EP3344379B1 - Verfahren und vorrichtung zur kontinuierlichen behandlung eines gemischs - Google Patents

Verfahren und vorrichtung zur kontinuierlichen behandlung eines gemischs Download PDF

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Publication number
EP3344379B1
EP3344379B1 EP16777711.9A EP16777711A EP3344379B1 EP 3344379 B1 EP3344379 B1 EP 3344379B1 EP 16777711 A EP16777711 A EP 16777711A EP 3344379 B1 EP3344379 B1 EP 3344379B1
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EP
European Patent Office
Prior art keywords
transducers
tube
mixture
phase
stages
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EP16777711.9A
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English (en)
French (fr)
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EP3344379A1 (de
Inventor
Guillaume Gillet
Justine GATEAUX
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Genialis SAS
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Genialis SAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/411—Emulsifying using electrical or magnetic fields, heat or vibrations
    • B01F23/4111—Emulsifying using electrical or magnetic fields, heat or vibrations using vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/414—Emulsifying characterised by the internal structure of the emulsion
    • B01F23/4145—Emulsions of oils, e.g. fuel, and water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
    • B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
    • B01F31/84—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations for material continuously moving through a tube, e.g. by deforming the tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/811—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles in two or more consecutive, i.e. successive, mixing receptacles or being consecutively arranged
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/82—Combinations of dissimilar mixers
    • B01F33/821—Combinations of dissimilar mixers with consecutive receptacles
    • B01F33/8212—Combinations of dissimilar mixers with consecutive receptacles with moving and non-moving stirring devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0436—Operational information
    • B01F2215/0454—Numerical frequency values

Definitions

  • the invention relates to a method for continuously treating a mixture and a device for such treatment.
  • the invention relates to a method for treating a mixture by high-frequency piezoelectric vibration.
  • US 4,071,225 discloses a method according to the preamble of claim 1 and a device according to the preamble of claim 11.
  • the invention thus aims to solve this drawback.
  • the invention relates to a process for treating a mixture according to claim 1.
  • the treatment method according to the invention makes it possible to treat the mixture continuously, while allowing incorporation of a large dispersed, aqueous or lipid phase, in a controlled manner and without degradation of materials.
  • a dispersion is obtained, in particular a rapid emulsification of the mixture.
  • the dispersion of 20% by weight of oil in water requires sixteen hours to obtain a final volume of 500 mL with an already known emulsion preparation process such as that described in the patent FR 2 947 186 .
  • an already known emulsion preparation process such as that described in the patent FR 2 947 186 .
  • the invention also relates to a device for treating a mixture according to claim 11.
  • the cross section of the tube wall is polygonal. According to one embodiment, the polygonal section comprising an odd number of sides p.
  • the figure 1 represents an embodiment of a device 1 configured to implement the method for processing a mixture 2 according to the invention.
  • Mixture 2 comprises at least a first phase 2a and a second phase 2b.
  • the first phase 2a and the second phase 2b are in particular fluid products, in particular liquid or in powder form.
  • the first phase 2a and the second phase 2b are not mutually miscible. By immiscible, it is therefore understood that the first phase 2a and the second phase 2b cannot be mixed, in particular at ambient temperature (ie approximately twenty degrees Celsius), to obtain a completely homogeneous mixture.
  • ambient temperature ie approximately twenty degrees Celsius
  • the first phase 2a can be an aqueous phase, while the second phase 2b is a lipid phase, or vice versa.
  • lipid phase designates all oily substances, liquid at the temperature of implementation of the process, natural, vegetable or animal, or synthetic having or not having one or more proven biological activities, and insoluble in the water (less than 2% by weight at room temperature).
  • lipid phases designates all oily substances, liquid at the temperature of implementation of the process, natural, vegetable or animal, or synthetic having or not having one or more proven biological activities, and insoluble in the water (less than 2% by weight at room temperature).
  • vegetable oils oil
  • rapeseed peanut, mixtures of vegetable oils, etc.
  • animal oils fish, etc.
  • butters butters.
  • Mention may also be made, as an example of a lipid phase, in particular for dermatology and cosmetics, of avocado, argan and other vegetable oils, essential oils, mineral oils.
  • aqueous (or hydrophilic) phase denotes any phase containing water and/or alcohol. Mention may be made of water that is softened or not, distilled or not, mineral or not, spring water, ultra-pure water, floral waters, fruit waters.
  • mixture 2 may comprise one or more additives.
  • An additive can be added to one of the first or second phases 2a, 2b, depending on whether it is fat-soluble or water-soluble. If necessary, such an additive can be solubilized beforehand in a solvent.
  • a biomolecule of interest can be added in the aqueous phase (peptides, vitamins, flavonoids, etc.) or in the lipid phase (triacylglycerols, fatty acids, aromas, etc. ).
  • the composition of mixture 2 typically depends on the intended end use of mixture 2 once treated by the process.
