EP2992950A1 - Procédé de production d'émulsions ou de suspensions aqueuses - Google Patents

Procédé de production d'émulsions ou de suspensions aqueuses Download PDF

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Publication number
EP2992950A1
EP2992950A1 EP14183319.4A EP14183319A EP2992950A1 EP 2992950 A1 EP2992950 A1 EP 2992950A1 EP 14183319 A EP14183319 A EP 14183319A EP 2992950 A1 EP2992950 A1 EP 2992950A1
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EP
European Patent Office
Prior art keywords
liquid
premixing chamber
premix
displacement pump
phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14183319.4A
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German (de)
English (en)
Inventor
John Wesner
Oliver Fey
Patrick Mccall
Stephen Ruszkowski
James Barton
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP14183319.4A priority Critical patent/EP2992950A1/fr
Publication of EP2992950A1 publication Critical patent/EP2992950A1/fr
Withdrawn legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/41Emulsifying
    • B01F23/411Emulsifying using electrical or magnetic fields, heat or vibrations
    • B01F23/4111Emulsifying using electrical or magnetic fields, heat or vibrations using vibrations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/41Emulsifying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/48Mixing liquids with liquids; Emulsifying characterised by the nature of the liquids
    • B01F23/482Mixing liquids with liquids; Emulsifying characterised by the nature of the liquids using molten solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/49Mixing systems, i.e. flow charts or diagrams
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/45Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
    • B01F25/452Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
    • B01F25/4521Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F31/00Mixers with shaking, oscillating, or vibrating mechanisms
    • B01F31/80Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
    • B01F31/81Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations by vibrations generated inside a mixing device not coming from an external drive, e.g. by the flow of material causing a knife to vibrate or by vibrating nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71Feed mechanisms
    • B01F35/717Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/7174Feed mechanisms characterised by the means for feeding the components to the mixer using pistons, plungers or syringes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71Feed mechanisms
    • B01F35/717Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/71755Feed mechanisms characterised by the means for feeding the components to the mixer using means for feeding components in a pulsating or intermittent manner
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/41Emulsifying
    • B01F23/414Emulsifying characterised by the internal structure of the emulsion
    • B01F23/4146Emulsions including solid particles, e.g. as solution or dispersion, i.e. molten material or material dissolved in a solvent or dispersed in a liquid

Definitions

  • the present invention relates to a method of making aqueous emulsions or suspensions and, more particularly, to a method of making aqueous emulsion or suspensions with a homogenizer of the shear/cavitation type.
  • the present invention further relates to an apparatus for the preparation of aqueous emulsion or suspensions.
  • Disperse preparations of the emulsion or suspension type play a prominent role in the preparation of cosmetics, pharmaceutical products and foods.
  • the optimization of the production process is therefore of particular importance.
  • a review of modem methods of producing semisolid and liquid emulsions is given in the article in SOFW-Journal, volume 124, 5/98, pages 308 to 313 , as well as in the article in S ⁇ FW-Journal, volume 118, 5/92, pages 287 to 296 .
  • the methods can be divided into hot/hot, hot/cold and cold/cold methods.
  • hot/cold and cold/cold methods have been developed.
  • a hot oily phase (generally a melt) is added to the emulsifying tank and is emulsified with water, which has a lower temperature than the molten oil phase.
  • the prerequisites for this method were a very slow addition of water to avoid crystallization of the melt by shock cooling, as well as a sufficiently high proportion of hot oil phase to prevent a drop in temperature to below the solidification point of the melt during the addition of water.
  • the WO 95/13787 discloses that, for producing emulsions, it is possible to mix the fatty phase and the aqueous phase at ambient temperature, however, only under the condition that, first of all, a suitable emulsifier is present and, secondly, that the fatty phase is an oil of moderate polarity.
  • a suitable emulsifier for emulsifying oils with a high or low polarity at room temperature, it is necessary that additional metal soaps be present. To begin with, these metal soaps must be dissolved in the oil at elevated temperatures and subsequently cooled; this is also time-consuming and cost- intensive.
  • US 6,479,041 B2 describes a method for producing aqueous emulsions or suspensions, in which a liquid phase is added to a supply tank, which is connected to a homogenizer having a stator, a rotor mounted rotatably in the stator and an additional connection, through which a second phase, which is to be homogenized, can be added directly onto the rotor and comes into contact with the previously added phase only in the toothed rings of the rotor.
  • the homogenizer is started, subsequently the second phase, which is insoluble in the previously added phase and is to be homogenized, is supplied in liquid form through the additional connection.
  • At least one of the two phases is an aqueous phase and at least one of the two phases is not heated.
  • the process suffers from the disadvantage that, when the hot phase is a molten component, often crystallization of the hot phase occurs. This is especially problematic when the emulsification process is stopped or is a discontinuous process, since an interruption of the emulsification process often results in the necessity of a cleaning operation of the homogenizer in which crystallized material must be removed. Further, during the starting process of the homogenizer, the two phases are not supplied with the target ratio as the motors driving the pumps and the homogenizer, respectively, have to start up. Thus, during the starting process of the homogenizer, a homogenous product may not be produced and, therefore, the amounts of the product produced during the starting process are disposed.
  • US 8,517,595 B2 describes an apparatus and method for mixing by producing shear and/or cavitation, and components for the apparatus. Further apparatuses and methods for producing cavitation are described in U.S. Pat. Nos. 3,399,031 ; 4,675,194 ; 5,026,167 ; and 5,837,272 .
  • One particular apparatus for producing hydrodynamic cavitation is known as a SONOLATOR® high pressure homogenizer, which is manufactured by Sonic Corp. of Stratford, Conn., U.S.A.
