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WO2019008147A1 - Method for producing dry emulsions from biosourced particles - Google Patents

Method for producing dry emulsions from biosourced particles Download PDF

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Publication number
WO2019008147A1
WO2019008147A1 PCT/EP2018/068400 EP2018068400W WO2019008147A1 WO 2019008147 A1 WO2019008147 A1 WO 2019008147A1 EP 2018068400 W EP2018068400 W EP 2018068400W WO 2019008147 A1 WO2019008147 A1 WO 2019008147A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
oil
dry
emulsions
particles
Prior art date
Application number
PCT/EP2018/068400
Other languages
French (fr)
Inventor
Chrystel Faure
Cécile JOSEPH
Fernando Leal-Calderon
Didier Pintori
Maud CANSELL
Original Assignee
Pivert
Centre National De La Recherche Scientifique
Iterg
Université De Bordeaux
Institut Polytechnique De Bordeaux
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
Application filed by Pivert, Centre National De La Recherche Scientifique, Iterg, Université De Bordeaux, Institut Polytechnique De Bordeaux filed Critical Pivert
Priority to EP18737272.7A priority Critical patent/EP3648737A1/en
Publication of WO2019008147A1 publication Critical patent/WO2019008147A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/28—Asteraceae or Compositae (Aster or Sunflower family), e.g. chamomile, feverfew, yarrow or echinacea
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/31—Brassicaceae or Cruciferae (Mustard family), e.g. broccoli, cabbage or kohlrabi
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0275—Containing agglomerated particulates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present invention relates to a process for preparing dry emulsions from an emulsion obtained from biosourced particles. It also relates to the dry emulsions thus obtained and their uses, preferably in the cosmetics, food or in bitumen, as well as a redispersion process of said emulsions and redispersed emulsions.
  • An emulsion consists of a mixture of two immiscible liquids together rendered stable over time by an emulsifier.
  • the emulsions are generally divided into two categories, the so-called “water-in-oil” emulsions, where water droplets are suspended in an oily phase, and the so-called “oil-in-water” emulsions, where droplets of oil are suspended in an aqueous phase.
  • Milk, butter and vinaigrette are examples of common emulsions in the agri-food sector.
  • Emulsifiers also called emulsifiers, surfactants or surfactants, are compounds capable of stabilizing emulsions over time. These compounds may be of artificial origin, such as synthetic polymers, or of natural origin, such as phospholipids or proteins.
  • emulsion systems can be used to increase the resistance of oils to oxidation phenomena.
  • the oxidation of unsaturated fatty acids such as linoleic acid, is a complex phenomenon that comprises several phases: primary oxidation, which degrades fatty acids into hydrogen peroxide and hydroperoxide derivatives, and degrading secondary oxidation. peroxide derivatives and hydroperoxides of hydrogen to aldehyde derivatives.
  • the degree of oxidation of fatty acids can be evaluated by the method of the peroxide index, which consists of a method of determination defined according to standards NF ISO 3976, NF EN ISO 27107 or NF EN ISO 3960.
  • the limit The oxidation rate of an oil for food use is set at a maximum of 15 meq of active oxygen / kg of oil (15 meq 2 kg -1 ) according to CODEX STAN 19-1981.
  • Amphiphilic solid particles are also used to stabilize the emulsions.
  • the resulting systems known as Pickering emulsions, often have extraordinary kinetic stability (F. Leal-Calderon, V. Schmitt, Solid-stabilized emulsions, Current Opinion in Colloid and Interface Science, 13, 217-227 ( 2008)).
  • the solid particles are capable of strongly and irreversibly adsorbing at the interface of the immiscible phases, forming a rigid and thick layer capable of permanently preventing the phenomena of destruction of the emulsions such as the recombination of the drops (coalescence).
  • dry emulsions are powders consisting of lipid particles covered with a solid protective zone. Dry emulsions are able to regenerate oil-in-water emulsions after rehydration and can be transported and stored more easily.
  • Proteins and galactolipids are known emulsifiers for the production of dry emulsions.
  • the international application WO2014 / 076432 relates to a method for manufacturing a dry emulsion.
  • the emulsifier employed is preferably chosen from whey proteins. The advantage of this emulsion is that it allows the administration of polysaccharides in the field of food.
  • An alternative for obtaining stable emulsions over time consists in using amphiphilic solid particles capable of adsorbing at the interface of the two immiscible liquids. Such emulsions are called "Pickering emulsions”.
  • the present invention aims to provide a stable dry emulsion that can be used in various fields of application including cosmetics, food or in bitumen compositions.
  • the present invention also aims to provide a stable dry emulsion that can be redispersed satisfactorily.
  • Another object of the invention is to provide a process for preparing stable dry emulsions from biosourced particles.
  • the present invention relates to a method for preparing a dry emulsion, comprising a step of drying an oil-in-water Pickering emulsion containing plant powder particles.
  • the rehydrated dry emulsion has characteristics that are identical (or very similar) to the oil-in-water emulsion before drying.
  • the Pickering emulsions used according to the invention comprise particles of vegetable powder, preferably of at least one oleaginous species.
  • the method of the invention therefore consists in implementing a drying step of these Pickering emulsions.
  • This method thus makes it possible to obtain dry emulsions having improved stability.
  • the dry emulsions are obtained from Pickering emulsions stabilized with an emulsifier consisting of vegetable powder.
  • the dry emulsions according to the invention are obtained from Pickering emulsions stabilized with an emulsifier consisting of vegetable powder obtained from oilseed meal.
  • the dry emulsions according to the invention contain a protective saccharide compound, especially chosen from the group consisting of sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars, sorbitol, polydextrose, starch syrup, glucose syrup and mixtures thereof.
  • a protective saccharide compound especially chosen from the group consisting of sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars, sorbitol, polydextrose, starch syrup, glucose syrup and mixtures thereof.
  • the protective saccharide compound is lactose.
  • This embodiment is particularly advantageous in that it makes it possible to obtain even more stable emulsions, and in that the emulsions thus obtained once dried and then redispersed have properties similar to those obtained before drying.
  • the method according to the invention therefore consists in implementing the following steps:
  • the preparation of the stabilized Pickering emulsion can be carried out by any method known to those skilled in the art.
  • the Pickering emulsion according to the invention is prepared by shaking a vegetable powder in the aqueous phase of the emulsion and then adding the oily phase in order to obtain an "oil-in-water" dispersion stabilized by the vegetable particles.
  • a preferred embodiment of preparation is described below.
  • the drying of the emulsion can be carried out by any method known to those skilled in the art.
  • the emulsion is dried by lyophilization or by zeodration, by evaporation in an oven or spray tower.
  • the drying of the emulsion is carried out by lyophilization.
  • the term "zeodration” denotes a dehydration process using zeolites, materials capable of absorbing the water vapor released by the dried material.
  • the drying step is carried out by lyophilization.
  • Lyophilization is a process of vacuum dehydration of a previously frozen product by sublimation. This batch process is used in particular in the biochemical, cosmetic, food and pharmaceutical industries to extract a dry product from an aqueous solution.
  • the method comprises a step of freezing the product and then at least one drying step of the product under vacuum. This process makes it possible to stabilize products sensitive to heat by turning them into solid powders. The freeze-dried product can then be regenerated by simply moistening the solid powder.
  • the freeze-drying step according to the invention comprises freezing the above-mentioned Pickering emulsion at a temperature between -200 ° C and -18 ° C, preferably at -80 ° C, for a period of time between a few minutes and 24 hours, preferably for 12 hours, then to sublimate the ice at a pressure of between 0.1 mbar and 1 mbar, preferably equal to 0.3 mbar, at a temperature of between 20 ° C. and 35 ° C. C, preferably equal to 25 ° C, for a period between 24 and 72 hours, preferably for 24 hours.
  • the aforementioned freezing step can be carried out by conventional means or else by liquid nitrogen.
  • the drying step is carried out in an oven.
  • this step consists in placing the aforementioned Pickering emulsion in an oven at a temperature of between 60 ° C. and 120 ° C., preferably equal to 70 ° C., for a period of between 12 hours and 72 hours, preferably for 12 hours. h.
  • the drying step is carried out by atomization.
  • this step consists in spraying the emulsion in a drying tank.
  • the emulsion / drying air mixture is introduced at a given flow rate via a nozzle or a turbine, at a temperature generally between 110 ° C. and 270 ° C.
  • the exit temperature of dry pulverized material is controlled and is generally between 65 ° C and 110 ° C.
  • the abovementioned plant powder is obtained from at least one oleaginous species.
  • the plant powder according to the invention is obtained from a part of an oleaginous plant.
  • the vegetable powder is obtained from seeds of oleaginous species, hulls of oleaginous species, films of oleaginous species, oily meal and mixtures thereof. According to a particularly preferred embodiment, the vegetable powder is obtained from cake of oleaginous species.
  • an advantageous process according to the invention consists in preparing a dry emulsion by drying a Pickering emulsion comprising vegetable powder particles of at least one oleaginous species, preferably vegetable powder obtained from cake of species oil.
  • the oleaginous species are chosen from the group consisting of rapeseed, sunflower, soybean, flax, hemp, pea, beans, lupine, cocoa, castor oil, olive, lemon almonds, corn germ, poppy, sesame, walnut, oil palm, shuttle, safflower, and mixtures thereof.
  • the plant powder thus obtained is in the form of particles of average size between 0.1 ⁇ and 100 ⁇ , and preferably between 0.5 ⁇ and 50 ⁇ .
  • the term “average size” refers to the average number diameter of the particles.
  • the size distribution of the particles is determined by statistical analysis of images (for example by optical microscopy, objective x60, 2 images of 1 19 ⁇ 88 ⁇ ). The largest dimension of all particles in the images is noted. The total number of particles measured varies from sample to sample but is never less than 100.
  • the anchoring rate of the plant particles at the interface between the two phases of the emulsion is between 60% and 95%, preferably between 70% and 95%. % and 90%.
  • the anchoring rate is defined as the mass ratio between the plant particles adsorbed at the interfaces and the particles used to make the emulsion. An anchoring rate of less than 100% reveals the presence of free particles in the continuous phase.
  • the anchoring rate is determined by weighing the non-anchored particles on the surface of the drops.
  • the lipid drops decorated with particles are separated from the aqueous phase containing the unanchored particles by natural creaming (about 3 days).
  • the cream is removed and the aqueous phase is treated with lyophilization to collect the un-anchored particles which are then weighed.
  • the anchoring rate is calculated by difference:
  • the Pickering emulsion containing plant powder particles is obtained according to a process comprising the following steps:
  • the aqueous phase contains at least one protective saccharide compound.