  • mixture 2 does not include an emulsifier or compound suitable for facilitating the dispersion of the first phase 2a in the second phase 2b during the treatment of mixture 2.
  • mixture 2 does not include an emulsifier, surfactant, stabilizer, or any other additive of any kind suitable for preventing or slowing down the separation of the dispersion of the first phase 2a and of the second phase 2b of the mixture 2.
  • mixture 2 may comprise an emulsifier such as phospholipids.
  • the device 1 comprises at least one tube 3.
  • tube 3 there is understood a conduit which is not necessarily cylindrical, but which may have other shapes as will be described below.
  • the tube 3 comprises a wall 4 delimiting an interior space 5 in which the mixture 2 is intended to circulate continuously. By continuous, it should be understood that the treatment of mixture 2 is carried out when mixture 2 circulates in tube 3.
  • the wall 4 is thin, in practice 1 to 2 mm, for a useful section of the tube of several cm 2 , in practice for example between 2 cm 2 and 30 cm 2 , typically between 5 cm 2 and 15 cm 2 .
  • the wall 4 is thin and fully transmits the ultrasonic vibrations; the wall 4 produces no attenuation or amplification because its main natural frequencies are much lower than those of the forced excitation.
  • the tube 3 extends more particularly between an inlet portion 3a and an outlet portion 3b. This defines a direction of circulation Sc of the mixture 2 in the tube 3 going from the inlet portion 3a to the outlet portion 3b.
  • the tube 3 is straight between the inlet portion 3a and the outlet portion 3b as shown in the figure 1 .
  • This also defines a circulation direction Dc of the mixture 2 in the tube 3.
  • the tube 3 can be placed vertically.
  • the inlet portion 3a of the tube 3 is located downwards while the outlet portion 3b is located upwards (the terms “top” and “bottom” to be understood according to their current meanings).
  • this embodiment is not limiting and the tube 3 can also be arranged horizontally, for example as shown in the figures 1 and 2 , or according to any other inclination.
  • the tube 3 may further comprise at least one or more curved portions.
  • the tube 3 can then have the shape of a serpentine, a spiral or be corrugated, in order to minimize the space occupied by the device 1.
  • the wall 4 of the tube 3 can be made of stainless steel, glass, Plexiglas, plastic or other materials.
  • the tube 3 is made of stainless steel and/or a plastic material.
  • the wall 4 of the tube is thin with regard to the length of each side and/or the useful passage section of the treated product.
  • the material of the wall 4 of the tube 3 is neutral, or inert, with respect to the mixture 2.
  • the material of the wall 4 of the tube 3 is not degraded in contact with the mixture 2.
  • a tube 3 made of polytetrafluoroethylene (PTFE) is not degraded on contact with essential oils.
  • the wall 4 of the tube 3 is advantageously of substantially polygonal section.
  • the wall 4 of the tube 3 may in particular comprise slightly rounded corners between its different faces as shown in the Figure 1A .
  • the wall 4 of the tube 3 is of regular polygonal section (all its faces having the same dimension) over at least one length L.
  • the polygonal wall 4 of the tube 3 preferably comprises an odd number of faces.
  • the polygonal section includes an odd number of sides p.
  • the figures 9A to 9D show examples of realization in perspective of the tube 3 whose sections of the wall 4 are respectively triangular, pentagonal, heptagonal and enneagonal.
  • the device 1 also comprises transducer elements 6. These transducers 6 make it possible to apply vibratory energy to the mixture 2 in a determined frequency range.
  • the transducers 6 chosen are more particularly of the piezoelectric type, in particular ceramic. Such transducers are suitable for stable operation in the chosen frequency range and their manufacturing technology is well mastered.
  • the transducers 6 can have various shapes, in particular in the form of a disc or more or less elongated and extended elements.
  • the transducers 6 are arranged on the wall 4 of the tube 3.
  • the transducers 6 are in particular fixed to the wall 4 of the tube 3, by glue, a joint or any other fixing element.
  • the transducers 6 can be placed on the wall 4 inside the tube 3, that is to say in the interior space 5 delimited by the tube 3.
  • the transducers 6 can be advantageously placed outside outside the tube 3 on the wall 4, that is to say outside the interior space 5 delimited by the tube 3.
  • the vibrations emitted by the transducers 6 then cross the wall 4 of the tube 3 to reach the mixture 2
  • Such an arrangement makes it possible not to put the transducers 6 directly in contact with the mixture 2 and to keep the interior space 5 of the tube, for example sterile, which may be necessary for cosmetic and pharmaceutical applications of the mixture 2.
  • This also facilitates the cleaning of the tube 3 and limits the possible contamination of the mixture 2 by a degradation of the elements fixing the transducers 6 to the wall 4.
  • each of the transducers 6 can be arranged in a cavity passing through the wall 4. A seal lets nsuite sealing the cavity once the transducer disposed inside thereof.
