMC molecules. The pH of the aqueous phase is then lowered by the addition of citric acid, or other food grade acid, resulting in the protonation of the
CMC carboxylic acid groups. The resulting hydrogen bond cross-linking of the protonated carboxylic acid groups enhances the integrity of the particles. Figure 7d shows the second stage of the encapsulation process wherein CMC provides an outer shell for the particles.
Figure 8 is an expanded version of the Figure 7d enabling the structure of the micro-capsule encapsulating the particles of whey-protein and oil to be more clearly seen.
The structure of the capsules encapsulating the whey protein and oil, obtained by the process described herein, are believed to be the same, or at least similar in structure to those obtained by the previously described process which utilises two freeze drying steps in the production of the micro-capsules. The whey protein and carboxyl methyl cellulose used in the process described herein are food grade materials.
The processes described herein provides efficient and cost-effective means for encapsulating edible oils.
With respect to the processes described above all percentages (%) given are by weight.
It is envisaged that the capsules and microcapsules described herein could be used to manufacture larger capsules, for example capsules which are sized for consumption by humans and animals.
The claims of the present invention are not intended to be limited with respect to the size of the capsules or microcapsules claimed.
It will be appreciated by those skilled in the art that various modifications may be made to the invention described herein without departing from the scope thereof.
For instance the temperatures at which the various steps disclosed above are carried out may be varied by +/-150C. It may be possible to remove or dispense with the use of citric acid.

Claims

L A capsule or micro-capsule for the encapsulation of edible oils characterised in that the material used to form the capsule comprises a whey protein.
2. A capsule or micro-capsule as claimed in claim 1 wherein the capsule comprises a major portion of whey protein.
3. A capsule or micro-capsule as claimed in either of claim 1 or claim 2 wherein the edible oil comprises up to 50% by weight of the total.
4. A capsule or micro-capsule as claimed in claim 1 or claim 2 wherein the edible oil comprises up to 25% by weight of the whey protein.
5. A capsule or micro-capsule as claimed in any preceding claim wherein the capsule or micro-capsule further comprises carboxyl methyl cellulose.
6. A capsule or micro-capsule as claimed in any preceding claim wherein the edible oil is chosen from the group comprising; nutritional oils, flavour oils, phytosterols, oryzanol, tocopherol, tocotrienol and polyphenol.
7. A capsule or micro-capsule as claimed in claim 6 wherein the nutritional oils are chosen from the group comprising omega-3 oils, polyunsaturated vegetable oils, rice bran oil, wheat germ oil, maize germ oil and other vegetable oils.
8. A capsule or micro-capsule as claimed in claim 7 wherein the omega-3 oil contains a high proportion of eicosapentanoic acid (EPA) and/or docosohexanoic acid (DHA).
9. A capsule or micro-capsule as claimed in claim 8 wherein the omega-3 oil is derived from fish, mono-cellular fungi or mono-cellular algae.
10. A capsule or micro-capsule as claimed in claim 9 wherein the omega-3 oil is preferably derived from mono-cellular algae.
11. A capsule or micro-capsule as claimed in any previous claim wherein the capsule further comprises a food grade acid chosen from the group comprising; citric acid, tartaric acid, lactic acid and phosphoric acid.
12. A micro-capsule as claimed in any preceding claim comprising (by weight):
Water 3.5 to 4.2%
Whey Protein 40.3 to 47.8%
Carboxy methyl cellulose 8.0 to 9.5% Oil 5 to 20%
Citric acid 28.2 to 33.5%
13. A micro-capsule as claimed in any of claims 1 to 11 comprising (by % weight on a dry basis):
Whey protein 51.7 to 61.3% Carboxyl methyl cellulose 10.3 to 12.2%
Oil 5 to 20%
Citric acid . 18 to 21.4%
14. A food product comprising capsules or micro-capsules according to any preceding claim.
15. A food product as claimed in claim 14 wherein the food product is chosen from the group comprising hard cheese, cottage cheese and cream cheese, yoghurt, quark, margarine, low fat spreads, mayonnaise and salad dressings, ice cream, and baked goods.
16. A food product as claimed in either one of claim 14 or claim 15 wherein the capsules or micro-capsules are mixed to form a slurry which is sprayed onto the food product to provide a coating.
17. A food product as claimed in claim 14 or claim 15 wherein the capsules or micro- capsules are mixed into a semi-solid product.
18. A process for forming capsules or micro-capsules comprising encapsulating an edible oil in whey protein.
19. A process as claimed in claim 18 for forming capsules or micro-capsules comprising an edible oil and whey protein comprising the steps of: a) blending a mixture of whey protein, carboxyl methyl cellulose and water; b) denaturing the whey protein by heating; c) adding an edible oil to the mixture containing the denatured whey protein; d) adding an acid to gel the mixture; e) homogenising the resulting product f) freeze drying and milling the product;
20. A process as claimed in claim 19 wherein the freeze dried product of step f) is added to a solution of carboxyl methyl cellulose in water; and al) further acid is added to gel the mixture; and, a2) freeze drying the mixture gives the desired micro-capsules
21. A process as claimed in claim 19 wherein the homogenised product of step e) is subsequently: i) allowed to stand for a period of time before adding a solution of carboxyl methyl cellulose in water: and, ii) the resultant mixture is then spray dried to give the desired micro-capsules.
22. A process as claimed in any of claims 19 to 22 wherein the acid is a food grade acid chosen from the group comprising; citric acid, tartaric acid, lactic acid and phosphoric acid.
23. A process as claimed in any of claims 19 to 22 wherein in the gelling steps
sufficient acid is added to lower the pH of the mixture to 3.0 at a temperature of 100C.
24. A process as claimed in any of claims 19 to 23 wherein the homogenised product has a droplet size of 60 to 80 microns.
25. A process as claimed in claim 24 wherein the homogenised product has a droplet size of 40 microns.
26. A process as claimed in any of claims 18 to 25 wherein the whey protein is denatured by use of a multistage heating process, the mixture being heated initially to
6O0C for 5 minutes, then to 7O0C for 10 minutes and finally to 77°C for 15 minutes.
27. A process as claimed in claim 20 or claims 22 to 26 wherein following the initial freeze drying step the product of the freeze drying step is added to the solution of
carboxyl methyl cellulose at a temperature of 400C
PCT/GB2006/003546 2005-09-24 2006-09-25 Process for encapsulation of edible oil products with whey protein and encapsulated edible oil products WO2007034213A1 (en)