  • the saccharide compound or compounds, introduced into the aqueous phase are chosen from sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars, sorbitol, polydextrose, sodium syrup and starch, glucose syrup and mixtures thereof.
  • Step a) of the process described above consists of refining particles of at least one oleaginous species, preferably oilseed meal, in order to obtain a vegetable powder.
  • step a) consists of a wet or dry mechanical treatment step. This first step aims to refine the average particle diameter.
  • step a) is carried out by means of a universal mill.
  • grinding means that the material is subjected to striking, shearing and percussive effects within a grinding apparatus.
  • sieving means that it is possible to select the desired grinding fineness.
  • the fineness of grinding of the raw material can be chosen between 0.12 and 10 mm by means of interchangeable sieves.
  • Sieves commonly used in grinders have openings of 120 ⁇ , 200 ⁇ , 250 ⁇ , 500 ⁇ , 750 ⁇ , 1 mm, 1, 5 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm and 10 mm.
  • step a) grinding and sieving according to step a) are carried out by a grinder at 120 ⁇ .
  • step a) makes it possible to obtain a plant powder in the form of particles of suitable size.
  • the plant powder thus obtained is in the form of particles of average size between 0.1 ⁇ and 100 ⁇ , and preferably between 0.5 ⁇ and 50 ⁇ .
  • the term "average size" refers to the average diameter of the particles.
  • the size distribution of the particles is determined by statistical analysis of images (for example by optical microscopy, objective x60, 2 images of 1 19 ⁇ 88 ⁇ ). The largest dimension of all particles in the images is noted. The total number of particles varies from one sample to another but is never less than 100.
  • the refining consists of a step of grinding and sieving the cake of oleaginous species in order to obtain a vegetable powder.
  • the vegetable powder obtained after step a) is preferably produced from sunflower cake, cocoa, rapeseed or lupine.
  • cake refers to solid co-products obtained after grinding oleaginous seeds and solvent extraction of the oils. Cakes are generally valued as a source of protein feed for livestock. The cakes thus obtained are then milled and sieved to produce a powder.
  • Step b) of the process described above consists in adding the powder obtained at the end of step a) in an aqueous phase to prepare an emulsion.
  • Step b) consists in adding the vegetable powder in an aqueous phase to obtain a suspension (S) followed by the incorporation of oil in the said suspension (S) to obtain an oil-in-water emulsion.
  • the emulsion contains from 5% to 40% of oil and from 60% to 95% of water, more preferably from 10% to 30% of oil and from 70% to 90% of water, for example. relative to the total weight of said emulsion.
  • the aqueous phase of the emulsion is buffered.
  • the aqueous phase has a pH of between 5 and 9, more preferably between 6 and 8.
  • the buffer used can be any type of buffer.
  • the buffer employed is an inorganic salt and / or a mixture of inorganic salts, more preferably the buffer contains at least 0.1 M phosphate buffer (KH 2 PO 4 / K 2 HPO 4 ).
  • the aqueous phase contains between 0% and 20% by weight of protective saccharide compound, preferably lactose, preferably 18% of lactose.
  • Step c) of the method described above consists in supplying energy to the mixture obtained at the end of step b), containing the vegetable powder, in order to obtain a stabilized emulsion.
  • an emulsion consists of fine drops of a phase dispersed in a continuous dispersing phase, immiscible with the first.
  • Step c) consists of supplying energy to the emulsion obtained at the end of step b) to stabilize said emulsion.
  • Such a step can also be likened to an emulsification step.
  • Step c) can be done by various means.
  • step c) is performed by means of a rotor / stator type stirrer.
  • a rotor / stator stirrer comprises a mobile part, called a rotor, fixed on a stationary part, called a stator, and capable of causing stirring in a medium.
  • the stirring step c) is carried out by means of an ultrasonic apparatus.
  • step c) is carried out using a high-pressure homogenizer.
  • a high-pressure homogenizer is a device comprising numerous pistons that make it possible to vary the pressure within of the medium, causing vacuum effects, entrainment effects and or shear effects.
  • the homogenization pressure of the homogenizer at high pressure is between 50 bar and 1000 bar, preferably between 100 bar and 300 bar.
  • a high pressure homogenizer is particularly advantageous in that it allows for finer powder sizes and smaller drop sizes. This embodiment thus makes it possible to obtain more stable emulsions with time.
  • the stirring step c) is carried out by means of a ball mill.
  • ball mills are devices capable of grinding by involving multiple friction and impact effects between the sample, the balls and the inner walls of the bowl or mortar. Ball mills are suitable for the mixing and homogenization process.
  • the invention relates to a method for preparing a dry emulsion, comprising a step of drying a Pickering emulsion containing plant powder particles, said Pickering emulsion being obtained according to the aforementioned method, wherein step c) stirring is performed by means of a high pressure homogenizer.
  • the present invention also relates to a dry emulsion obtainable by the process as defined above.
  • the dry emulsions according to the invention have the following physicochemical characteristics:
  • D 1 is the number of drops of diameter D 1), drops of the emulsion before drying and after drying / redispersion, is between 1 and 4, preferably between 1 and 2.
  • the redispersion is carried out by simply stirring with a spatula or with the aid of a magnetic bar of the dry emulsion in distilled water (buffered to pH 7) or distilled water viscosified with 3% by weight of water. sodium alginate.
  • the average diameters of the initial emulsions and emulsions obtained by redispersion are determined by laser granulometry.
  • the presence of solid particles in the emulsions which distort the measurement of conventional particle size, these are detached from the interfaces of the drops by dilution and agitation of the emulsion in a solution containing a surfactant, sodium dodecyl sulfate (SDS), at 10%.
  • SDS sodium dodecyl sulfate
  • the SDS causes the desorption of the particles. It then becomes easy to separate the drops of the particles by centrifugation. Once the separation is carried out, the particle size distribution of the drops is measured by laser granulometry.
  • the present invention also relates to the use of a dry emulsion as defined above, in cosmetic, pharmaceutical, food or bitumen compositions.
  • the present invention therefore also relates to a cosmetic composition
  • a cosmetic composition comprising at least one dry emulsion as defined above.
  • the present invention thus also relates to a pharmaceutical composition
  • a pharmaceutical composition comprising at least one dry emulsion as defined above.
  • the present invention therefore also relates to an agrifood composition comprising at least one dry emulsion as defined above.
  • the present invention therefore also relates to a bitumen composition comprising at least one dry emulsion as defined above.
  • the present invention also relates to a method for preparing a Pickering emulsion comprising a step of dispersing a dry emulsion as defined above in an aqueous phase containing water.
  • This process consists of redispersing the dry emulsions according to the invention in an aqueous phase.
  • this process comprises the addition of water or water viscosified with alginate, followed by manual stirring with a spatula.
  • the present invention also relates to a Pickering emulsion obtainable by the above method.
  • the invention therefore also relates to the redispersed emulsions obtained from the dry emulsions according to the invention.
  • a vegetable powder is obtained from oleaginous rapeseeds, delipidated with hexane, crushed / sieved at 120 ⁇ , sorted by centrifugation to remove large particles likely to clog the apparatus (a 10% dispersion of rapeseed is centrifuged 10min to 54xg where g is the acceleration of gravity, the upper phase is lyophilized to recover the so-called "sorted" powder).
  • This vegetable powder is introduced into an aqueous phase (distilled water buffered at pH 7 with a 0.1 M phosphate buffer) at 2.5% by weight. This mixture is stirred with a magnetic bar for 20 minutes to obtain a dispersion.
  • the dispersion is then stirred for 2 min by means of a rotor / stator type stirrer (Ultra-Turrax T25 digital) at 6000 rpm (rotation per minute).
  • the oily phase (sunflower oil, 20% by weight of the total emulsion) is gradually added to the mixture once stirring is increased to 8000 rpm.
  • the speed is then increased to 12,000 rpm and the mixture is subjected to this speed an additional 10 minutes to obtain an emulsion.
  • a given volume (20 ml) of emulsion obtained by means of a rotor-stator stirrer (emulsion of Example 1) is introduced into the tank of the high-pressure homogenizer (Microfluidizer M-1 10S).
  • the homogenization is carried out with an inlet pressure of 3.44 bar and a chamber pressure of 801 bar.
  • the emulsion undergoes 20 strokes of pistons.
  • the apparatus operates in closed circuit and each emulsion makes an average of 6 passages in the apparatus.
  • a Pickering emulsion stabilized by 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipid rapeseed meal containing 15% by weight of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1.
  • This emulsion is placed for 12 hours in a freezer at -80 ° C (Thermo Scientific, Forma 900 Series) and is lyophilized for 24h at 0.3 mbar at room temperature (FTS Systems, Dura-Dry).
  • the dry emulsion obtained is a powder stable in storage and containing 1/3 of rapeseed meal and 2/3 of sunflower oil in mass proportion.
  • Example 3 Preparation of a Dry Emulsion by a Drying Process in an Oven
  • a Pickering emulsion stabilized at 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipidated cocoa cake, containing 15% by mass of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1. This emulsion is placed for 12 hours in an oven at 70 ° C. (DRY-Line, VWR).
  • the dry emulsion obtained is a dry powder stable in storage and containing 1/3 cocoa cake and 2/3 sunflower oil in mass proportion.
  • a Pickering emulsion stabilized at 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipidated cocoa cake, containing 15% by mass of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1.
  • This emulsion is spray dried (Mobile Minor, NIRO).
  • the injected air is at about 220 ° C.
  • the outlet air temperature is 90 ° C.
  • the emulsion is pumped at a flow rate of about 1.5 L / h.
  • the dry emulsion obtained is a dry powder stable in storage and containing 1/3 cocoa cake and 2/3 sunflower oil in mass proportion.
  • a defined quantity of dry emulsion obtained according to Example 2 is added to distilled water containing 3% by weight of sodium alginate.
  • the mixture is homogenized by simple stirring with a spatula.
  • the redispersed emulsion obtained has the same macroscopic appearance as the emulsion before drying and does not have any oil on the surface.
  • the volume mean diameter, D v gives a greater statistical weight to the large diameter drops, relative to the average surface diameter, D s .
  • the R Dv ratio is therefore a more "sensitive" indicator than the R Ds ratio.
  • Pickering emulsions of the following compositions are obtained by means of a high pressure homogenizer.
  • the homogenization is carried out with an inlet pressure of 3.44 bar and with a chamber pressure of 801 bar (Microfluidizer M-1 10S).
  • the emulsion undergoes 20 strokes of pistons.
  • the apparatus operates in closed circuit and the emulsion makes on average 6 passages in the apparatus (% expressed with respect to the total emulsion):
  • lactose 7.5% cocoa, 15% sunflower oil, 15.5% lactose 7.5% cocoa, 15% sunflower oil, 15.5% lactose.