  • the transducers 6 are arranged against the wall 4 of the tube 3, the transducers 6 being for example in the form of discs, one of the faces of which is applied to the wall 4 of the tube 3.
  • the energy vibration emitted by the transducers 6 has a component perpendicular to the wall 4 of the tube 3, and in particular perpendicular to the direction of circulation Dc of the mixture 2.
  • part or all of the transducers 6 can also be inclined with respect to the wall 4 of the tube 3, so that the vibratory energy emitted presents, in addition to its component perpendicular to the direction of circulation Dc of the mixture 2, a component parallel to the direction of circulation Dc and oriented for example in the opposite direction to the direction of circulation Sc.
  • This positioning of the transducers 6 can indeed make it possible to increase the efficiency of the method.
  • the transducers 6, in particular all the transducers 6, are suitable for operating in a so-called high-frequency frequency range, that is to say greater than 900 kHz, or even greater than 1000 kHz.
  • the transducers 6, in particular all the transducers 6, are adapted to operate in a range of frequencies comprised between 900 kHz and 3 MHz, more preferably between 900 kHz and 2000 kHz, even more preferably between 1400 and 1800kHz.
  • the application of high frequency vibratory energy by means of transducers 6 has the advantage of eliminating the phenomenon of cavitation generally used for its shear intensity.
  • This cavitation shears the mixture 2 which allows rapid emulsification but causes the physico-chemical and biochemical alteration of the mixture 2.
  • the use of high frequencies in accordance with the present invention does not cause such alterations and preserves the mixture 2, by making it possible to obtain stable dispersions.
  • the transducers 6 do not all operate at the same frequency.
  • the use of several different frequencies, while remaining in the high frequency range (this term to be understood as previously), can make it possible to obtain more stable emulsions and in which the quantity of dispersed phase is greater while reducing the required treatment time.
  • the transducers 6 can for example operate according to three different frequencies F1, F2, F3, the transducers 6 being arranged in an order of increasing frequency. In other words, the transducers 6 having the lowest frequency F1 are located close to the inlet portion 3a of the tube 3.
  • the transducers 6, in particular the active transducers (that is to say which emit vibrational energy during the treatment of the mixture 2), are arranged discretely on the polygonal wall 4 of the tube 3 by "floor".
  • a stage is defined by a plane of section transverse to the wall 4 of the tube 3.
  • a plane of section transverse to the wall 4 of the tube 3 defining a stage passes in particular through the center of the transducers 6 of this stage. It can also be said that a stage is provided with transducers situated in the plane transverse to the direction of local circulation of the product to be treated.
  • nine stages of transducers 6 can be arranged on the tube 3.
  • all the transducers 6 represented on the figures 9A to 9D are not necessarily active, and some may be inactive as will be explained below.
  • two consecutive stages of transducers 6 are spaced apart by a distance d of less than 30 centimeters, in particular of the order of 10 centimeters.
  • the stages of transducers 6 are not all necessarily spaced apart by the same distance d.
  • the distance d is more particularly measured between the centers of two transducers 6 arranged on the same face of the tube 3 and belonging respectively to two consecutive stages.
  • the transducers 6 are arranged on the faces of the polygonal wall 4 of the tube 3.
  • the arrangement of the transducers in different stages forms a "pattern" or a succession of patterns capable of responding to determined construction rules in order to optimize the treatment of the mixture 2.
  • two transducers 6 of a stage are not arranged facing each other.
  • two transducers 6 are not arranged facing directly parallel to each other.
  • the interaction of the vibratory waves emitted by two face-to-face transducers is capable of causing the appearance of a stationary wave of the mixture 2 creating zones without treatment in the tube 3 during the process.
  • the device 1 also comprises a container 7 in fluid communication with the inlet portion 3a of the tube 3.
  • the container 7 is intended to contain the mixture 2 before its circulation in the tube 3.
  • the first phase 2a and the second phase 2b can initially be simply combined without prior mixing in container 7.
  • the first phase 2a and the second phase 2b can also be the subject of a premix.
  • a mechanical or membrane mixing device 8 can be used in the container 7.
  • the pre-mixing can be carried out by applying vibrational energy to the mixture 2 using transducers, in particular low frequencies .
  • This mixing device 8 allows rapid shearing of the first phase 2a in the second phase 2b which makes it possible to shorten the subsequent stage of treatment of the mixture 2 without, however, allowing a stable mixture 2 to be obtained alone.
  • a pump can also be used to introduce one of the phases gradually into the container 7 during this pre-mixing.
  • several pumps can also be used to introduce each phase 2a, 2b and possibly other additives, of the mixture 2 into the container 7.
  • a heating system 9 makes it possible to heat the mixture 2 (or one of the phases 2a, 2b) beforehand or during its treatment according to the method.
  • the mixture 2 can thus be heated, insofar as this does not lead to a degradation of the materials of the wall 4 of the tube 3 or of the other elements of the device 1.