  • the SONOLATOR® high pressure homogenizer directs liquid under pressure through an orifice into a chamber having a knife-like blade therein. The liquid is directed at the blade, and the action of the liquid on the blade causes the blade to vibrate at sonic or ultrasonic frequencies. This produces hydrodynamic cavitation in the liquid in the area around the blade.
  • Producing different types of emulsions or dispersions within a short timeframe thus requires many different containers for storage and different equipment for portioning and filling, since after production and storage of the product a different container must be used to take up the subsequent product.
  • the product would have to be portioned and filled and the storage container to be cleaned in order to be ready for the next product.
  • the first alternative is very room and equipment intensive, while the second alternative is slow and time intensive.
  • a further problem associated with the intermittent, pulsating operating conditions necessary for portioning and filling is the fact that conventional pumps often do not provide for a pressure profile that provides a steep, almost immediate increase in pressure with every pulse. Such a steep increase is, however, necessary in order to generate the shear and cavitation conditions necessary for producing a stable and high quality emulsion or dispersion with every intermittent stroke or pulse.
  • This method necessarily comprises the contact of the molten hot material with the cold aqueous component, which results in rapid cooling of the melt and successive formation of a well-mixed dispersion.
  • This is generally a smooth process in a continuous state.
  • the supply of heat decreases and the molten material tends to solidify and crystallize on those surfaces which have a temperature below the melting point of the material.
  • Such a solidification results in an interruption of the process and often necessitates disassembly and cleaning of the apparatus for removal of the solidified material.
  • An apparatus used for the preparation of emulsions in the hot/cold method generally is made of steel components due to the high pressure and temperature conditions the apparatus is subjected to. While the steel components have been known to be reliable construction elements for high-pressure homogenizers, they suffer from the disadvantage of a high thermal conductivity, being one of the reasons for the problems described above.
  • a discontinuous production process may not only be of importance in case of unintended or intended discontinuities or interruptions in the production process but is particularly, if the product is to be directly filled into respective comparatively small containers, often designed for end-use, without being temporarily stored in a large tank or any other storing container.
  • the object of the invention is solved by a method for the production of an aqueous emulsion or suspension, wherein a hydrophobic liquid phase is brought into contact with an aqueous phase in a premixing chamber to form a premix.
  • the premixing chamber comprises an inlet from a feed line for a first liquid and at least one inlet from a feed line for at least a second liquid.
  • the premix is forced to leave the premixing chamber through a spray element with an orifice therein forming the outlet of the premixing chamber.
  • the orifice is configured to spray the premix in a jet and produce shear or cavitation in the premix jet.
  • the hydrophobic liquid phase and the aqueous phase are fed in a discontinuous manner, particularly, in a pulsating manner.
  • the hydrophobic liquid phase and the aqueous phase may be premixed in the premix chamber.
  • This premix corresponds to a first step for improving the mixing efficiency.
  • the premix is discharged through the orifice of the spray element.
  • the hydrophobic liquid phase and the aqueous phase are intensively mixed.
  • This intensive mixing corresponds to a second step for improving the mixing efficiency.
  • the hydrophobic liquid phase and the aqueous phase are fed in a discontinuous manner.
  • predetermined volumes of the hydrophobic liquid phase and the aqueous phase may be conveyed.
  • separate and subsequent quantities of the hydrophobic liquid phase and the aqueous phase are conveyed.
  • This method may be combined with any one of the so called hot/hot, hot/cold and cold/cold methods.
  • An emulsion in the sense of the present invention is a mixture of two or more liquids that do not form a single phase upon mixing.
  • one liquid i.e. the dispersed phase
  • the other i.e. the continuous phase.
  • Two liquids can form different types of emulsions.
  • oil and water can form, first, an oil-in-water emulsion, wherein the oil is the dispersed phase, and water is the dispersion medium.
  • they can form a water-in-oil emulsion, wherein water is the dispersed phase and oil is the external phase.
  • Multiple emulsions are also possible, including a "water-in-oil-in-water” emulsion and an "oil-in-water-in-oil” emulsion.
  • a dispersion in the sense of the present invention is a heterogeneous mixture of a liquid containing solid particles.
  • the internal phase (solid) is dispersed throughout the external phase (fluid) through mechanical agitation, with the use of certain excipients or suspending agents.
  • the term solid particles is used as with the present invention one of the two liquids may be a melt, which may crystallize or solidify within the mix and, therefore form solid particles. Dispersed particles can be suspended with the aid of emulsifiers or suspending agents.
  • Shear or shearing in the sense of the present invention refers to the occurrence of a shear strain, which is a deformation of a material substance in which parallel internal surfaces slide past one another. It is induced by a shear stress in the material.
  • Cavitation in the sense of the present invention is the formation of vapor cavities in a liquid, i.e. small liquid-free zones that are the consequence of forces acting upon the liquid. It usually occurs when a liquid is subjected to rapid changes of pressure that cause the formation of cavities where the pressure is relatively low. When subjected to higher pressure, the voids implode and can generate an intense shockwave. Such shockwaves are used to mix the premix consisting of the first liquid and the second liquid.
  • a spray element in the sense of the present invention is any device that facilitates dispersion of liquid or a mix of liquids into a spray.
  • the spray element is used for three purposes: to distribute a liquid over an area, to increase liquid surface area, and to create impact force on a solid surface.
  • the orifice of the spray element causes the formation of a jet of the liquid or mix of liquids.
  • a discontinuous feeding process in the sense of the present is a process which is not continuous, i.e. the material to be conveyed is not fed with a steady flow rate but in separate amounts or doses. With other words, separate and subsequent quantities of the material to be fed are conveyed.
  • the premix may leave the premixing chamber with a pressure of at least 5 bar, preferably at least 20 or at least 50 bar. This allows to convey the premix even if the premix has a high viscosity.
  • the pressure in the premix chamber may vary intermittently.