  • the lactose is added after obtaining the emulsion just before the drying step
  • the ratios R Dv and R Ds are lower in the presence of lactose.
  • lactose thus makes it possible to improve the resistance of the emulsion during drying + redispersion.
  • This protector can be indifferently added to the system before making the emulsion or once the emulsion obtained, just before the drying step.
  • Example 7 Measurement of Pickering Emulsion Stabilized Oil Peroxide Index.
  • An oil used in the food industry must have an oxidation limit of not more than 15 meq0 2 / kg- 1 according to CODEX STAN 19-1981 This value is measured by a method of determination of the peroxide value according to standard NF EN ISO 27107.
  • the peroxide number was measured for:
  • Formulation A serves as a reference and allows to see the behavior of linseed oil vis-à-vis the oxidation over time.
  • the advantage of formulation B is to show the impact of a mechanical stirring in oxygenated medium on the resistance of the oil vis-à-vis the oxidation. The results show that the oil according to formulation B is no longer considered edible from 48h, against 72h for formulation A.
  • Formulation C shows the interest of the stabilization of the oil by means of a Pickering emulsion according to the invention.
  • the results show that the resistance of an oil to oxidation can be increased by making a Pickering emulsion.

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Abstract

The present invention relates to a method of producing a dry emulsion, involving a step of drying an oil-in-water Pickering emulsion that contains particles of plant powder. The invention also relates to the dry emulsions which can be obtained by following said method.

Description

PROCÉDÉ DE PRÉPARATION D'ÉMULSIONS SÈCHES À PARTIR DE PARTICULES BIOSOURCEES  PROCESS FOR PREPARING DRY EMULSIONS FROM BIOSOURCE PARTICLES
La présente invention a pour objet un procédé de préparation d'émulsions sèches à partir d'une émulsion obtenue de particules biosourcées. Elle a également pour objet les émulsions sèches ainsi obtenues et leurs utilisations, de préférence dans le domaine cosmétique, agroalimentaire ou dans du bitume, ainsi qu'un procédé de redispersion desdites émulsions et les émulsions redispersées. The present invention relates to a process for preparing dry emulsions from an emulsion obtained from biosourced particles. It also relates to the dry emulsions thus obtained and their uses, preferably in the cosmetics, food or in bitumen, as well as a redispersion process of said emulsions and redispersed emulsions.
Une émulsion consiste en un mélange de deux liquides non miscibles entre eux rendu stable dans le temps grâce à un émulsifiant. Les émulsions sont en général réparties en deux catégories, les émulsions dites « eau-dans-huile », où des gouttelettes d'eau sont en suspension dans une phase huileuse, et les émulsions dites « huile-dans-eau », où des gouttelettes d'huile sont en suspension dans une phase aqueuse. Le lait, le beurre et la vinaigrette sont des exemples d'émulsions courantes dans le domaine de l'agroalimentaire. An emulsion consists of a mixture of two immiscible liquids together rendered stable over time by an emulsifier. The emulsions are generally divided into two categories, the so-called "water-in-oil" emulsions, where water droplets are suspended in an oily phase, and the so-called "oil-in-water" emulsions, where droplets of oil are suspended in an aqueous phase. Milk, butter and vinaigrette are examples of common emulsions in the agri-food sector.
Les émulsifiants, aussi appelés émulsionnants, tensioactifs ou agents de surfaces, sont des composés capables de stabiliser les émulsions au cours du temps. Ces composés peuvent être d'origine artificielle, tel que des polymères synthétiques, ou bien d'origine naturelle, tels que les phospholipides ou les protéines.  Emulsifiers, also called emulsifiers, surfactants or surfactants, are compounds capable of stabilizing emulsions over time. These compounds may be of artificial origin, such as synthetic polymers, or of natural origin, such as phospholipids or proteins.
A l'heure actuelle, on observe, notamment dans le domaine de l'agroalimentaire et de la cosmétique, une élimination progressive des tensioactifs synthétiques jugés nocifs pour la santé et l'environnement. Il existe donc un réel besoin de nouveaux émulsifiants d'origine naturelle (biosourcés).  At present, we observe, especially in the field of food and cosmetics, a gradual elimination of synthetic surfactants deemed harmful to health and the environment. There is therefore a real need for new emulsifiers of natural origin (biobased).
Dans le domaine de l'alimentaire, des systèmes d'émulsions peuvent être employés pour augmenter la résistance des huiles vis-à-vis des phénomènes d'oxydation. L'oxydation des acides gras insaturés, comme par exemple l'acide linoléique, est un phénomène complexe qui comprend plusieurs phases : une oxydation primaire, qui dégrade les acides gras en dérivés de type peroxydes et hydroperoxydes d'hydrogène, et une oxydation secondaire dégradant les dérivés de type péroxyde et hydroperoxydes d'hydrogène en dérivés de type aldéhydes. Le degré d'oxydation des acides gras peut être évalué par la méthode de l'indice de péroxyde, qui consiste en une méthode de dosage définie selon les normes NF ISO 3976, NF EN ISO 27107 ou NF EN ISO 3960. De façon générale, la limite d'oxydation d'une huile pour un usage alimentaire est fixée à un maximum de 15 méq d'oxygène actif/kg d'huile (15 meq02.kg"1), selon la norme CODEX STAN 19- 1981 . In the field of food, emulsion systems can be used to increase the resistance of oils to oxidation phenomena. The oxidation of unsaturated fatty acids, such as linoleic acid, is a complex phenomenon that comprises several phases: primary oxidation, which degrades fatty acids into hydrogen peroxide and hydroperoxide derivatives, and degrading secondary oxidation. peroxide derivatives and hydroperoxides of hydrogen to aldehyde derivatives. The degree of oxidation of fatty acids can be evaluated by the method of the peroxide index, which consists of a method of determination defined according to standards NF ISO 3976, NF EN ISO 27107 or NF EN ISO 3960. In general, the limit The oxidation rate of an oil for food use is set at a maximum of 15 meq of active oxygen / kg of oil (15 meq 2 kg -1 ) according to CODEX STAN 19-1981.
Des particules solides amphiphiles sont aussi employées pour stabiliser les émulsions. Les systèmes obtenus, appelés émulsions de Pickering, sont souvent dotés d'une stabilité cinétique hors du commun (F. Leal-Calderon, V. Schmitt, Solid- stabilized emulsions, Current Opinion in Colloid and Interface Science, 13, 217-227 (2008)). Les particules solides sont capables de s'adsorber fortement et irréversiblement à l'interface des phases non miscibles, formant une couche rigide et épaisse capable d'empêcher durablement les phénomènes de destruction des émulsions tels que la recombinaison des gouttes (coalescence).  Amphiphilic solid particles are also used to stabilize the emulsions. The resulting systems, known as Pickering emulsions, often have extraordinary kinetic stability (F. Leal-Calderon, V. Schmitt, Solid-stabilized emulsions, Current Opinion in Colloid and Interface Science, 13, 217-227 ( 2008)). The solid particles are capable of strongly and irreversibly adsorbing at the interface of the immiscible phases, forming a rigid and thick layer capable of permanently preventing the phenomena of destruction of the emulsions such as the recombination of the drops (coalescence).
Il est connu que la phase aqueuse des émulsions peut être éliminée par un procédé de séchage. On parle alors d'émulsions « sèches ». Les émulsions « sèches » sont des poudres constituées de particules lipidiques recouvertes d'une zone protectrice solide. Les émulsions sèches sont capables de régénérer des émulsions huile-dans-eau après réhydratation et peuvent être transportées et stockées plus facilement. It is known that the aqueous phase of the emulsions can be removed by a drying process. This is called "dry" emulsions. "Dry" emulsions are powders consisting of lipid particles covered with a solid protective zone. Dry emulsions are able to regenerate oil-in-water emulsions after rehydration and can be transported and stored more easily.
Les protéines et les galactolipides sont des émulsifiants connus pour la réalisation d'émulsions sèches. La demande internationale WO2014/076432 concerne un procédé de fabrication d'une émulsion sèche. L'émulsifiant employé est de préférence choisi parmi les protéines issues du lactosérum. L'intérêt de cette émulsion est qu'elle permet l'administration de polysaccharides dans le domaine de l'alimentaire.  Proteins and galactolipids are known emulsifiers for the production of dry emulsions. The international application WO2014 / 076432 relates to a method for manufacturing a dry emulsion. The emulsifier employed is preferably chosen from whey proteins. The advantage of this emulsion is that it allows the administration of polysaccharides in the field of food.
La demande internationale WO2009/090249 concerne des émulsions sèches obtenues par utilisation de galactolipides comme émulsifiants.  International application WO2009 / 090249 relates to dry emulsions obtained using galactolipids as emulsifiers.
La demande internationale W098/19652 concerne des émulsions sèches obtenues par utilisation de protéines isolées de pois jaunes.  International application WO98 / 19652 relates to dry emulsions obtained using proteins isolated from yellow peas.
Une alternative pour l'obtention d'émulsions stables au cours du temps consiste à utiliser des particules solides amphiphiles capables de s'adsorber à l'interface des deux liquides non miscibles. De telles émulsions sont appelées « émulsions de Pickering ».  An alternative for obtaining stable emulsions over time consists in using amphiphilic solid particles capable of adsorbing at the interface of the two immiscible liquids. Such emulsions are called "Pickering emulsions".
Il existe actuellement un besoin de disposer d'émulsions sèches stables pouvant être utilisées dans tout domaine d'application. Il existe aussi actuellement un besoin de disposer d'un procédé permettant d'augmenter la résistance des huiles vis-à-vis des phénomènes d'oxydation dans le domaine de l'alimentaire. There is currently a need for stable dry emulsions that can be used in any field of application. There is also a current need to have a method for increasing the resistance of oils vis-à-vis oxidation phenomena in the field of food.
La présente invention a pour but de fournir une émulsion sèche stable pouvant être utilisée dans divers domaines d'application notamment cosmétique, alimentaire ou dans des compositions de bitume. The present invention aims to provide a stable dry emulsion that can be used in various fields of application including cosmetics, food or in bitumen compositions.
La présente invention a également pour but de fournir une émulsion sèche stable pouvant être redispersée de façon satisfaisante.  The present invention also aims to provide a stable dry emulsion that can be redispersed satisfactorily.
Un autre but de l'invention consiste à fournir un procédé de préparation d'émulsions sèches stables à partir de particules biosourcées.  Another object of the invention is to provide a process for preparing stable dry emulsions from biosourced particles.