  • a cooling system 10 makes it possible to cool the mixture 2 beforehand or during the treatment according to the method. This makes it possible in particular to treat the mixture 2 cold, to easily limit the losses and/or degradations of the mixture 2 linked to an excessively high temperature.
  • the heating 9 and/or cooling 10 systems make it possible in particular, for specific implementation or fragility needs, to keep the temperature of the treated phases 2a, 2b constant throughout the process.
  • a pH control system 11, or possibly several systems 11 distributed over the tube 3, make it possible to regulate the pH of the mixture 2 during its treatment.
  • the treatment of the mixture is likely to lead to an acidification of the treated mixture 2, due to the specific organization of the HO - ions induced by the process in the mixture 2.
  • a pH-stat coupled to a soda pump mounted on the tube 3 make it possible, for example, to regulate the pH of the mixture 2 to a determined value during the treatment.
  • the device can also comprise a pump 12, in particular peristaltic, adapted to allow the circulation of the mixture 2 in the tube 3.
  • a pump 12 in particular peristaltic, adapted to allow the circulation of the mixture 2 in the tube 3.
  • the circulation of the mixture is carried out by the effect of gravity, in particular when the tube 3 is vertical or inclined in the device 1.
  • the treatment of the mixture 2 is carried out continuous manner by circulation of the mixture 2 in the tube 3 on the wall 4 of which the transducers 6 are arranged.
  • the flow rate of the mixture 2 in the tube 3 is for example between 10 g/min and 2 kg/min, or even between 50 g / min and 900 g / min, in some special cases of the order of 60 g / min.
  • a vibratory energy is then applied to the mixture 2 during its circulation in the tube 3.
  • the tube 3 does not include any free interior space, in order to limit the exchanges between the mixture 2 and the air which would be contained in this free space and which would be liable to lead to the dissolution of gas in mixture 2 or losses of volatile compounds.
  • the mixture 2 can circulate continuously in a tube 3 which can comprise several wall portions 4 of polygonal section as shown in the figure 2 .
  • the tube 3 can thus have different configurations, and can in particular have a length adapted to the mixture 2 to be treated.
  • mixture 2 outlets or diversion passages may be provided located at different places on the tube 3 of the device 1 in order to adapt the duration of the treatment of the mixture 2.
  • the mixture 2 can also circulate several times in a tube 3 in a recurring manner by a closed-loop system, until the desired treatment of the mixture 2 is obtained.
  • the processing times given in the embodiments described below relate to the time during which the mixture 2 circulates in a closed loop in the device 1.
  • the dimensions and the shape of the tube can vary according to the type of mixture 2 as well as the volume to be treated.
  • the tube 3 may have an equilateral triangular section over a length L equal to one hundred and twenty centimeters. Each side p of the section of the tube 3 is then equal to five centimeters and the transducers 6 have the shape of a disc of the order of approximately two centimeters in diameter.
  • the method thus makes it possible to treat the mixture 2 in order to obtain a dispersion of the first phase 2a in the second phase 2b.
  • a dispersion can be obtained by mixing 2 at the micrometric, submicron or nanometric scale of the first phase 2a in the second phase 2b in the form of droplets or particles.
  • the first phase 2a then constitutes the dispersed phase while the second phase 2b constitutes the continuous phase.
  • the treatment of the mixture 2 does not lead to any alteration or chemical modification of the first and second phases 2a, 2b.
  • the generic terms “direct dispersion” or “oil-in-water dispersion” designate a dispersed mixture in which a lipid phase is dispersed in an aqueous phase (also denoted O/W).
  • the generic terms “inverse dispersion” or “water-in-oil dispersion” denote a dispersed mixture in which an aqueous phase is dispersed in a lipid phase (also denoted W/O).
  • the mixture is recovered after obtaining the desired final particle size of the first phase 2a, or more simply when the maximum dispersion of the first phase 2a is reached.
  • the average particle size of the first phase 2a in the second phase 2b after treatment is less than 50 micrometers, more preferably less than 20 micrometers.
  • the method is all the more rapid when it comprises a large number of stages of transducers 6.
  • the processing time of the method also depends on the percentage by mass of the first phase 2a with respect to the second phase 2b.
  • the method makes it possible to obtain an emulsion. It is thus possible to obtain a simple, direct or inverse emulsion, or a multiple emulsion.
  • the method can also make it possible to obtain a structured mixture.
  • the process makes it possible to obtain mixtures structured in monolayer, such as micelles or colloidosomes, in bilayer such as vesicles, simple liposome, membranes, or else in multilayer such as multilamellar liposomes.
  • Liposomes are in the form of lamellar capsules, whose layers consist alternately of lipid phase and aqueous phase.
  • a lipid phase allowing such structuring can be chosen from glycerides, phospholipids, glycolipids, terpenoids, essential oils and/or polar lipids.