  • this method provides the basis of a direct portioning and filling process of a mix or emulsion made of the hydrophobic liquid phase and the aqueous phase.
  • a direct filling process is to be understood as a filling process wherein the mix may be directly portioned and filled into corresponding container without being temporarily stored in a tank or any other storing container.
  • the hydrophobic liquid phase and the aqueous phase may be fed in intermittent strokes, preferably in pulsating strokes.
  • a direct portioning and filling process is to be understood as a filling process wherein a predetermined portion of the emulsion or suspension may be directly filled into a corresponding container, generally a container designed for an end-user, without being temporarily stored in a tank or any other storing container.
  • the hydrophobic liquid phase and the aqueous phase may be fed where one stroke can take 0.5 to 25 seconds.
  • the hydrophobic liquid phase and the aqueous phase may be conveyed in fast subsequent, predetermined doses.
  • this method provides the basis of a fast direct filling process of the mix. It has been determined to be advantageous if the maximum pressure in the premixing chamber is reached in a very short timespan after a mixing event is initiated. It has thus been found to be favourable that the liquids to be mixed are delivered to the mixing apparatus by means of a pump which can provide a fast and steep pressure increase within milliseconds (ms), preferably a displacement pump. Further, it is to be noted that the value for the feed concerns one stroke and the time is related to the pressure and the amount of the product. Needless to say, the more pressure and less volume the shorter is the time/stroke.
  • the maximum pressure in the premixing chamber is favourably reached within 5 to 500 bar, preferably within 20 to 180 bar.
  • Each of the hydrophobic liquid phase and the aqueous phase may be fed into the premixing chamber with a volume of 1 ml to 4,000 ml, preferably 2 ml to 250 ml per stroke.
  • the hydrophobic liquid phase and the aqueous phase may be fed into the premixing chamber with flow rates of 1 ml/s to 4,000 ml/s.
  • the hydrophobic liquid phase and the aqueous phase may have a temperature difference of at least 5°C, preferably at least 10°C. As a result of this temperature difference, a cooling device is not necessary as the hot hydrophobic liquid phase within the emulsion may be cooled by means of the aqueous phase.
  • the aqueous emulsion or suspension obtained by the above method may be directly filled into a container, generally a container designed for final use of the product..
  • a container in the sense of the present invention is any receptacle adapted to be filled with an emulsion or suspension made of a hydrophobic liquid phase and an aqueous phase which is filled at the end of a production process of the emulsion or suspension.
  • Such containers are not stationary but portable and are configured to be distributed to end-users, e.g., consumers.
  • Possible receptacles are bottles, vessels, tubes, pots and the like.
  • the hydrophobic liquid phase may be fed into the premixing chamber by means of a first displacement pump and the aqueous phase be fed into the premixing chamber by means of a second displacement pump.
  • predetermined volumes of the hydrophobic liquid phase and the aqueous phase may be conveyed.
  • a (positive) displacement pump in the sense of the present invention is any pump that makes a fluid move by trapping a fixed amount and forcing (displacing) that trapped volume into a discharge pipe or the like.
  • the displacement pump is adapted to convey separate and subsequent quantities of the fluid, i.e. the first liquid and the second liquid.
  • the first displacement pump and/or the second displacement pump is a piston pump or a plunger pump.
  • the first displacement pump and/or the second displacement pump is a metering pump.
  • a piston pump in the sense of the present invention is a type of displacement pump where a high-pressure seal reciprocates with a piston during operation of the pump.
  • a plunger pump in the sense of the present invention is a type of displacement pump where a high-pressure seal is stationary and a smooth cylindrical plunger slides through the seal during operation of the pump.
  • a metering pump in the sense of the present invention is a type of pump that moves a precise volume of liquid in a specified time period providing an accurate flow rate. Delivery of fluids in precise adjustable flow rates is defined as metering.
  • the jet may be directed to a vibrating blade.
  • the action of the jet on the blade causes the blade to vibrate at sonic or ultrasonic frequencies.
  • the emulsion or suspension is prepared via shear or cavitation and consistently good results regarding the mixing efficiency are produced. This generation of cavitation and shear corresponds to a third step for improving the mixing efficiency.
  • the jet may be sprayed with a velocity of 30 m/s to 350 m/s, preferably 50 m/s to 200 m/s.
  • the object of the invention is solved by an apparatus for mixing a first liquid and at least a second liquid by producing shear and/or cavitation, said apparatus comprising a premixing chamber.
  • the premixing chamber is configured in that at least a first liquid and at least a second liquid are mixed to form a premix.
  • the premixing chamber comprises an inlet from a feed line for a first liquid and at least one inlet from a feed line for at least a second liquid.
  • the apparatus further comprises a spray element with an orifice therein forming the outlet of the premixing chamber.
  • the orifice is configured to discharge the premix from the premixing chamber in a jet and produce shear or cavitation in the premix jet.
  • the apparatus further comprises a mixing chamber with an outlet.
  • the mixing chamber is configured to collect the jet exiting the premix chamber as a mix and to discharge the mix through the outlet.
  • the apparatus further comprises a first displacement pump for feeding the first liquid through the feed line for the first liquid and a second displacement pump for feeding the second liquid through the feeding line for the second liquid.
  • the first liquid and the second liquid may be premixed in the premix chamber.
  • This premix corresponds to a first step for improving the mixing efficiency.
  • the premix is discharged through the orifice of the spray element.
  • the premix is dispensed.
  • the orifice is adapted to produce shear or cavitation in the premix jet
  • the first liquid and the second liquid are intensively mixed and collected within the mixing chamber. Thereafter, the so provided mix may be discharged from the outlet of the mixing chamber. Further, predetermined volumes of the first liquid and the second liquid may be conveyed.
  • first displacement pump and the second displacement pump may be adapted to feed the first liquid and the second liquid in pulsating strokes.