Ainsi, la présente invention concerne un procédé de préparation d'une émulsion sèche, comprenant une étape de séchage d'une émulsion de Pickering huile-dans-eau contenant des particules de poudre végétale. L'émulsion sèche réhydratée présente des caractéristiques identiques (ou très proches) à l'émulsion huile-dans-eau avant séchage. Thus, the present invention relates to a method for preparing a dry emulsion, comprising a step of drying an oil-in-water Pickering emulsion containing plant powder particles. The rehydrated dry emulsion has characteristics that are identical (or very similar) to the oil-in-water emulsion before drying.
Les émulsions de Pickering mises en œuvre selon l'invention comprennent des particules de poudre végétale, de préférence d'au moins une espèce oléagineuse. The Pickering emulsions used according to the invention comprise particles of vegetable powder, preferably of at least one oleaginous species.
Le procédé de l'invention consiste donc à mettre en œuvre une étape de séchage de ces émulsions de Pickering.  The method of the invention therefore consists in implementing a drying step of these Pickering emulsions.
Ce procédé permet ainsi d'obtenir des émulsions sèches présentant une stabilité améliorée. This method thus makes it possible to obtain dry emulsions having improved stability.
Selon un mode de réalisation, les émulsions sèches sont obtenues à partir d'émulsions de Pickering stabilisées par un émulsifiant consistant en de la poudre végétale.  According to one embodiment, the dry emulsions are obtained from Pickering emulsions stabilized with an emulsifier consisting of vegetable powder.
Selon un mode préférentiel, les émulsions sèches selon l'invention sont obtenues à partir d'émulsions de Pickering stabilisées par un émulsifiant consistant en de la poudre végétale obtenue à partir de tourteaux d'espèces oléagineuses.  According to a preferred embodiment, the dry emulsions according to the invention are obtained from Pickering emulsions stabilized with an emulsifier consisting of vegetable powder obtained from oilseed meal.
Selon un mode préférentiel, les émulsions sèches selon l'invention contiennent un composé saccharidique protecteur, notamment choisi dans le groupe constitué du saccharose, du lactose, du fructose, du tréhalose, des dextrines, des maltodextrines, des dextrines jaunes, des sucres invertis, du sorbitol, du polydextrose, du sirop d'amidon, du sirop de glucose et de leurs mélanges. De préférence, le composé saccharidique protecteur est le lactose. According to a preferred embodiment, the dry emulsions according to the invention contain a protective saccharide compound, especially chosen from the group consisting of sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars, sorbitol, polydextrose, starch syrup, glucose syrup and mixtures thereof. Preferably, the protective saccharide compound is lactose.
Ce mode de réalisation est particulièrement avantageux en ce qu'il permet d'obtenir des émulsions encore plus stables, et en ce que les émulsions ainsi obtenues une fois séchées puis redispersées présentent des propriétés similaires à celles obtenues avant le séchage.  This embodiment is particularly advantageous in that it makes it possible to obtain even more stable emulsions, and in that the emulsions thus obtained once dried and then redispersed have properties similar to those obtained before drying.
Selon un mode de réalisation, le procédé selon l'invention consiste donc à mettre en œuvre les étapes suivantes : According to one embodiment, the method according to the invention therefore consists in implementing the following steps:
- la préparation d'une émulsion de Pickering stabilisée, et  the preparation of a stabilized Pickering emulsion, and
- le séchage de l'émulsion de Pickering afin d'obtenir une émulsion sèche.  drying the Pickering emulsion in order to obtain a dry emulsion.
La préparation de l'émulsion de Pickering stabilisée peut être effectuée par tout procédé connu de l'homme du métier. De préférence, l'émulsion de Pickering selon l'invention est préparée par agitation d'une poudre végétale dans la phase aqueuse de l'émulsion puis ajout de la phase huileuse afin d'obtenir une dispersion « huile dans eau », stabilisée par les particules végétales. Un mode de réalisation préféré de préparation est décrit plus loin. The preparation of the stabilized Pickering emulsion can be carried out by any method known to those skilled in the art. Preferably, the Pickering emulsion according to the invention is prepared by shaking a vegetable powder in the aqueous phase of the emulsion and then adding the oily phase in order to obtain an "oil-in-water" dispersion stabilized by the vegetable particles. A preferred embodiment of preparation is described below.
Le séchage de l'émulsion peut être effectué par tout procédé connu de l'homme du métier. De préférence, le séchage de l'émulsion est effectué par lyophilisation ou par zéodratation, par évaporation dans une étuve ou une tour d'atomisation. Préférentiellement, le séchage de l'émulsion est effectué par lyophilisation. The drying of the emulsion can be carried out by any method known to those skilled in the art. Preferably, the emulsion is dried by lyophilization or by zeodration, by evaporation in an oven or spray tower. Preferably, the drying of the emulsion is carried out by lyophilization.
Selon l'invention, le terme « zéodratation » désigne un procédé de déshydratation par utilisation de zéolithes, des matériaux capables d'absorber la vapeur d'eau libérée par la matière séchée.  According to the invention, the term "zeodration" denotes a dehydration process using zeolites, materials capable of absorbing the water vapor released by the dried material.
Selon un mode de réalisation, l'étape de séchage est effectuée par lyophilisation. According to one embodiment, the drying step is carried out by lyophilization.
La lyophilisation est un procédé de déshydratation sous vide d'un produit préalablement congelé par sublimation. Ce procédé discontinu est notamment utilisé dans les industries biochimiques, cosmétiques, alimentaires et pharmaceutiques pour extraire un produit sec à partir d'une solution aqueuse. Le procédé comporte une étape de congélation du produit puis au moins une étape de dessiccation du produit sous vide. Ce procédé permet de stabiliser des produits sensibles à la chaleur en les transformant en poudres solides. Le produit lyophilisé peut ensuite être régénéré par simple humidification de la poudre solide. Lyophilization is a process of vacuum dehydration of a previously frozen product by sublimation. This batch process is used in particular in the biochemical, cosmetic, food and pharmaceutical industries to extract a dry product from an aqueous solution. The method comprises a step of freezing the product and then at least one drying step of the product under vacuum. This process makes it possible to stabilize products sensitive to heat by turning them into solid powders. The freeze-dried product can then be regenerated by simply moistening the solid powder.
De préférence, l'étape de séchage par lyophilisation selon l'invention consiste à congeler l'émulsion de Pickering susmentionnée à une température comprise entre -200°C et -18°C, de préférence à -80°C, pendant une durée comprise entre quelques minutes et 24h, de préférence pendant 12 heures, puis à sublimer la glace à une pression comprise entre 0,1 mbar et 1 mbar, de préférence égale à 0,3 mbar, à une température comprise entre 20°C et 35°C , de préférence égale à 25°C, pendant une durée comprise entre 24h et 72h, de préférence pendant 24 h.  Preferably, the freeze-drying step according to the invention comprises freezing the above-mentioned Pickering emulsion at a temperature between -200 ° C and -18 ° C, preferably at -80 ° C, for a period of time between a few minutes and 24 hours, preferably for 12 hours, then to sublimate the ice at a pressure of between 0.1 mbar and 1 mbar, preferably equal to 0.3 mbar, at a temperature of between 20 ° C. and 35 ° C. C, preferably equal to 25 ° C, for a period between 24 and 72 hours, preferably for 24 hours.
Selon l'invention, l'étape de congélation susmentionnée peut être effectuée par des moyens classiques ou encore par de l'azote liquide.  According to the invention, the aforementioned freezing step can be carried out by conventional means or else by liquid nitrogen.
Selon un autre mode de réalisation, l'étape de séchage est effectuée dans une étuve. According to another embodiment, the drying step is carried out in an oven.
De préférence, cette étape consiste à placer l'émulsion de Pickering susmentionnée dans une étuve à une température comprise entre 60°C et 120°C, de préférence égale à 70°C, pendant une durée comprise entre 12h et 72h de préférence pendant 12 h.  Preferably, this step consists in placing the aforementioned Pickering emulsion in an oven at a temperature of between 60 ° C. and 120 ° C., preferably equal to 70 ° C., for a period of between 12 hours and 72 hours, preferably for 12 hours. h.
Selon un autre mode de réalisation, l'étape de séchage est effectuée par atomisation. According to another embodiment, the drying step is carried out by atomization.
De préférence, cette étape consiste à pulvériser l'émulsion dans une cuve de séchage. Le mélange émulsion/air de séchage est introduit à un débit donné via une buse ou une turbine, à une température généralement comprise entre 1 10°C et 270°C. La température de sortie du matériel pulvérisé sec est contrôlée et est généralement comprise entre 65°C et 1 10°C.  Preferably, this step consists in spraying the emulsion in a drying tank. The emulsion / drying air mixture is introduced at a given flow rate via a nozzle or a turbine, at a temperature generally between 110 ° C. and 270 ° C. The exit temperature of dry pulverized material is controlled and is generally between 65 ° C and 110 ° C.
Selon un mode de réalisation, la poudre végétale susmentionnée est obtenue à partir d'au moins une espèce oléagineuse. According to one embodiment, the abovementioned plant powder is obtained from at least one oleaginous species.
Selon un mode de réalisation, la poudre végétale selon l'invention est obtenue à partir d'une partie d'une plante oléagineuse.  According to one embodiment, the plant powder according to the invention is obtained from a part of an oleaginous plant.
Selon un mode de réalisation, la poudre végétale est obtenue à partir de graines d'espèces oléagineuses, de coques d'espèces oléagineuses, de pellicules d'espèces oléagineuses, de tourteaux d'espèces oléagineuses et de leurs mélanges. Selon un mode particulièrement préféré, la poudre végétale est obtenue à partir de tourteaux d'espèces oléagineuses. According to one embodiment, the vegetable powder is obtained from seeds of oleaginous species, hulls of oleaginous species, films of oleaginous species, oily meal and mixtures thereof. According to a particularly preferred embodiment, the vegetable powder is obtained from cake of oleaginous species.
Ainsi, un procédé avantageux selon l'invention consiste à préparer une émulsion sèche par séchage d'une émulsion de Pickering comprenant des particules de poudre végétale d'au moins une espèce oléagineuse, de préférence de poudre végétale obtenue à partir de tourteaux d'espèces oléagineuses.  Thus, an advantageous process according to the invention consists in preparing a dry emulsion by drying a Pickering emulsion comprising vegetable powder particles of at least one oleaginous species, preferably vegetable powder obtained from cake of species oil.