  • the structuring of mixture 2 can also make it possible to obtain a vectorization of active principles or of molecules of interest, cosmetics and pharmaceuticals, such as coenzyme Q10.
  • Liposomes allow for example the nano-encapsulation of active agents in the dispersed phase in order to protect these active agents from possible degradation during the storage of the mixture.
  • the principles thus vectorized are more effective and more bioavailable when they are released into living organisms.
  • Liposomes are particularly suitable for use in the food industry as a controlled release system for active agents because they are easily made, adaptable, they are biocompatible and are generally considered safe ( Generally Recognized As Safe - GRAS - by the United States Food and Drug Administration (FDA)).
  • Liposomes are also widely used in the cosmetics and health sectors for the stabilization and vectorization of active ingredients.
  • the process according to the invention also makes it possible to obtain a maximum electrostatic charge on the surface of the liposome in order to obtain a satisfactory stability of the mixture 2 over time.
  • the treated mixture 2 obtained is stable.
  • the stability of mixture 2, that is to say the macroscopic non-separation of the first phase 2a and the second phase 2b from each other, can last two weeks, several months, two years, or more and is therefore suitable for a industrial use.
  • Mixture 2, once treated, can be used as it is or can be incorporated into other lipid or aqueous phases.
  • Construction rules have been established on the basis of analyzes and measurements in order to determine the configuration of the transducers emitting vibratory energy, or the pattern formed by the transducers and the number of stages on the wall 4 of the tube 3 during the implementation of the process. These rules have been established in particular for a tube 3 of triangular section, although these apply or can be transposed to the walls of tubes having other polygonal shapes.
  • the construction rules can be combined with each other, by selectively choosing some of them or taking them into account in total, in order to form an optimal configuration of transducers 6 arranged on the tube 3.
  • the configuration of the transducers 6 in stages of a pattern is noted as follows: (nc 1 , nc 2 , nc 3 , nc 4 , etc.).
  • the configuration noted (2, 3, 2, 2) thus comprises two transducers on the first stage, three transducers on the second stage, and two transducers on the third and fourth stages.
  • each stage comprises at most one transducer 6 on each face of the polygon constituting the section of the tube in which the mixture circulates.
  • the maximum number of transducers at a given stage is therefore equal to the number of sides p of the polygon. In other words, nc i ⁇ p.
  • At least one stage comprises transducers 6 not regularly distributed around the periphery of the tube 3 More precisely, according to the invention, there are several successive processing stages along the tube and on at least one particular stage, there is an arrangement of active transducers not regularly distributed around the periphery of the tube 3 (in other words the stage has no active transducers regularly distributed/spaced around its periphery).
  • a first face comprises an active transducer, and the other two faces do not contain an active transducer;
  • a first face comprises an active transducer and a second face comprises an active transducer, but the third face does not contain an active transducer (it is in fact absent or passive/non-active).
  • n 1 0.
  • At least the first stage comprises two transducers.
  • nc 1 2.
  • This third construction rule differs in particular from known transducer configurations which generally seek to maximize the number of transducers for each of the stages in order to allow a greater vibratory shear applied to the mixture.
  • the number of transducers on each stage is at least equal to the number of transducers on the previous stage. In other words, nc i+1 ⁇ nc i . Increasing the number of transducers on the last stages of a pattern makes it possible to accelerate the process and to process large volumes of mixture.
  • the number of successive stages comprising the same number k of transducers is decreasing.
  • n k+1 ⁇ n k is decreasing.
  • This fifth rule of construction also differs from known transducer configurations which seek to have stages have more transducers and apply more vibrational energy to the mix to speed up mixing processing.
  • certain stages comprise two transducers and certain stages comprise three transducers. Between 50% and 75% of the stages include 2 transducers.
  • the distance d between consecutive floors can be variable.
  • the distance d is in particular less than thirty centimeters, preferably between ten and twenty centimeters.
  • a stage without a transducer can be considered as a spacing between two adjacent stages.
  • the figure 10A to 10M represent possible configurations established from the construction rules described above.
  • the transducers represented in white are active while the transducers represented in dark and in dotted lines are then inactive, that is to say that they do not emit vibrational energy during the treatment of the mixture 2 (which corresponds de facto to an absence of transducer).
  • a 30% emulsion in continuous phase is produced with 2000 g of demineralized water at twenty degrees Celsius and 860 g of mint essential oil at twenty degrees Celsius.
  • the pre-mixing of the emulsion is done by sonication. It is then processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section. The transducer stages are 10 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • the emulsion circulates in the pilot at a speed of 60 g/min.
  • the emulsion produced shows no phase separation after 30 days. storage at room temperature.
  • transducer configuration comprising stages of two and three transducers in alternating five stages (2, 3, 2, 3, 2), approximately 6% of the emulsified oil separated from the emulsion after 30 days of storage at room temperature, which therefore exhibits phase separation.