Applications Claiming Priority (4)

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GB0519509A GB0519509D0 (en) 2005-09-24 2005-09-24 Encapsulation of edible oil products and encapsulated edible oil products
GB0519509.4 2005-09-24
GB0616102.0 2006-08-12
GB0616102A GB0616102D0 (en) 2006-08-12 2006-08-12 Encapsulation of edible oil products and encapsulated oil products

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010057852A1 (en) * 2008-11-19 2010-05-27 Nestec S.A. Solid oil powders
WO2010119041A3 (en) * 2009-04-13 2011-01-13 Agriculture And Food Development Authority (Teagasc) Method of producing microbeads
WO2012089676A1 (en) * 2010-12-29 2012-07-05 Nestec S.A. Filling composition comprising an encapsulated oil
CN103859025A (en) * 2014-03-22 2014-06-18 吉林大学 Panaxoside microcapsule yoghourt and preparation method thereof
CN105193766A (en) * 2015-11-04 2015-12-30 李孟平 Preparation method of vitamin E soft capsules with good stability
EP2811846B1 (en) 2012-02-08 2016-11-30 Pepsico, Inc. Acidic aqueous product comprising oil-containing microcapsules and method for the manufacture thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336662A2 (en) * 1988-04-04 1989-10-11 Clinical Technologies Associates, Inc. Microencapsulation of fish oil
US5601760A (en) * 1994-09-01 1997-02-11 The Regents Of The University Of California, A California Corporation Milk derived whey protein-based microencapsulating agents and a method of use
WO2005048998A1 (en) * 2003-11-21 2005-06-02 Commonwealth Scientific & Industrial Research Organisation G i tract delivery systems

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336662A2 (en) * 1988-04-04 1989-10-11 Clinical Technologies Associates, Inc. Microencapsulation of fish oil
US5601760A (en) * 1994-09-01 1997-02-11 The Regents Of The University Of California, A California Corporation Milk derived whey protein-based microencapsulating agents and a method of use
WO2005048998A1 (en) * 2003-11-21 2005-06-02 Commonwealth Scientific & Industrial Research Organisation G i tract delivery systems

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE FSTA [online] INTERNATIONAL FOOD INFORMATION SERVICE (IFIS), FRANKFURT-MAIN, DE; KOLANOWSKI W ET AL: "Fish oil stabilisation by microencapsulation with modified cellulose.", XP002412078, Database accession no. 2004-00-n0913 *
KOLANOWSKI W ET AL: "Fish oil stabilisation by microencapsulation with modified cellulose.", INTERNATIONAL JOURNAL OF FOOD SCIENCES AND NUTRITION, vol. 55, no. 4, 2004, WARSAW, POLAND, pages 333 - 343 *
YOUNG S.L. AND ROSENBERG, M.: "MICROENCAPSULATING PROPERTIES OF WHEY PROTEINS 2 COMBINATION OF WHEY PROTEINS WITH CARBOHYDRATES", JOURNAL OF DAIRY SCIENCE, AMERICAN DAIRY SCIENCE ASSOCIATION, SAVOY, IL, US, vol. 76, no. 10, 1 October 1993 (1993-10-01), pages 2878 - 2885, XP000404482, ISSN: 0022-0302 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010057852A1 (en) * 2008-11-19 2010-05-27 Nestec S.A. Solid oil powders
EP2191730A1 (en) * 2008-11-19 2010-06-02 Nestec S.A. Solid oil powders
US8609118B2 (en) 2008-11-19 2013-12-17 Nestec S.A. Solid oil powders
AU2009317352B2 (en) * 2008-11-19 2014-10-16 Société des Produits Nestlé S.A. Solid oil powders
WO2010119041A3 (en) * 2009-04-13 2011-01-13 Agriculture And Food Development Authority (Teagasc) Method of producing microbeads
WO2012089676A1 (en) * 2010-12-29 2012-07-05 Nestec S.A. Filling composition comprising an encapsulated oil
JP2014501115A (en) * 2010-12-29 2014-01-20 ネステク ソシエテ アノニム Filling composition containing encapsulated oil
US9504265B2 (en) 2010-12-29 2016-11-29 Nestec S.A. Filling composition comprising an encapsulated oil
EP2811846B1 (en) 2012-02-08 2016-11-30 Pepsico, Inc. Acidic aqueous product comprising oil-containing microcapsules and method for the manufacture thereof
EP2811846B2 (en) † 2012-02-08 2022-01-19 Pepsico, Inc. Acidic aqueous product comprising oil-containing microcapsules and method for the manufacture thereof
CN103859025A (en) * 2014-03-22 2014-06-18 吉林大学 Panaxoside microcapsule yoghourt and preparation method thereof
CN105193766A (en) * 2015-11-04 2015-12-30 李孟平 Preparation method of vitamin E soft capsules with good stability

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