De préférence, les espèces oléagineuses sont choisies dans le groupe constitué du colza, du tournesol, du soja, du lin, du chanvre, du pois, de la fèverole, du lupin, du cacao, du ricin, de l'olive, de l'amande, du germe de maïs, du pavot, du sésame, de la noix, du noyau de palmier à huile, de la navette, du carthame, et de leurs mélanges. Preferably, the oleaginous species are chosen from the group consisting of rapeseed, sunflower, soybean, flax, hemp, pea, beans, lupine, cocoa, castor oil, olive, lemon almonds, corn germ, poppy, sesame, walnut, oil palm, shuttle, safflower, and mixtures thereof.
Selon un mode de réalisation, la poudre végétale ainsi obtenue est sous forme de particules de taille moyenne comprise entre 0,1 μηι et 100 μηι, et de préférence entre 0,5 μηι et 50 μηι. According to one embodiment, the plant powder thus obtained is in the form of particles of average size between 0.1 μηι and 100 μηι, and preferably between 0.5 μηι and 50 μηι.
Selon l'invention, le terme « taille moyenne » désigne le diamètre moyen en nombre des particules.  According to the invention, the term "average size" refers to the average number diameter of the particles.
La répartition en taille des particules est déterminée par analyse statistique d'images (par exemple par microscopie optique, objectif x60, 2 images de 1 19χ88μηι). La plus grande dimension de toutes les particules présentes sur les images est relevée. Le nombre total de particules mesurées varie d'un échantillon à l'autre mais n'est jamais inférieur à 100.  The size distribution of the particles is determined by statistical analysis of images (for example by optical microscopy, objective x60, 2 images of 1 19χ88μηι). The largest dimension of all particles in the images is noted. The total number of particles measured varies from sample to sample but is never less than 100.
Selon un mode de réalisation, dans les émulsions de Pickering selon l'invention, le taux d'ancrage des particules végétales à l'interface entre les deux phases de l'émulsion est compris entre 60% et 95%, de préférence compris entre 70% et 90%. According to one embodiment, in the Pickering emulsions according to the invention, the anchoring rate of the plant particles at the interface between the two phases of the emulsion is between 60% and 95%, preferably between 70% and 95%. % and 90%.
Le taux d'ancrage est défini comme le rapport massique entre les particules végétales adsorbées aux interfaces et les particules utilisées pour fabriquer l'émulsion. Un taux d'ancrage inférieur à 100% révèle la présence de particules libres dans la phase continue.  The anchoring rate is defined as the mass ratio between the plant particles adsorbed at the interfaces and the particles used to make the emulsion. An anchoring rate of less than 100% reveals the presence of free particles in the continuous phase.
Par exemple, le taux d'ancrage est déterminé par pesée des particules non ancrées à la surface des gouttes. Les gouttes lipidiques décorées de particules sont séparées de la phase aqueuse contenant les particules non ancrées par crémage naturel (environ 3 jours). La crème est prélevée et la phase aqueuse est traitée par lyophilisation pour collecter les particules non ancrées qui sont alors pesées. Le taux d'ancrage est calculé par différence : For example, the anchoring rate is determined by weighing the non-anchored particles on the surface of the drops. The lipid drops decorated with particles are separated from the aqueous phase containing the unanchored particles by natural creaming (about 3 days). The cream is removed and the aqueous phase is treated with lyophilization to collect the un-anchored particles which are then weighed. The anchoring rate is calculated by difference:
ta = 100*(masse de particules totales - masse de particules non ancrées) / (masse de particules totales) t a = 100 * (mass of total particles - mass of non-anchored particles) / (mass of total particles)
Selon un mode de réalisation, l'émulsion de Pickering contenant des particules de poudre végétale est obtenue selon un procédé comprenant les étapes suivantes : According to one embodiment, the Pickering emulsion containing plant powder particles is obtained according to a process comprising the following steps:
a) la préparation d'une poudre végétale d'au moins une espèce oléagineuse ; b) l'addition de ladite poudre végétale dans une phase aqueuse pour obtenir une suspension (S), suivie de l'incorporation d'huile dans la suspension (S) pour obtenir une émulsion de type huile-dans-eau ; et  a) preparing a vegetable powder of at least one oleaginous species; b) adding said plant powder in an aqueous phase to obtain a suspension (S), followed by the incorporation of oil into the suspension (S) to obtain an oil-in-water emulsion; and
c) l'agitation de l'émulsion obtenue à l'issue de l'étape précédente.  c) stirring the emulsion obtained at the end of the previous step.
Selon un mode préférentiel, la phase aqueuse contient au moins un composé saccharidique protecteur. Le ou les composés saccharidiques, introduits dans la phase aqueuse, sont choisis parmi le saccharose, le lactose, le fructose, le tréhalose, les dextrines, les maltodextrines, les dextrines jaunes, les sucres invertis, le sorbitol, le polydextrose, le sirop d'amidon, le sirop de glucose et leurs mélanges. In a preferred embodiment, the aqueous phase contains at least one protective saccharide compound. The saccharide compound or compounds, introduced into the aqueous phase, are chosen from sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars, sorbitol, polydextrose, sodium syrup and starch, glucose syrup and mixtures thereof.
L'étape a) du procédé décrit ci-dessus consiste à affiner des particules d'au moins une espèce oléagineuse, de préférence de tourteaux d'espèces oléagineuses, afin d'obtenir une poudre végétale. Step a) of the process described above consists of refining particles of at least one oleaginous species, preferably oilseed meal, in order to obtain a vegetable powder.
De préférence, l'étape a) consiste en une étape de traitement mécanique en voie sèche ou humide. Cette première étape a pour but d'affiner le diamètre moyen des particules.  Preferably, step a) consists of a wet or dry mechanical treatment step. This first step aims to refine the average particle diameter.
Parmi les traitements mécaniques pouvant être mis en œuvre selon l'invention, on peut citer les techniques suivantes : hélices, homogénéisation à haute pression, ou encore broyage à billes ou à meule.  Among the mechanical treatments that can be implemented according to the invention, mention may be made of the following techniques: propellers, homogenization at high pressure, or ball or grinding.
De préférence, l'étape a) est effectuée au moyen d'un broyeur universel.  Preferably, step a) is carried out by means of a universal mill.
Le terme « broyage » signifie que le matériau est soumis à des effets de frappe, de cisaillement et de percussion au sein d'un appareil de broyage.  The term "grinding" means that the material is subjected to striking, shearing and percussive effects within a grinding apparatus.
Le terme « tamisage » signifie qu'il est possible de sélectionner la finesse de broyage désirée. En général, la finesse de broyage de la matière première peut être choisie entre 0,12 et 10 mm au moyen de tamis interchangeables. Les tamis couramment employés dans des broyeurs présentent des ouvertures de 120 μηι, 200 μηι, 250 μηι, 500 μηι, 750 μηι, 1 mm, 1 ,5 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm et 10 mm. The term "sieving" means that it is possible to select the desired grinding fineness. In general, the fineness of grinding of the raw material can be chosen between 0.12 and 10 mm by means of interchangeable sieves. Sieves commonly used in grinders have openings of 120 μηι, 200 μηι, 250 μηι, 500 μηι, 750 μηι, 1 mm, 1, 5 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm and 10 mm.
De préférence, le broyage et le tamisage selon l'étape a) sont effectués par un broyeur à 120 μηι.  Preferably, grinding and sieving according to step a) are carried out by a grinder at 120 μηι.
Ainsi, l'étape a) permet d'obtenir une poudre végétale sous forme de particules de taille adaptée.  Thus, step a) makes it possible to obtain a plant powder in the form of particles of suitable size.
Selon un mode de réalisation, la poudre végétale ainsi obtenue est sous forme de particules de taille moyenne comprise entre 0,1 μηι et 100 μηι, et de préférence entre 0,5 μηι et 50 μηι.  According to one embodiment, the plant powder thus obtained is in the form of particles of average size between 0.1 μηι and 100 μηι, and preferably between 0.5 μηι and 50 μηι.
Selon l'invention, le terme « taille moyenne » désigne le diamètre moyen des particules.  According to the invention, the term "average size" refers to the average diameter of the particles.
La répartition en taille des particules est déterminée par analyse statistique d'images (par exemple par microscopie optique, objectif x60, 2 images de 1 19χ88μηι). La plus grande dimension de toutes les particules présentes sur les images est relevée. Le nombre total de particules varie d'un échantillon à l'autre mais n'est jamais inférieur à 100.  The size distribution of the particles is determined by statistical analysis of images (for example by optical microscopy, objective x60, 2 images of 1 19χ88μηι). The largest dimension of all particles in the images is noted. The total number of particles varies from one sample to another but is never less than 100.
De préférence, l'affinage consiste en une étape de broyage et de tamisage des tourteaux d'espèces oléagineuses afin d'obtenir une poudre végétale. Preferably, the refining consists of a step of grinding and sieving the cake of oleaginous species in order to obtain a vegetable powder.
La poudre végétale obtenue après l'étape a) est produite de préférence à partir de tourteaux de tournesol, de cacao, de colza ou de lupin.  The vegetable powder obtained after step a) is preferably produced from sunflower cake, cocoa, rapeseed or lupine.
Le terme « tourteau » désigne des coproduits solides obtenus après broyage des graines oléagineuses et extraction par solvant des huiles. Les tourteaux sont généralement valorisés comme source d'alimentation protéique pour le bétail. Les tourteaux ainsi obtenus sont ensuite broyés et tamisés afin de produire une poudre.  The term "cake" refers to solid co-products obtained after grinding oleaginous seeds and solvent extraction of the oils. Cakes are generally valued as a source of protein feed for livestock. The cakes thus obtained are then milled and sieved to produce a powder.
L'étape b) du procédé décrit ci-dessus consiste à ajouter la poudre obtenue à l'issue de l'étape a) dans une phase aqueuse pour préparer une émulsion. Step b) of the process described above consists in adding the powder obtained at the end of step a) in an aqueous phase to prepare an emulsion.
L'étape b) consiste à additionner la poudre végétale dans une phase aqueuse pour obtenir une suspension (S) suivie de l'incorporation d'huile dans ladite suspension (S), pour obtenir une émulsion huile-dans-eau.  Step b) consists in adding the vegetable powder in an aqueous phase to obtain a suspension (S) followed by the incorporation of oil in the said suspension (S) to obtain an oil-in-water emulsion.
De préférence, l'émulsion contient de 5% à 40% d'huile et de 60% à 95% d'eau, plus préférentiellement de 10% à 30% d'huile et de 70% à 90% d'eau, par rapport au poids total de ladite émulsion. Selon un mode de réalisation, la phase aqueuse de l'émulsion est tamponnée. De préférence, la phase aqueuse présente un pH compris entre 5 et 9, plus préférentiellement entre 6 et 8. Preferably, the emulsion contains from 5% to 40% of oil and from 60% to 95% of water, more preferably from 10% to 30% of oil and from 70% to 90% of water, for example. relative to the total weight of said emulsion. According to one embodiment, the aqueous phase of the emulsion is buffered. Preferably, the aqueous phase has a pH of between 5 and 9, more preferably between 6 and 8.