  • a direct filling process is to be understood as a filling process wherein the mix may be directly filled into a corresponding container without being temporarily stored in a tank or any other storing container.
  • the mix may be conveyed in fast subsequent, predetermined doses.
  • this construction provides the basis of a fast direct filling process of the mix.
  • the first displacement pump and the second displacement pump may be each adapted to provide an operating pressure within 5 to 500 bar, preferably within 20 to 180 bar.
  • This construction ensures that the first liquid and the second liquid are reliably premixed due to the rapid pressure increase.
  • the first displacement pump and/or the second displacement pump is a piston pump or a plunger pump.
  • the first displacement pump and/or the second displacement pump is a metering pump.
  • the first displacement pump and the second displacement pump may be each adapted to feed a volume of 1 ml to 4,000 ml, preferably 2 ml to 250 ml per stroke.
  • the feed line for the first liquid at least partially consists of a material with a specific thermal conductivity of less than 15 W/(m*K), preferably less than 5 W/(m*K) or less than 2 W/(m*K).
  • the feed line may be at least partially made of a material having a low specific thermal conductivity.
  • the feed line for the first liquid may form a part of the wall of the premixing chamber.
  • the portion of the feed line having a low specific thermal conductivity is arranged close to or at the premixing chamber.
  • Suitable materials for the feed may be selected in that the feed line for the first liquid at least partially comprises glass, or mineral material or polymeric material or a mixture of two or more thereof.
  • the feed line for the first liquid at least partially comprises a mineral material selected from quartz, concrete, or a thermoset or thermoplastic polymer such as polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyoxybenzylmethylenglycolanhydride, poly(etherketone)s (PEK), poly(etheretherketone)s (PEEK), poly(etherketonekteone)s (PEKK), poly(etheretheretherketone)s (PEEEK), poly(etheretherketoneketone)s (PEEKK) or poly(etherketonetherketonketon)s (PEKEKK).
  • PP polypropylene
  • PE polyethylene
  • PVC polyvinyl chloride
  • PEKK poly(etherketone)s
  • PEEK poly(etherketonekteone)s
  • PEKK poly(etheretheretherketone)s
  • PEEKK poly(etherketoneketone)s
  • PEEKK poly(etherketoneketone)s
  • PEKEKK poly(etherketonetherketon
  • the apparatus may be designed in that at least a part of the feed line for the first liquid forms part of the boundary of the premixing chamber.
  • the portion of the feed line having a low specific thermal conductivity is arranged as close as possible to the premixing chamber by means of forming a part thereof.
  • the feed line for the first liquid may comprise a front portion facing the premixing chamber and a rear portion facing away from the premixing chamber.
  • the front portion may be made of a material with a specific thermal conductivity of less than 15 W/(m*K), preferably 5 W/(m*K) or less than 5 W/(m*K) or 2 W/(m*K) or less than 2 W/(m*K). It can be especially preferred to use a material having a thermal conductivity of 1 W/(m*K) or less, or 0,5 W/(m*K) or less or 0,3 W/(m*K) or less.
  • Suitable polymers are polymers selected from the group of poly(etherketone)s (PEK), poly(etheretherketone)s (PEEK), poly(etherketonekteone)s (PEKK), poly(etheretheretherketone)s (PEEEK), poly(etheretherketoneketone)s (PEEKK) or poly(etherketonetherketonketon)s (PEKEKK) (all 0,23 - 0,27), Polyethylenterephthalate (PET 0,24) Polyurethane (PUR 0,245), Polyimide (PI 0,37 - 0,52), Polyetherimide (PEI 0,24), Polytetrafluoroethylene (PTFE 0,25), Polyvinylchloride (PVC 0,17), Polyamide (PA 0,25 - 0,35), Polypropylene (PP 0,23), Polycarbonate 0,20), Epoxyresin (EP 0,20), Polymethylmethacrylat (PMMA 0,19), Polyethylene (PE 0,33 - 0,57), Polystyrene (PS 0,17), Polysilox
  • the feed line for the first liquid at least partially comprises a material with a comparable low specific thermal conductivity
  • this apparatus is advantageous particularly in cases the first liquid is a molten hot material which comes into contact with a cold material as the second liquid.
  • the comparable low specific thermal conductivity prevents a rapid cooling of the melt, for example in case of a production interruption, an intermittent production or the like.
  • Thermal conductivity in the sense of the present invention is the property of a material to conduct heat. Thermal conductivity is measured in watts per meter kelvin (W/(m*K))
  • the feed line may be at least partially made of a material having a low specific thermal conductivity.
  • the feed line for the first liquid may form a part of the wall of the premixing chamber.
  • the portion of the feed line having a low specific thermal conductivity is arranged close to or at the premixing chamber.
  • the front portion may comprise a first inner diameter and the rear portion may comprise a second inner diameter.
  • the first inner diameter may be smaller than the second inner diameter.
  • the front portion may comprise a wall thickness of 1 mm to 20 mm, preferably of 2 mm to 6 mm.
  • the wall thickness may be decreased.
  • the wall thickness may be decreased if the material for the front portion has a low specific thermal conductivity, the wall thickness may be decreased if compared to a material having a higher specific thermal conductivity.
  • the mixing chamber may comprise a vibrating blade.
  • the premix is directed at the blade, and the action of the premix on the blade causes the blade to vibrate at sonic or ultrasonic frequencies. This produces hydrodynamic cavitation in the premix in the area around the blade.
  • the mix is prepared via shear or cavitation and consistently good results regarding the mixing efficiency are produced.
  • the vibrating blade may be omitted.
  • This construction may be preferred in cases the premix is fed into the mixing chamber in a intermittent or pulsating manner.
  • the object of the invention is solved by use of an apparatus as described above to produce an aqueous emulsion or suspension.