  • transducer configuration comprising stages of two and three transducers out of five stages but with the first stages comprising 3 transducers, (3, 3, 2, 2, 2), approximately 25% of the emulsified oil separates from the emulsion after 30 days of storage at room temperature, which therefore exhibits phase separation.
  • a 30% emulsion in continuous phase is produced with 2000 g of demineralized water at twenty degrees Celsius to which is gradually added 860 g of sunflower oil at twenty degrees Celsius.
  • a membrane emulsification system allows the addition of oil during processing.
  • the emulsion is processed for four hours by piezoelectric transducers placed on the faces of a stainless steel tube with a triangular section. The transducer stages are 10 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 7.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • the oil is added at a rate of 10 g/min.
  • the emulsion circulates in the pilot at a speed of 900 g/min.
  • the emulsion produced shows no phase separation after 30 days of storage at ambient temperature.
  • a configuration comprising at least four stages of transducers makes it possible to obtain better stability of the mixture treated in accordance with the sixth construction rule specified above.
  • An emulsion is made with 1500 g of demineralized water at seventy degrees Celsius to which is gradually added 1500 g of shea butter at 70 degrees Celsius. It is processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section. The transducer stages are 8 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at 70 degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • a mechanical pre-mixing system is used upstream of the tube.
  • the butter is gradually added to the level of the premix at a rate of 10 g/min.
  • the mixture circulates in the device at a speed of 900 g/min.
  • the emulsion produced shows no phase separation after 30 days of storage at room temperature, this being stable.
  • the emulsion produced shows a significant phase separation after 30 days of storage at room temperature.
  • approximately 45% of the emulsified shea butter separates from the emulsion.
  • the emulsion produced shows a significant phase separation after 30 days of storage at room temperature.
  • approximately 72% of the emulsified shea butter separates from the emulsion.
  • a 30% emulsion is produced with 2000 g of demineralized water at twenty degrees Celsius and 860 g of rapeseed oil at twenty degrees Celsius.
  • the pre-mixing of the emulsion is done via a high pressure homogenizer. It is then processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section. The transducer stages are 6 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • the emulsion circulates in the pilot at a speed of 60 g/min.
  • the emulsion produced shows no phase separation after 30 days of storage at room temperature, which is stable.
  • the emulsion produced shows no phase separation after 30 days of storage at room temperature, which is stable.
  • the emulsion produced shows a significant phase separation after 30 days of storage at room temperature.
  • about 7% of the emulsified oil separates from the emulsion.
  • a 30% emulsion in continuous phase is produced with 2000 g of demineralised water at twenty degrees Celsius to which is gradually added 860 g of liquid paraffin oil, very apolar, at twenty degrees Celsius. It is processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section. The transducer stages are 20 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • a mechanical pre-mixing system and a peristaltic pump allowing the addition of oil during the treatment are used upstream of the transducers. The oil is added at a rate of 10 g/min.
  • the emulsion circulates in the pilot at a speed of 60 g/min.
  • the emulsion produced shows no phase separation after 30 days of storage at ambient temperature.
  • the emulsion produced does not shows no phase separation after 30 days storage at room temperature.
  • two consecutive stages comprising transducers are 18 centimeters apart.
  • the emulsion produced exhibits significant phase separation after 30 days of storage at room temperature.
  • about 75% of the emulsified oil separates from the emulsion.
  • two consecutive stages comprising transducers are 28 centimeters apart.
  • a 30% emulsion in continuous phase is produced with 2000 g of demineralized water at twenty degrees Celsius to which is gradually added 860 g of olive oil at twenty degrees Celsius. It is processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section. The transducer stages are 1.5 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • a mechanical pre-mixing system and a peristaltic pump allowing the addition of oil during the treatment are used upstream of the transducers. The oil is added at a rate of 10 g/min.
  • the emulsion circulates in the pilot at a speed of 60 g/min.
  • the emulsion produced shows no phase separation after 30 days of storage at room temperature. .
  • the emulsion produced shows no phase separation. after 30 days of storage at room temperature.
  • the emulsion produced shows no phase separation. after 30 days of storage at room temperature.
  • approximately 43% of the emulsified oil separates from the emulsion after 30 days of storage at room temperature.
  • the duration of treatment as well as the number of stages of transducers influence the stability of the mixture treated in accordance with the tenth rule of construction specified above.
  • a 90% emulsion in continuous phase is produced with 900 g of demineralized water at twenty degrees Celsius to which is added 100 g of phospholipids at twenty degrees Celsius. It is processed for two hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section.
  • the configuration implemented includes stages with two transducers and three transducer stages on four stages (2, 2, 3, 3). Each of the transducer stages are 6 centimeters apart.
  • the pH of the mixture is maintained at 6.5 during the treatment.
  • a cryostat set at ten degrees Celsius keeps the temperature of the mixture constant during the treatment.