Le tampon employé peut être n'importe quel type de tampon. De préférence, le tampon employé est un sel inorganique et/ou un mélange de sels inorganiques, plus préférentiellement le tampon contient au moins contient 0,1 M de tampon phosphate (KH2P04/K2HP04). The buffer used can be any type of buffer. Preferably, the buffer employed is an inorganic salt and / or a mixture of inorganic salts, more preferably the buffer contains at least 0.1 M phosphate buffer (KH 2 PO 4 / K 2 HPO 4 ).
Selon un mode de réalisation, la phase aqueuse contient entre 0% et 20% massique de composé saccharidique protecteur, de préférence de lactose, préférentiellement 18% de lactose.  According to one embodiment, the aqueous phase contains between 0% and 20% by weight of protective saccharide compound, preferably lactose, preferably 18% of lactose.
L'étape c) du procédé décrit ci-dessus consiste à apporter de l'énergie au mélange obtenu à l'issue de l'étape b), contenant la poudre végétale, afin d'obtenir une émulsion stabilisée. Step c) of the method described above consists in supplying energy to the mixture obtained at the end of step b), containing the vegetable powder, in order to obtain a stabilized emulsion.
Par définition, une émulsion est constituée de fines gouttes d'une phase dispersée dans une phase dispersante continue, non miscible avec la première.  By definition, an emulsion consists of fine drops of a phase dispersed in a continuous dispersing phase, immiscible with the first.
L'étape c) consiste à apporter de l'énergie à l'émulsion obtenue à l'issue de l'étape b) pour stabiliser ladite émulsion. Une telle étape peut également être assimilée à une étape d'émulsification.  Step c) consists of supplying energy to the emulsion obtained at the end of step b) to stabilize said emulsion. Such a step can also be likened to an emulsification step.
L'étape c) peut être effectuée par divers moyens.  Step c) can be done by various means.
Selon un mode de réalisation, l'étape c) est effectuée au moyen d'un agitateur de type rotor/stator. According to one embodiment, step c) is performed by means of a rotor / stator type stirrer.
De façon générale, un agitateur rotor/stator comporte une partie mobile, appelée rotor, fixée sur une partie immobile, appelée stator, et capable de provoquer une agitation dans un milieu.  In general, a rotor / stator stirrer comprises a mobile part, called a rotor, fixed on a stationary part, called a stator, and capable of causing stirring in a medium.
Selon un mode de réalisation, l'étape d'agitation c) est effectuée au moyen d'un appareil à ultrasons.  According to one embodiment, the stirring step c) is carried out by means of an ultrasonic apparatus.
De façon générale, l'utilisation d'ultrasons est un moyen efficace et économe en énergie pour apporter un stress mécanique et une énergie intenses à des mélanges de solutions telles que des mélanges de poudre et de liquide.  In general, the use of ultrasound is an efficient and energy efficient way to bring intense mechanical stress and energy to mixtures of solutions such as powder and liquid mixtures.
Selon un mode de réalisation, l'étape c) est effectuée au moyen d'un homogénéisateur à haute pression.  According to one embodiment, step c) is carried out using a high-pressure homogenizer.
De façon générale, un homogénéisateur haute pression est un appareil comportant de nombreux pistons qui permettent de faire varier la pression au sein du milieu, provoquant des effets de vide, des effets d'entraînement et ou des effets de cisaillement. Generally speaking, a high-pressure homogenizer is a device comprising numerous pistons that make it possible to vary the pressure within of the medium, causing vacuum effects, entrainment effects and or shear effects.
De préférence, la pression d'homogénéisation de l'homogénéisateur à haute pression est comprise entre 50 bar et 1 000 bar, de préférence entre 100 bar et 300 bar.  Preferably, the homogenization pressure of the homogenizer at high pressure is between 50 bar and 1000 bar, preferably between 100 bar and 300 bar.
L'utilisation d'un homogénéisateur haute pression est particulièrement avantageuse en ce qu'elle permet d'obtenir des tailles de poudre plus fine et des tailles de gouttes plus petites. Ce mode de réalisation permet ainsi d'obtenir des émulsions plus stables avec le temps.  The use of a high pressure homogenizer is particularly advantageous in that it allows for finer powder sizes and smaller drop sizes. This embodiment thus makes it possible to obtain more stable emulsions with time.
Selon un mode de réalisation, l'étape d'agitation c) est effectuée au moyen d'un broyeur à billes.  According to one embodiment, the stirring step c) is carried out by means of a ball mill.
De façon générale, les broyeurs à billes sont des appareils capables de broyer en faisant intervenir des effets de friction et d'impacts multiples entre l'échantillon, les billes et les parois internes du bol ou du mortier. Les broyeurs à billes sont des appareils adaptés au processus de mélange et d'homogénéisation.  In general, ball mills are devices capable of grinding by involving multiple friction and impact effects between the sample, the balls and the inner walls of the bowl or mortar. Ball mills are suitable for the mixing and homogenization process.
Selon un mode de réalisation préféré, l'invention concerne un procédé de préparation d'une émulsion sèche, comprenant une étape de séchage d'une émulsion de Pickering contenant des particules de poudre végétale, ladite émulsion de Pickering étant obtenue selon le procédé susmentionné, dans lequel l'étape c) d'agitation est effectuée au moyen d'un homogénéisateur à haute pression. According to a preferred embodiment, the invention relates to a method for preparing a dry emulsion, comprising a step of drying a Pickering emulsion containing plant powder particles, said Pickering emulsion being obtained according to the aforementioned method, wherein step c) stirring is performed by means of a high pressure homogenizer.
L'utilisation d'un homogénéisateur à haute pression permet d'obtenir des émulsions sèches qui présentent la meilleure stabilité une fois redispersées en milieu aqueux.  The use of a high-pressure homogenizer makes it possible to obtain dry emulsions which have the best stability once redispersed in an aqueous medium.
La présente invention concerne également une émulsion sèche susceptible d'être obtenue selon le procédé tel que défini ci-dessus. The present invention also relates to a dry emulsion obtainable by the process as defined above.
Selon un mode de réalisation, les émulsions sèches selon l'invention présentent les caractéristiques physico-chimiques suivantes : According to one embodiment, the dry emulsions according to the invention have the following physicochemical characteristics:
- RDs, le rapport entre les diamètres moyens en surface (Ds = ou N,
Figure imgf000011_0001
- R Ds , the ratio between the mean surface diameters (D s = or N,
Figure imgf000011_0001
est le nombre de gouttes de diamètre D,), des gouttes de l'émulsion avant séchage et après séchage/redispersion, est compris entre 1 et 4, préférentiellement compris entre 1 et 2. - RDv, le rapport entre les diamètres moyens en volume (Dv = — ), ou N, est le nombre de gouttes de diamètre D,), des gouttes de l'émulsion avant séchage et après séchage/redispersion, est compris entre 1 et 6, préférentiellement compris entre 1 et 4. is the number of drops of diameter D 1), drops of the emulsion before drying and after drying / redispersion, is between 1 and 4, preferably between 1 and 2. - R Dv , the ratio between the average diameters by volume (D v = -), or N, is the number of drops of diameter D,), drops of the emulsion before drying and after drying / redispersion, is between 1 and 6, preferably between 1 and 4.
- Apparition ou non d'une couche d'huile en surface de l'émulsion obtenue par redispersion de l'émulsion sèche.  - Appearance or not of an oil layer on the surface of the emulsion obtained by redispersion of the dry emulsion.
La redispersion est réalisée par simple agitation à la spatule ou à l'aide d'un barreau aimanté de l'émulsion sèche dans de l'eau distillée (tamponnée à pH 7) ou de l'eau distillée viscosifiée par 3% massique d'alginate de sodium. The redispersion is carried out by simply stirring with a spatula or with the aid of a magnetic bar of the dry emulsion in distilled water (buffered to pH 7) or distilled water viscosified with 3% by weight of water. sodium alginate.
Les diamètres moyens des émulsions initiales et des émulsions obtenues par redispersion sont déterminés par granulométrie laser. La présence de particules solides au sein des émulsions faussant la mesure de granulométrie classique, celles-ci sont détachées des interfaces des gouttes par dilution et agitation de l'émulsion dans une solution contenant un agent tensioactif, le dodécyl sulfate de sodium (SDS), à 10%. En se fixant aux interfaces, le SDS provoque la désorption des particules. Il devient alors aisé de séparer les gouttes des particules par centrifugation. Une fois la séparation effectuée, la distribution granulométrique des gouttes est mesurée par granulométrie laser.  The average diameters of the initial emulsions and emulsions obtained by redispersion are determined by laser granulometry. The presence of solid particles in the emulsions which distort the measurement of conventional particle size, these are detached from the interfaces of the drops by dilution and agitation of the emulsion in a solution containing a surfactant, sodium dodecyl sulfate (SDS), at 10%. By attaching itself to the interfaces, the SDS causes the desorption of the particles. It then becomes easy to separate the drops of the particles by centrifugation. Once the separation is carried out, the particle size distribution of the drops is measured by laser granulometry.
La présente invention concerne également l'utilisation d'une émulsion sèche telle que définie ci-dessus, dans des compositions cosmétiques, pharmaceutiques, agroalimentaires ou de bitume. The present invention also relates to the use of a dry emulsion as defined above, in cosmetic, pharmaceutical, food or bitumen compositions.
La présente invention concerne donc également une composition cosmétique comprenant au moins une émulsion sèche telle que définie ci-dessus.  The present invention therefore also relates to a cosmetic composition comprising at least one dry emulsion as defined above.
La présente invention concerne donc également une composition pharmaceutique comprenant au moins une émulsion sèche telle que définie ci- dessus.  The present invention thus also relates to a pharmaceutical composition comprising at least one dry emulsion as defined above.
La présente invention concerne donc également une composition agroalimentaire comprenant au moins une émulsion sèche telle que définie ci- dessus.  The present invention therefore also relates to an agrifood composition comprising at least one dry emulsion as defined above.
La présente invention concerne donc également une composition de bitume comprenant au moins une émulsion sèche telle que définie ci-dessus. La présente invention concerne également un procédé de préparation d'une émulsion de Pickering comprenant une étape de dispersion d'une émulsion sèche telle que définie ci-dessus dans une phase aqueuse contenant de l'eau. The present invention therefore also relates to a bitumen composition comprising at least one dry emulsion as defined above. The present invention also relates to a method for preparing a Pickering emulsion comprising a step of dispersing a dry emulsion as defined above in an aqueous phase containing water.