  • the apparatus may be used to produce an aqueous emulsion or suspension according to the methods described above.
  • the first liquid may be a hydrophobic liquid phase and the second liquid may be an aqueous phase.
  • the hydrophobic liquid phase may be brought into contact with the aqueous phase in the premixing chamber to form the premix.
  • the premix may be forced to leave the premixing chamber through the spray element with the orifice therein forming the outlet of the premixing chamber.
  • the orifice may be configured to spray the premix in a jet and produce shear or cavitation in the premix jet.
  • the first liquid and the second liquid may have a temperature difference of at least 10°C.
  • the hydrophobic liquid phase and the aqueous phase are fed in a discontinuous manner, particularly, in a pulsating manner.
  • the hydrophobic liquid phase and the aqueous phase may be premixed in the premix chamber.
  • This premix corresponds to a first step for improving the mixing efficiency.
  • the premix is discharged through the orifice of the spray element.
  • the orifice is adapted to produce shear or cavitation in the premix jet
  • the hydrophobic liquid phase and the aqueous phase are intensively mixed.
  • a cooling device is not necessary as the hydrophobic liquid phase within the mix may be cooled by the aqueous phase.
  • hydrophobic liquid phase and the aqueous phase are fed in a discontinuous manner.
  • predetermined volumes of the hydrophobic liquid phase and the aqueous phase may be conveyed.
  • separate and subsequent quantities of the hydrophobic liquid phase and the aqueous phase are conveyed.
  • Emulsions or dispersion which can be produced with a method and apparatus according to the invention generally have two phases, an "aqueous phase” and a “non-aqueous phase", often also called an “oil phase”. It is within the scope of the invention to produce emulsions of the O/W type as well as of the W/O type.
  • aqueous phase can comprise water as well as mixtures of water with water-soluble solvents, such as low molecular weight alcohols, for example, ethanol or isopropanol or polyols, such as ethylene glycol, diethylene glycol, butylene glycol or glycerin.
  • water-soluble solvents such as low molecular weight alcohols, for example, ethanol or isopropanol or polyols, such as ethylene glycol, diethylene glycol, butylene glycol or glycerin.
  • the particles, of the disperse phase generally have a particle size of, for example, about 0.1 ⁇ m to about 10 ⁇ m, and a large effective surface.
  • waxes or wax-like materials such as natural waxes, which can be regenerated (insect wax, animal wax and plant wax), fossil waxes (crude oil wax, brown coal wax, peat wax or ozokerites), synthetic waxes (Fischer-Tropsch wax, polyethylene wax or amide wax), higher melting paraffins, esters, fats, long-chain carboxylic acids or long-chain alcohols, each having a melting or solidifying point above room temperature.
  • the temperatures of the aqueous phase and of the hot melt supplied ideally are selected so that the resulting temperature of the mixture is below the crystallization or solidification point of the substance, which is to be homogenized into the previously added phase. For example, if the temperature of the molten wax is 70°C to 90° C. and the temperature of the aqueous phase is 10° to 25° C.
  • the hot phase which is to be homogenized, especially a molten wax or a melt of a substance, which has a wax-like consistency at room temperature, is homogenized without an emulsifier.
  • the phase, which is to be homogenized is a liquid at room temperature, it is preferably added without being heated.
  • Such a phase may be an oil or an oil-like material, such as naturally occurring oils (vegetable or animal fatty oils), which can be regenerated, synthetic oils, silicone oils, mineral oils, essential oils, water-insoluble, branched or linear aliphatic hydrocarbons, linear or branched alcohols, especially fatty alcohols as well as long-chain ethers or esters.
  • Suitable hydrocarbons are, for example, liquid paraffins, squalane or squalane.
  • esters of trihydric and multihydric alcohols especially vegetable triglycerides, such as olive oil, almond oil, peanut oil, sunflower oil as well as synthetic triglycerides, such as C 2 to C 10 fatty acid triglycerides or also jojoba oil, are suitable.
  • monoesters or diesters of the formula R 1 -COOR 2 , R 1 -COO-R 3 -OOCR 1 and R 2 COO-R 3 -OOCR 2 in which R 1 represents a C 8 to C 22 alkyl group, R 2 a C 3 to C 22 alkyl group and R 3 a C 2 to C 16 alkylene group, are suitable as oil phase.
  • materials, which are usually used as opacifying agents in cosmetic materials are suitable as substances, which are to be homogenized.
  • R 1 -COO(CHR 4 CHR 5 O) n -COR 6 wherein R 1 represents a C 8 to C 22 alkyl group, R 4 and R 5 represent hydrogen or methyl and R 6 represents hydrogen or R 1 and n is a number between 1 and 12 and preferably 1, 2, 3 or 4. Diesters of glycol and fatty acids are preferred.
  • oil phase is a liquid at room temperature, it is particularly advantageous and saves time and energy, if neither of the phases is heated (cold/cold emulsification).
  • the method according to the invention can be carried out without an emulsifier.
  • an emulsifier or a surfactant, as emulsifier may also be present and preferably is introduced before the substance, which is to be homogenized, was supplied over the additional connection of the homogenizer.
  • the emulsifier may be present in amounts of 0.5 to 30% by weight of the finished composition.
  • Nonionic, anionic, cationic, amphoteric or zwitterionic emulsifiers are suitable. Suitable emulsifiers are listed, for example, in the " International Cosmetic Ingredient Dictionary and Handbook", 7th edition, volume 2 , in the "Surfactants” section and especially in the "Surfactants-Emulsifier Agents".
  • Nonionic emulsifier are, for example, ethoxylated fatty alcohols, ethoxylated nonylphenols, monoglycerides and diglycerides of fatty acids, ethoxylated castor oil and ethoxylated, hydrogenated castor oil, fatty acid alkanolamides and ethoxylated fatty esters.