  • a mechanical premix is carried out prior to the circulation of the phases in the tube 3. The dispersion circulates in the tube at a speed of 60 g/min.
  • FIG. 11B a microscopic observation as represented on the figure 11B reveals the presence of liposomes in the mixture 2 having a diameter of the order of 200 nanometers.
  • the figure 11A represents in particular the particle size distribution of these liposomes in the mixture 2.
  • the mixture 2 produced shows no phase separation.
  • a 15% continuous phase emulsion is produced with 1800g of demineralised water at twenty degrees Celsius and a mixture of 167g of rapeseed oil and 33g of coenzyme Q10 at twenty degrees Celsius.
  • the pre-mixing of the emulsion is done via a high pressure homogenizer. It is then processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section.
  • the implemented configuration includes stages of two transducers and three transducers on four stages (2, 2, 3, 3). Each of the transducer stages are 6 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • the emulsion circulates in the pilot at a speed of 60 g/min.
  • Such an emulsion thus makes it possible to obtain a vectorization of coenzyme Q10, having all the properties, in particular antioxidant, of the molecule of interest. After 30 days of storage at room temperature, the emulsion produced shows no phase separation. .
  • a 5% suspension in continuous phase is produced with 1425 g of demineralised water at twenty degrees Celsius and a mixture of 75 g of an iron oxide powder at twenty degrees Celsius.
  • the pre-mixing of the emulsion is done via a mechanical agitation system. It is then processed for four hours by piezoelectric transducers arranged on the three sides of a stainless steel tube with a triangular section.
  • the implemented configuration includes stages of two transducers and three transducers on four stages (2, 2, 3, 3). Each of the floors of transducers are 8 centimeters apart.
  • a pH-stat and a caustic pump (0.1% by mass) make it possible to maintain the pH of the emulsion at 8.
  • a cryostat set at ten degrees Celsius makes it possible to keep the temperature of the emulsion constant during the treatment.
  • the emulsion circulates in the pilot at a speed of 600 g/min.
  • the figures 3 to 6 illustrate the particle size dispersion of the water droplets which remain suspended in the lipid phase thus forming an inverse emulsion.
  • inverse emulsions can be characterized by dynamic light diffraction.
  • the figure 7 represents the particle size distribution of water droplets (5%) in inverse emulsion (W/O) in olive oil (95%) after six hours of treatment according to the process.
  • the droplets have a diameter of less than 500 nanometers and 90% of the population has a diameter of less than 314 nanometers.
  • the average droplet diameter of this emulsion is 175 nanometers.
  • FIG. 8 shows the particle size distribution of the particles of the emulsion measured just after its treatment (curve in solid line) as well as measured after its storage for two years (in dotted line).
  • the measurement of the particle size distribution of the emulsion two years after its treatment shows that the water droplets have slightly increased in size, which reflects a very slight phenomenon of coalescence after the long storage period of the emulsion.
  • this emulsion does not show any phase separation phenomenon and the average size of the droplets remains of the order of 100 nm to 200 nanometers.
  • the emulsion stored for a period of two years does not show any apparent phenomenon of destabilization, phase separation, or decantation of water.
  • the process is of general application in all sectors of industry, and finds a particularly interesting application when the use of emulsifiers in a mixture can pose problems of comfort, irritation, allergy or intolerance. such as in the agri-food, dermatology, cosmetics, relaxation products and pharmacy sectors. Other interesting sectors are, for example, paint or polymers.
  • emulsifiers make it possible to reduce costs, and therefore has an appeal in all the preparations of emulsions on an industrial scale.
  • the mixtures treated by the process according to the invention can be creams, lotions, sprays and any other form of distribution of pharmaceutical and/or cosmetic product.
  • the mixture 2 can be treated first of all in a first container in which the transducer(s) operate at a frequency F1 and then be transferred into a second container in which the transducer(s) operate at a frequency F2 different from the frequency F1, and so on continue if necessary until the complete treatment of the mixture.
  • F1 the first container in which the transducer(s) operate at a frequency F1
  • F2 the frequency of the transducer

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mixers With Rotating Receptacles And Mixers With Vibration Mechanisms (AREA)

Claims (12)

  1. Verfahren zum Behandeln einer Mischung (2), umfassend mindestens eine erste Phase (2a) und eine zweite Phase (2b), die nicht miteinander mischbar sind, wobei das Verfahren die folgenden Schritte umfasst:
    - Umwälzen der Mischung (2) in einem Rohr (3), das eine Wand (4) umfasst und sich zwischen einem Einlassabschnitt (3a) und einem Auslassabschnitt (3b) erstreckt, wobei das Rohr einen polygonalen Querschnitt aufweist, und
    - Beaufschlagen der Mischung (2) mit einer Vibrationsenergie mittels mehrerer Wandler (6), die an der Wand (4) des Rohrs (3) angeordnet sind und mit einer Frequenz von über 900 kHz arbeiten, wobei die Vibrationsenergie es ermöglicht, die erste Phase (2a) in der zweiten Phase (2b) zu dispergieren, wobei die Wandler (6) in mehreren Positionen angeordnet sind, die mehrere aufeinanderfolgende Behandlungsstufen entlang des Rohrs (3) bilden,
    dadurch gekennzeichnet, dass jede Stufe höchstens einen Wandler auf jeder Seite des polygonalen Querschnitts umfasst;
    dass mindestens auf einer Stufe die aktiven Wandler nicht gleichmäßig über den Umfang des Rohrs (3) verteilt sind;
    dass mindestens zwei Wandler pro Stufe vorhanden sind;
    dass Stufen mit zwei Wandlern und Stufen mit drei Wandlern vorhanden sind; und
    dass die Anzahl der Wandler in 50 % bis 75 % der Stufen zwei ist.