Ce procédé consiste à redisperser les émulsions sèches selon l'invention dans une phase aqueuse.  This process consists of redispersing the dry emulsions according to the invention in an aqueous phase.
Selon un mode de réalisation, ce procédé comprend l'ajout d'eau ou d'eau viscosifiée par de l'alginate, suivie d'une agitation manuelle à la spatule.  According to one embodiment, this process comprises the addition of water or water viscosified with alginate, followed by manual stirring with a spatula.
La présente invention concerne également une émulsion de Pickering susceptible d'être obtenue selon le procédé ci-dessus. L'invention concerne donc également les émulsions redispersées obtenues à partir des émulsions sèches selon l'invention. The present invention also relates to a Pickering emulsion obtainable by the above method. The invention therefore also relates to the redispersed emulsions obtained from the dry emulsions according to the invention.
EXEMPLES EXAMPLES
Exemple 1 : Préparation d'une émulsion de Pickering au moyen d'un homogénéisateur haute pression Example 1 Preparation of a Pickering Emulsion Using a High Pressure Homogenizer
Une poudre végétale est obtenue à partir de graines oléagineuses de colza, délipidées à l'hexane, broyées/tamisées à 120 μηι, triées par centrifugation pour éliminer les grosses particules susceptibles d'obstruer les appareils (une dispersion à 10% de colza est centrifugée 10min à 54xg où g est l'accélération de la pesanteur, la phase supérieure est lyophilisée pour récupérer la poudre dite « triée »). Cette poudre végétale est introduite dans une phase aqueuse (eau distillée tamponnée à pH 7 par un tampon phosphate à 0,1 M) à 2,5% massique. Ce mélange est agité au moyen d'un barreau magnétique pendant 20 minutes afin d'obtenir une dispersion. La dispersion est ensuite agitée 2 min au moyen d'un agitateur de type rotor/stator (Ultra-Turrax T25 digital) à 6 000 tpm (rotation par minute). La phase huileuse (huile de tournesol, 20% massique de l'émulsion totale) est progressivement additionnée au mélange une fois l'agitation augmentée à 8 000 tpm. La vitesse est ensuite augmentée à 12 000 tpm et le mélange est soumis à cette vitesse 10 min supplémentaires afin d'obtenir une émulsion. Un volume donné (20 ml) d'émulsion obtenue au moyen d'un agitateur rotor-stator (émulsion de l'exemple 1 ) est introduit dans le réservoir de l'homogénéisateur haute pression (Microfluidizer M-1 10S). L'homogénéisation est effectuée avec une pression d'entrée de 3,44 bar et avec une pression dans la chambre de 801 bar. L'émulsion subit 20 coups de pistons. L'appareil fonctionne en circuit fermé et chaque émulsion effectue en moyenne 6 passages dans l'appareil.  A vegetable powder is obtained from oleaginous rapeseeds, delipidated with hexane, crushed / sieved at 120 μηι, sorted by centrifugation to remove large particles likely to clog the apparatus (a 10% dispersion of rapeseed is centrifuged 10min to 54xg where g is the acceleration of gravity, the upper phase is lyophilized to recover the so-called "sorted" powder). This vegetable powder is introduced into an aqueous phase (distilled water buffered at pH 7 with a 0.1 M phosphate buffer) at 2.5% by weight. This mixture is stirred with a magnetic bar for 20 minutes to obtain a dispersion. The dispersion is then stirred for 2 min by means of a rotor / stator type stirrer (Ultra-Turrax T25 digital) at 6000 rpm (rotation per minute). The oily phase (sunflower oil, 20% by weight of the total emulsion) is gradually added to the mixture once stirring is increased to 8000 rpm. The speed is then increased to 12,000 rpm and the mixture is subjected to this speed an additional 10 minutes to obtain an emulsion. A given volume (20 ml) of emulsion obtained by means of a rotor-stator stirrer (emulsion of Example 1) is introduced into the tank of the high-pressure homogenizer (Microfluidizer M-1 10S). The homogenization is carried out with an inlet pressure of 3.44 bar and a chamber pressure of 801 bar. The emulsion undergoes 20 strokes of pistons. The apparatus operates in closed circuit and each emulsion makes an average of 6 passages in the apparatus.
Exemple 2 : Préparation d'une émulsion sèche par un procédé de séchage par lyophilisation Example 2 Preparation of a Dry Emulsion by a Freeze-Drying Process
Une émulsion de Pickering stabilisée par 8,8% massique (par rapport à la phase aqueuse, 7,5% par rapport à l'émulsion totale) de tourteau de colza délipidé, contenant 15% massique d'huile de tournesol est obtenue au moyen d'un homogénéisateur à haute pression selon le protocole de l'exemple 1 . Cette émulsion est placée pendant 12h dans un congélateur à -80°C (Thermo scientific, Forma 900 Séries) et est lyophilisée pendant 24h à 0,3 mbar à température ambiante (FTS Systems, Dura-Dry).  A Pickering emulsion stabilized by 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipid rapeseed meal containing 15% by weight of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1. This emulsion is placed for 12 hours in a freezer at -80 ° C (Thermo Scientific, Forma 900 Series) and is lyophilized for 24h at 0.3 mbar at room temperature (FTS Systems, Dura-Dry).
L'émulsion sèche obtenue est une poudre stable au stockage et contenant 1/3 de tourteau de colza et 2/3 d'huile de tournesol en proportion massique. Exemple 3 : Préparation d'une émulsion sèche par un procédé de séchage dans une étuve The dry emulsion obtained is a powder stable in storage and containing 1/3 of rapeseed meal and 2/3 of sunflower oil in mass proportion. Example 3 Preparation of a Dry Emulsion by a Drying Process in an Oven
Une émulsion de Pickering stabilisée par 8,8% massique (par rapport à la phase aqueuse, 7,5% par rapport à l'émulsion totale) de tourteau de cacao délipidé, contenant 15% massique d'huile de tournesol est obtenue au moyen d'un homogénéisateur à haute pression selon le protocole de l'exemple 1 . Cette émulsion est placée 12h dans une étuve à 70°C (DRY-Line, VWR).  A Pickering emulsion stabilized at 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipidated cocoa cake, containing 15% by mass of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1. This emulsion is placed for 12 hours in an oven at 70 ° C. (DRY-Line, VWR).
L'émulsion sèche obtenue est une poudre sèche stable au stockage et contenant 1/3 de tourteau de cacao et 2/3 d'huile de tournesol en proportion massique.  The dry emulsion obtained is a dry powder stable in storage and containing 1/3 cocoa cake and 2/3 sunflower oil in mass proportion.
Exemple 4 : Préparation d'une émulsion sèche par un procédé de séchage par atomisation EXAMPLE 4 Preparation of a Dry Emulsion by a Spray Drying Process
Une émulsion de Pickering stabilisée par 8,8% massique (par rapport à la phase aqueuse, 7,5% par rapport à l'émulsion totale) de tourteau de cacao délipidé, contenant 15% massique d'huile de tournesol est obtenue au moyen d'un homogénéisateur à haute pression selon le protocole de l'exemple 1 . Cette émulsion est séchée par atomisation (Mobile Minor, NIRO). L'air injecté est à environ 220°C, la température de l'air en sortie est de 90°C et l'émulsion est pompée à un débit d'environ 1 ,5L/h.  A Pickering emulsion stabilized at 8.8% by weight (relative to the aqueous phase, 7.5% relative to the total emulsion) of delipidated cocoa cake, containing 15% by mass of sunflower oil is obtained by means of of a high-pressure homogenizer according to the protocol of Example 1. This emulsion is spray dried (Mobile Minor, NIRO). The injected air is at about 220 ° C., the outlet air temperature is 90 ° C. and the emulsion is pumped at a flow rate of about 1.5 L / h.
L'émulsion sèche obtenue est une poudre sèche stable au stockage et contenant 1/3 de tourteau de cacao et 2/3 d'huile de tournesol en proportion massique.  The dry emulsion obtained is a dry powder stable in storage and containing 1/3 cocoa cake and 2/3 sunflower oil in mass proportion.
Exemple 5 : Préparation d'une émulsion redispersée Example 5 Preparation of a Redispersed Emulsion
Une quantité définie d'émulsion sèche obtenue d'après l'exemple 2 est ajoutée à de l'eau distillée contenant 3% massique d'alginate de sodium. Le mélange est homogénéisé à l'aide d'une agitation simple à la spatule.  A defined quantity of dry emulsion obtained according to Example 2 is added to distilled water containing 3% by weight of sodium alginate. The mixture is homogenized by simple stirring with a spatula.
L'émulsion redispersée obtenue a le même aspect macroscopique que l'émulsion avant séchage et ne présente pas d'huile en surface.
Figure imgf000016_0001
The redispersed emulsion obtained has the same macroscopic appearance as the emulsion before drying and does not have any oil on the surface.
Figure imgf000016_0001
Ds en μηι 0,94 0,84 RDS = 1 ,1 D s in μηι 0.94 0.84 RDS = 1, 1
L'émulsion avant séchage et l'émulsion sèche redispersée en phase aqueuse sont observées à l'aide d'un microscope optique. Il apparaît ainsi que la structure de l'émulsion de départ est bien conservée après séchage et redispersion mais que quelques gouttes d'huile de taille supérieure sont présentes. Ces gouttes d'huile sont à l'origine de l'augmentation du diamètre moyen mesurée par granulométrie laser. The emulsion before drying and the redispersed dry emulsion in the aqueous phase are observed with the aid of an optical microscope. It thus appears that the structure of the starting emulsion is well preserved after drying and redispersion but that a few drops of oil of larger size are present. These drops of oil are at the origin of the increase in the average diameter measured by laser granulometry.
Le diamètre moyen en volume, Dv, donne un poids statistique plus important aux gouttes de diamètre élevé, par rapport au diamètre moyen en surface, Ds. De ce fait, le rapport RDv est donc un indicateur plus « sensible » que le rapport RDs. The volume mean diameter, D v , gives a greater statistical weight to the large diameter drops, relative to the average surface diameter, D s . As a result, the R Dv ratio is therefore a more "sensitive" indicator than the R Ds ratio.