  • Cationic emulsifiers are, for example, long-chain quaternary ammonium compounds such as those known under the CTFA name of "quaternium”, for example, alkyltrimethylammonium salts of dialkyldimethylammonium salts with C 8 to C 22 alkyl groups.
  • Anionic emulsifiers are, for example, fatty alcohol sulfates, alkyl ether sulfates and alkylbenzenesulfonates.
  • Amphoteric emulsifiers are, for example, the different known betaines, such as fatty acid amidoalkylbetaines and sulfobetaines and C 8 to C 22 alkyl betaines.
  • the inventive method is also suitable for producing an opacifier composition for cosmetic materials.
  • a concentrated alkyl ether sulfate such as lauryl ether sulfate
  • electrolyte-free water which has not been heated.
  • a water-insoluble opacifying agent such as a diester of ethylene glycol and fatty acid or of polyethylene glycol and fatty acid, for example, polyethylene glycol (3)-distearate, is homogenized in the liquid or molten state with the above mentioned water/ether sulfate mixture.
  • the method according to the invention is especially suitable for producing cosmetic and pharmaceutical materials. Since the emulsion or suspension produced pursuant to the invention is extremely fine and has a low viscosity, the further active and inactive ingredients can be incorporated significantly more easily and quickly than they can according to conventional methods, as a result of which the formulation times are clearly shortened.
  • hair dyeing creams are also particularly advantageous to produce hair dyeing creams according to the inventive method, particularly hair dyeing creams for oxidizing hair dyes containing dye intermediates, which respond to oxidation.
  • These hair dyeing creams are usually based on a wax-containing cream.
  • a hydrophobic, molten wax phase heated to about 70° to 80° C, is emulsified at a temperature of 70° to 80° C. in an aqueous phase, containing the dye intermediates as well as any additional conventional additives.
  • the emulsion must be cooled very slowly and with delay and stirring, in order to prevent uncontrolled crystallization of the wax (formation of wax specks).
  • undesirable oxidation reactions may occur as a result of the oxygen stirred in from the air.
  • there may be post-thickening which may cause difficulties with the finished product.
  • the desired final viscosity is obtained already by the homogenization.
  • the desired final viscosity can also be adjusted (preferably at the end of the manufacturing process) by the addition of an electrolyte, such as sodium chloride, or of a different, thickening material, such as celluloses or cellulose derivatives.
  • compositions produced by conventional methods, frequently show the effect of post-thickening, which means that the final viscosity and consistency are developed only after a certain period of time.
  • Compositions, produced by the method according to the invention do not have this disadvantage. Instead, they have their final viscosity generally immediately at the conclusion of the manufacturing process or very shortly thereafter.
  • the emulsions or suspensions produced pursuant to the invention at the same concentration and using the same amount of hydrophobic materials, have advantageous properties. Physically, this is observed in a higher viscosity of the compositions produced pursuant to the invention.
  • the application properties of the products are also improved. For example, for a hair care material, in the form of a pumpable foam, it was found that the feel and combability of the treated hair are better and the foam is creamier and softer than in the case of a product, not produced pursuant to the invention but having the identical chemical composition.
  • the improved consistency properties and application properties presumably are attributable to a better, finer dispersion of the internal phase or to a smaller particle diameter of the dispersed phase.
  • Figure 1 shows an overview of a system 10 for producing a mix of a first liquid 12 and a second liquid 12.
  • the system 10 is adapted to produce an emulsion or suspension.
  • the first liquid 12 may be an aqueous phase and the second liquid 14 may be a hydrophobic liquid phase.
  • the first liquid 12 may be stored within at least one tank 16.
  • the second liquid 14 may be stored within at least one tank 18.
  • the at least one tank 16 for the first liquid 12 and the at least one tank 18 for the second liquid 14 are connected to an apparatus 20 for mixing a first liquid and at least a second liquid by producing shear and/or cavitation, which will be described in more detail below.
  • the apparatus 20 is connected to a storing tank 22 for storing a mix 24 leaving the apparatus 20.
  • the mix 24 corresponds to the emulsion or suspension.
  • the storing tank 22 may be used as a buffering tank for buffering the mix 24 in a filling process as will be explained in more detail below.
  • the storing tank 22 may comprise an agitator 26 for agitating the mix 24 stored within the storing tank 22.
  • the agitation process may be used for preventing a separation of the respective components of the mix 24.
  • the storing tank 22 may be connected to a filler (not shown in detail) for directly filling the mix 24 into a container 25.
  • the system 10 comprises a pump 28.
  • the system 10 may additionally comprise a mill 30 for further dispersing the mix 24 before being supplied to the filler.
  • the apparatus 20 is directly connected to the filler in order to directly fill the mix 24 into the container 25.
  • FIG. 2 shows a cross-sectional view of the apparatus 20 for mixing the first liquid 12 and at least the second liquid 14 by producing shear and/or cavitation according to a first embodiment of the present invention.
  • the apparatus 20 comprises a feed line 32 for the first liquid 12 and a feed line 34 for the second liquid 14.
  • the feed line 32 for the first liquid 12 at least partially comprises a material 36 with a specific thermal conductivity of less than 15 W/(m*K).
  • the feed line 32 for the first liquid 12 at least partially consists of a material with a specific thermal conductivity of less than 15 W/(m*K), preferably less than 5 W/(m*K) or less than 2 W/(m*K), for example 0,5 W/(m*K).
  • the feed line 32 for the first liquid 12 at least partially comprises glass, or mineral material or polymeric material or a mixture of two or more thereof.
  • the feed line 32 for the first liquid 12 at least partially comprises a mineral material selected from quartz, concrete, or thermoset or thermoplastic polymer such as polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyoxybenzylmethylenglycolanhydride, poly(etherketone)s (PEK), poly(etheretherketone)s (PEEK), poly(etherketonekteone)s (PEKK), poly(etheretheretherketone)s (PEEEK), poly(etheretherketoneketone)s (PEEKK) or poly(etherketonetherketonketon)s (PEKEKK).