  2. Verfahren nach Anspruch 1, wobei die erste Phase (2a) eine Wasserphase ist, wohingegen die zweite Phase (2b) eine Lipidphase ist, oder umgekehrt.
  3. Verfahren nach Anspruch 1, wobei mindestens eine Stufe so beschaffen ist, dass sie keine zwei Wandler (6) aufweist, die einander gegenüberliegend und parallel zueinander angeordnet sind.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei der polygonale Querschnitt eine ungerade Anzahl von Seiten (p) umfasst.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Beaufschlagung mit Vibrationsenergie dazu geeignet ist, eine Emulsion und/oder Liposomen und/oder Wirkstoff-Vektorisierungselemente zu bilden.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Mischung (2) keinen zugesetzten Emulgator umfasst.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Mischung (2), nachdem sie behandelt wurde, bei Umgebungstemperatur mindestens für zwei Wochen oder sogar mindestens für zwei Jahre stabil ist.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Anzahl der Wandler in jeder Stufe größer als oder gleich der Anzahl der Wandler in der vorhergehenden Stufe ist.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Wand (4) einen Innenraum (5) begrenzt, in dem die Mischung (2) umgewälzt wird, wobei die Wandler (6) außerhalb des Innenraums (5) an der Wand (4) angeordnet sind.
  10. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Wandler (6) dazu geeignet sind, bei verschiedenen Frequenzen (F1, F2, F3) zu arbeiten, wobei die Wandler (6) in einer Reihenfolge steigender Frequenz an dem Rohr (3) angeordnet sind.
  11. Vorrichtung (1) für eine Behandlung einer Mischung (2), umfassend mindestens eine erste Phase (2a) und eine zweite Phase (2b), die nicht miteinander vermischbar sind, wobei die Vorrichtung (1) ein Rohr (3) umfasst, das eine Wand (4) umfasst und sich zwischen einem Einlassabschnitt (3a) und einem Auslassabschnitt (3b) erstreckt, wobei das Rohr einen polygonalen Querschnitt aufweist, Wandler (6), die mit einer Frequenz von über 900 kHz arbeiten, an der Wand (4) des Rohrs (3) in mehreren Positionen angeordnet sind, die mehrere aufeinanderfolgende Behandlungsstufen entlang des Rohrs (3) bilden, um die Mischung (2) mit einer Vibrationsenergie zu beaufschlagen,
    dadurch gekennzeichnet, dass jede Stufe höchstens einen Wandler auf jeder Seite des polygonalen Querschnitts umfasst;
    wobei die Wandler so konfiguriert sind, dass zumindest auf einer Stufe die aktiven Wandler nicht gleichmäßig über den Umfang des Rohrs (3) verteilt sind, dass mindestens zwei Wandler pro Stufe vorhanden sind, dass Stufen mit zwei Wandlern und Stufen mit drei Wandlern vorhanden sind und dass die Anzahl der Wandler von 50 % bis 75 % der Stufen zwei ist.
  12. Vorrichtung (1) nach Anspruch 11, wobei der Querschnitt der Wand (4) des Rohrs (3) polygonal ist, wobei der polygonale Querschnitt eine ungerade Anzahl von Seiten (p) umfasst.
EP16777711.9A 2015-08-31 2016-08-29 Verfahren und vorrichtung zur kontinuierlichen behandlung eines gemischs Active EP3344379B1 (de)

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FR1558061A FR3040312B1 (fr) 2015-08-31 2015-08-31 Procede de traitement en continu d'un melange
PCT/FR2016/052135 WO2017037372A1 (fr) 2015-08-31 2016-08-29 Procede et dispositif de traitement en continu d'un melange

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US6506584B1 (en) * 2000-04-28 2003-01-14 Battelle Memorial Institute Apparatus and method for ultrasonic treatment of a liquid
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PT3344379T (pt) 2022-05-11
EP3344379A1 (de) 2018-07-11
WO2017037372A1 (fr) 2017-03-09

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