Exemple 6 : Impact d'un composé saccharidique tel que le lactose Example 6 Impact of a saccharide compound such as lactose
Lors de la congélation et du séchage, les gouttes sont concentrées et donc comprimées, ce qui peut conduire à des phénomènes de recombinaison (coalescence). Il est connu que l'addition d'un composé saccharidique améliore la protection des émulsions lors du séchage. Le polysaccharide formerait une couche protectrice secondaire à la surface des gouttes lipidiques, empêchant le phénomène de coalescence.  During freezing and drying, the drops are concentrated and therefore compressed, which can lead to recombination phenomena (coalescence). It is known that the addition of a saccharide compound improves the protection of emulsions during drying. The polysaccharide would form a secondary protective layer on the surface of the lipid drops, preventing the phenomenon of coalescence.
5 émulsions de Pickering aux compositions suivantes sont obtenues au moyen d'un homogénéisateur à haute pression. L'homogénéisation est effectuée avec une pression d'entrée de 3,44 bar et avec une pression dans la chambre de 801 bar (Microfluidizer M-1 10S). L'émulsion subit 20 coups de pistons. L'appareil fonctionne en circuit fermé et l'émulsion effectue en moyenne 6 passages dans l'appareil (% exprimés par rapport à l'émulsion totale) :  Pickering emulsions of the following compositions are obtained by means of a high pressure homogenizer. The homogenization is carried out with an inlet pressure of 3.44 bar and with a chamber pressure of 801 bar (Microfluidizer M-1 10S). The emulsion undergoes 20 strokes of pistons. The apparatus operates in closed circuit and the emulsion makes on average 6 passages in the apparatus (% expressed with respect to the total emulsion):
7,5% de cacao, 15% d'huile de tournesol  7.5% cocoa, 15% sunflower oil
7,5% de cacao, 15% d'huile de tournesol, 15,5% de lactose 7,5% de cacao, 15% d'huile de tournesol, 15,5% de lactose. Le lactose est ajouté après l'obtention de l'émulsion, juste avant l'étape de séchage  7.5% cocoa, 15% sunflower oil, 15.5% lactose 7.5% cocoa, 15% sunflower oil, 15.5% lactose. The lactose is added after obtaining the emulsion just before the drying step
7,5% de tourteau de colza, 15% d'huile de tournesol  7.5% rapeseed meal, 15% sunflower oil
7,5% de tourteau de colza, 15% d'huile de tournesol, 15,5% de lactose Ces émulsions sont placées pendant 12h dans un congélateur à -80°C (Thermo scientific, Forma 900 Séries) et sont zéodratées pendant 24h à 1 mbar à 30°C (Bûcher, Drytech). 7.5% rapeseed cake, 15% sunflower oil, 15.5% lactose These emulsions are placed for 12 hours in a freezer at -80 ° C. (Thermo Scientific, Forma 900 Series) and are zeodrated for 24 hours at 1 mbar at 30 ° C. (Bûcher, Drytech).
Ces 5 émulsions sèches sont redispersées suivant l'exemple 5. These dry emulsions are redispersed according to Example 5.
Figure imgf000017_0001
Figure imgf000017_0001
Dans tous les cas, aucune couche d'huile n'est observée à la surface de l'émulsion. In any case, no oil layer is observed on the surface of the emulsion.
Les rapports RDv et RDs sont plus faibles en présence de lactose. L'ajout de lactose permet ainsi d'améliorer la résistance de l'émulsion au séchage + redispersion. The ratios R Dv and R Ds are lower in the presence of lactose. The addition of lactose thus makes it possible to improve the resistance of the emulsion during drying + redispersion.
Ce protecteur peut être indifféremment ajouté au système avant de réaliser l'émulsion ou une fois l'émulsion obtenue, juste avant l'étape de séchage.  This protector can be indifferently added to the system before making the emulsion or once the emulsion obtained, just before the drying step.
Exemple 7 : Mesure de l'indice de peroxyde d'huiles stabilisées par une émulsion de Pickering. Example 7: Measurement of Pickering Emulsion Stabilized Oil Peroxide Index.
Une huile employée dans le domaine alimentaire doit présenter une limite d'oxydation fixée à un maximum de 15 meq02/kg"1 selon la norme CODEX STAN 19-1981 . Cette valeur est mesurée par une méthode de dosage de l'indice de peroxyde selon la norme NF EN ISO 27107. An oil used in the food industry must have an oxidation limit of not more than 15 meq0 2 / kg- 1 according to CODEX STAN 19-1981 This value is measured by a method of determination of the peroxide value according to standard NF EN ISO 27107.
L'indice de peroxyde a été mesuré pour : The peroxide number was measured for:
- A) Une huile vierge de lin (Huilerie Philippe Vigean, France) - B) Une huile vierge de lin agitée mécaniquement (agitateur rotor-stator puis homogénéisateur haute pression) - A) A virgin linseed oil (Huilerie Philippe Vigean, France) - B) A mechanically agitated virgin linseed oil (rotor-stator stirrer then high-pressure homogenizer)
- C) Une huile de lin stabilisée sous la forme d'une émulsion de Pickering au moyen d'une poudre végétale issue de tourteaux de colza selon le protocole de l'exemple 1 .  C) Linseed oil stabilized in the form of a Pickering emulsion by means of a plant powder derived from rapeseed cake according to the protocol of Example 1.
Figure imgf000018_0001
Figure imgf000018_0001
La formulation A sert de référence et permet de voir le comportement de l'huile de lin vis-à-vis de l'oxydation au cours du temps. L'intérêt de la formulation B est de montrer l'impact d'une agitation mécanique en milieu oxygéné sur la résistance de l'huile vis-à-vis de l'oxydation. Les résultats montrent que l'huile selon la formulation B n'est plus considérée comme comestible à partir de de 48h, contre 72h pour la formulation A. Formulation A serves as a reference and allows to see the behavior of linseed oil vis-à-vis the oxidation over time. The advantage of formulation B is to show the impact of a mechanical stirring in oxygenated medium on the resistance of the oil vis-à-vis the oxidation. The results show that the oil according to formulation B is no longer considered edible from 48h, against 72h for formulation A.
La formulation C montre l'intérêt de la stabilisation de l'huile au moyen d'une émulsion de Pickering selon l'invention. Les résultats montrent que la résistance d'une huile vis-à-vis de l'oxydation peut être augmentée en réalisant une émulsion de Pickering.  Formulation C shows the interest of the stabilization of the oil by means of a Pickering emulsion according to the invention. The results show that the resistance of an oil to oxidation can be increased by making a Pickering emulsion.

Claims

REVENDICATIONS
1. Procédé de préparation d'une émulsion sèche, comprenant une étape de séchage d'une émulsion de Pickering huile-dans-eau contenant des particules de poudre végétale. A process for preparing a dry emulsion comprising a step of drying an oil-in-water Pickering emulsion containing plant powder particles.
2. Procédé selon la revendication 1 , dans lequel l'étape de séchage est effectuée par lyophilisation, zéodratation, dans une étuve ou par atomisation. 2. Method according to claim 1, wherein the drying step is carried out by lyophilization, zeodration, in an oven or by atomization.
3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel la poudre végétale est obtenue à partir d'au moins une espèce oléagineuse. 3. Method according to any one of claims 1 or 2, wherein the plant powder is obtained from at least one oleaginous species.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel la phase aqueuse contient un composé saccharidique protecteur parmi le saccharose, le lactose, le fructose, le tréhalose, les dextrines, les maltodextrines, les dextrines jaunes, les sucres invertis, le sorbitol, le polydextrose, le sirop d'amidon, le sirop de glucose et leurs mélanges. 4. Process according to any one of claims 1 to 3, wherein the aqueous phase contains a protective saccharide compound among sucrose, lactose, fructose, trehalose, dextrins, maltodextrins, yellow dextrins, invert sugars sorbitol, polydextrose, starch syrup, glucose syrup and mixtures thereof.
5. Procédé selon la revendication 3, dans lequel les espèces oléagineuses sont choisies dans le groupe constitué du colza, du tournesol, du soja, du lin, du chanvre, du pois, de la fèverole, du lupin, du cacao, du ricin, de l'olive, de l'amande, du germe de maïs, du pavot, du sésame, de la noix, du noyau de palmier à huile, de la navette, du carthame, et de leurs mélanges. 5. Method according to claim 3, wherein the oleaginous species are selected from the group consisting of rapeseed, sunflower, soybean, flax, hemp, pea, beans, lupine, cocoa, castor, olive, almond, corn germ, poppy, sesame, walnut, oil palm, shuttle, safflower, and mixtures thereof.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'émulsion de Pickering huile-dans-eau contenant des particules de poudre végétale est obtenue selon un procédé comprenant les étapes suivantes : The process according to any one of claims 1 to 5, wherein the oil-in-water Pickering emulsion containing plant powder particles is obtained by a process comprising the following steps:
a) la préparation d'une poudre végétale d'au moins une espèce oléagineuse ; b) l'addition de ladite poudre végétale dans une phase aqueuse pour obtenir une suspension (S), suivie de l'incorporation d'huile dans la suspension (S) pour obtenir une émulsion de type huile-dans-eau ; et  a) preparing a vegetable powder of at least one oleaginous species; b) adding said plant powder in an aqueous phase to obtain a suspension (S), followed by the incorporation of oil into the suspension (S) to obtain an oil-in-water emulsion; and
c) l'agitation de l'émulsion obtenue à l'issue de l'étape précédente. c) stirring the emulsion obtained at the end of the previous step.
7. Procédé selon la revendication 6, dans lequel l'étape d'agitation c) est effectuée au moyen d'un agitateur de type rotor/stator, d'un appareil à ultrasons, d'un homogénéisateur à haute pression ou d'un broyeur à billes. The process according to claim 6, wherein the stirring step c) is carried out by means of a rotor / stator stirrer, an ultrasonic apparatus, a high pressure homogenizer or a ball mill.
8. Emulsion sèche susceptible d'être obtenue selon le procédé selon l'une quelconque des revendications 1 à 7. 8. Dry emulsion obtainable by the method according to any one of claims 1 to 7.
9. Utilisation d'une émulsion sèche selon la revendication 8, dans des compositions cosmétiques, pharmaceutiques, agroalimentaires ou de bitume. 9. Use of a dry emulsion according to claim 8, in cosmetic, pharmaceutical, food or bitumen compositions.
10. Procédé de préparation d'une émulsion de Pickering huile-dans-eau comprenant une étape de dispersion d'une émulsion sèche selon la revendication 8dans une phase aqueuse contenant de l'eau. A process for preparing an oil-in-water Pickering emulsion comprising a step of dispersing a dry emulsion according to claim 8 in an aqueous phase containing water.
11. Emulsion de Pickering susceptible d'être obtenue selon le procédé de la revendication 10. 11. Pickering emulsion obtainable according to the process of claim 10.
PCT/EP2018/068400 2017-07-07 2018-07-06 Method for producing dry emulsions from biosourced particles WO2019008147A1 (en)

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