  • PP polypropylene
  • PE polyethylene
  • PVC polyvinyl chloride
  • PEKK poly(etherketone)s
  • PEEK poly(etherketonekteone)s
  • PEKK poly(etheretheretherketone)s
  • PEEKK poly(
  • the apparatus 20 further comprises a premixing chamber 38.
  • the premixing chamber 38 comprises an inlet 40 from the feed line 32 for the first liquid 12 and at least one inlet 42 from the feed line 34 for the at least one second liquid 14.
  • the first liquid 12 and the at least one second liquid 14 are mixed to form a premix 44.
  • At least a part 46 of the feed line 32 for the first liquid 12 forms part of a wall 48 of the premixing chamber 38. More particularly, at least a part 46 of the feed line 32 for the first liquid 12 forms part of a boundary 49 of the premixing chamber 38.
  • the feed line 32 for the first liquid 12 comprises a front portion 50 facing the premixing chamber 38 and a rear portion 52 facing away from the premixing chamber 38.
  • the front portion 50 is made of the material 36 with a specific thermal conductivity of less than 15 W/(m*K), preferably less than 5 W/(m*K) or less than 2 W/(m*K).
  • the front portion 50 comprises a first inner diameter 54 and the rear portion 52 comprises a second inner diameter 56.
  • the first inner diameter 54 is smaller than the second inner diameter 56.
  • a transition portion 58 may be provided between the front portion 50 and the rear portion 52.
  • the transition portion 58 may be shaped in that a third inner diameter 60 gradually decreases from the rear portion 52 to the front portion 50.
  • the third inner diameter 60 may conically narrow.
  • the front portion 50 comprises a wall thickness 62 of 1 mm to 20 mm, preferably of 2 mm to 6 mm.
  • the rear portion 52 may be made of metal.
  • the feed line 32 for the first liquid may be made completely of the material 36 with a specific thermal conductivity of less than 15 W/(m*K), preferably less than 5 W/(m*K) or less than 2 W/(m*K).
  • the apparatus 20 further comprises a spray element 64 with an orifice 66 therein forming an outlet 68 of the premixing chamber 38.
  • the orifice 66 is configured to discharge the premix 44 from the premixing chamber 38 in a jet 70 and to produce shear or cavitation in the premix jet 70.
  • Figure 3 shows a perspective view of the spray element 64 of the apparatus 20 for mixing a first liquid and at least a second liquid by producing shear and/or cavitation according to the first embodiment of the present invention.
  • the orifice 66 is formed similar to a cat eye.
  • the interior of the orifice 66 is a hemispherical dome.
  • the orifice 66 is made with a V-shaped cut from outside. The area of the orifice 66 is controlled by an angle of the V-shape, a radius of the dome and the depth of the cut.
  • the apparatus 20 further comprises a mixing chamber 72 with an outlet 74.
  • the mixing chamber 72 collects the jet 70 exiting the premix chamber 38 as the mix 24 and discharges the mix 24 through the outlet 74.
  • the mixing chamber 72 further comprises a vibrating blade 76.
  • the mix 24 is directed at the blade 76.
  • the action of the mix 24 on the blade 76 causes the blade 76 to vibrate at sonic or ultrasonic frequencies. Thereby, hydrodynamic cavitation in the mix 24 in the area around the blade 76 is produced, which increases the mixing efficiency.
  • the apparatus 20 In order to supply the first liquid 12 and the second liquid 14 from the tank 16 for the first liquid 12 and the tank 18 for the second liquid 14 to the apparatus 20, pumps are provided.
  • the system 10 is configured to discontinuous fill the storage tank 22, i.e. the storage tank 22 is filled with subsequent quantities of the mix 24.
  • the apparatus 20 comprises a first displacement pump 78 for feeding the first liquid 12 through the feed line 32 for the first liquid 12 and a second displacement pump 80 for feeding the second liquid 14 through the feeding line 34 for the second liquid 14.
  • the first displacement pump 78 and the second displacement pump 80 are adapted to feed the first liquid 12 and the second liquid 14 in pulsating or intermittent strokes.
  • the first displacement pump 78 and the second displacement pump 80 are adapted to feed the first liquid 12 and the second liquid 14 where one stroke can take 0.5 to 25 seconds.
  • the first displacement pump 78 and the second displacement pump 80 are each adapted to provide an operating pressure within 5 to 500 bar, preferably within 20 to 180 bar, for example 100 bar. This operating pressure is build-up at the same time within the premixing chamber 38.
  • the first displacement pump 78 and/or the second displacement pump 80 is a piston pump or a plunger pump.
  • the first displacement pump 78 and/or the second displacement pump 80 is a metering pump.
  • the first displacement pump 78 and the second displacement pump 80 are each adapted to feed a volume of 1 ml to 4,000 ml, preferably 2 ml to 250 ml per stroke, for example 80 ml per stroke.
  • the apparatus 20 is adapted to provide flow rates of 1 ml/s to 4,000 ml/s. It is explicitly stated that the storage tank 22 may be omitted and the mix 24 discharged through the outlet 74 may be directly filled into suitable containers such as bottles or receptacles.
  • the emulsion or suspension may be produced according to the so called hot/hot, hot/cold and cold/cold methods. If the apparatus 20 is used, this provides certain advantages in combination with the so called hot/cold method as will be described in further detail below.
  • the production is carried out using the apparatus 20.
  • the first liquid 12 is a hydrophobic liquid phase and the second liquid 14 is an aqueous phase.
  • the first displacement pump 78 and the second displacement pump 80 the first liquid 12 and the second liquid 14 are supplied to the apparatus 20 through the feed line 32 for the first liquid 32 and the feed line 34 for the second liquid 14.
  • the first liquid 12 and the second liquid 14 have a temperature difference of at least 10°C.
  • the first liquid 12 is a melt of the hydrophobic liquid phase which has a temperature that is at least 10 °C higher than the second liquid 14.
  • the first liquid 12 is heated and comprises a temperature of about 75 °C and the second liquid 14 comprises a temperature of about 15 °C.
  • the front portion 50 of the feed line 32 for the first liquid 12 is made of the material 36, a crystallization of the hot hydrophobic liquid phase within the feed line 32 is reliably prevented even when the emulsification process is stopped or is a discontinuous process as described above because the material 36 having a low specific thermal conductivity prevents the hydrophobic liquid phase from being cooled by the cooler aqueous phase.
  • the first liquid 12 and the second liquid 14 are fed into the premixing chamber 38 in a discontinuous manner. Due to the operation principle of the first displacement pump 78 and the second displacement pump 80, the first liquid 12 and the second liquid 14 are fed into the premixing chamber 38 in pulsating strokes. For example, the first liquid 12 and the second liquid 14 are fed into the premixing chamber 38 where one stroke can take 0.5 to 25 seconds.
  • the first liquid 12 and the second liquid 14 are fed with a volume of 1 ml to 4,000 ml, preferably 2 ml to 250 ml per stroke.
  • a flow rate of the first liquid 12 and the second liquid 14 are fed may be 1 ml/s to 4,000 ml/s. The more pressure and less volume the shorter is the time/stroke.
  • the first liquid 12 enters the premixing chamber 38 through the inlet 40 and the second liquid 14 enters the premixing chamber 38 through the inlet 42.
  • the pressure in the premix chamber 38 varies intermittently, wherein the pressure in the premixing chamber is provided within 5 to 500 bar, preferably within 20 to 180 bar, for example 100 bar.
  • the hydrophobic liquid phase is brought into contact with the aqueous phase in the premixing chamber 38 to form the premix 44.
  • the cooler aqueous phase starts to cool the hotter hydrophobic liquid phase not until coming into contact with one another within the premixing chamber 38.
  • the first displacement pump 78 and the second displacement pump 80 are adapted to feed the first liquid 12 and the second liquid 14 such that a pressure of 5 to 500 bar, preferably 20 180 bar is present in the premixing chamber 38. Subsequently, the premix 44 is forced to leave the premixing chamber 38 through the spray element 64 with the orifice 66 therein forming the outlet 68 of the premixing chamber 38. The premix 44 leaves 44 the premixing chamber 38 with a pressure of at least 5 bar, preferably at least 20 or at least 50 bar, for example 100 bar.
  • the orifice 66 sprays the premix 44 in a jet 70.
  • the jet 70 is sprayed with a velocity of 30 m/s to 350 m/s, preferably 50 m/s to 200 m/s, for example 120 m/s.
  • the orifice 66 is configured to produce shear or cavitation in the premix jet 70 as the jet 70 leaving the orifice 66 impinges on the vibrating blade 76.
  • the jet 70 is directed at the blade 76.
  • the action of the jet 70 on the blade 76 causes the blade 76 to vibrate at sonic or ultrasonic frequencies.
  • the premix 44 is intensively mixed so as to form the mix 24.
  • the mix 24 is collected within the mixing chamber 72.
  • the jet 70 after being intercepted by the blade 76, will exit directly from two holes 82 formed close to an axial center 84, both above and below the blade 76. This portion of the jet 70 will not recirculate in the mixing chamber 72.
  • the mixing chamber 72 comprises a large volume if compared to the premixing chamber 38, the pressure within the mixing chamber 72 decreases. For example, a pressure within the mixing chamber 72 may be 2 bar.
  • the mix 24 is discharged through the outlet 74 and is directly filled into the container 25.
  • the direct filling process is facilitated as the first displacement pump 78 and the second displacement pump 80 feed the first liquid 12 and the second liquid 14 batch-wise such that the mix is also produced batch-wise. It is explicitly stated that the mix 24 may also be filled into the storage tank 22 and then be filled into the container 25. Further, due to the pressures present in the premixing chamber 38 and the mixing chamber 72, the vibrating blade 76 may be omitted.
  • Figure 4 shows a cross-sectional view of an apparatus 20 for mixing a first liquid 12 and at least a second liquid 14 by producing shear and/or cavitation according to a second embodiment of the present invention.
  • apparatus 20 for mixing a first liquid 12 and at least a second liquid 14 by producing shear and/or cavitation according to a second embodiment of the present invention.
  • FIG. 4 shows a cross-sectional view of an apparatus 20 for mixing a first liquid 12 and at least a second liquid 14 by producing shear and/or cavitation according to a second embodiment of the present invention.
  • the apparatus 20 according to the second embodiment may be basically applied to the system 10 shown in Figure 1 .
  • the apparatus 20 according to the second embodiment is adapted to provide flow rates less than the apparatus 20 according to the first embodiment.
  • the apparatus 20 according to the second embodiment is adapted to provide flow rates up to ...ml/s.
  • the mixing chamber 72 of the apparatus 20 according to the second embodiment differs significantly in geometry from the mixing chamber 72 of the apparatus 20 according to the first embodiment.
  • the vibrating blade 76 is held by a blade holder 86.
  • the premix jet 70 from the orifice 66 which is first intercepted by the vibrating blade 76, is forced to turn by the surface of the blade holder 86 to form recirculation.
  • the thus formed mix 24 exits the mixing chamber 72 by two narrow tunnels 88 formed at a top 90 and a bottom 92 of the blade holder 86.

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CN105692923A (zh) * 2016-04-19 2016-06-22 林俊生 一种增压除垢装置及增压除垢设备

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