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WO1997036674A1 - Dispersion de phases immiscibles - Google Patents

Dispersion de phases immiscibles Download PDF

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Publication number
WO1997036674A1
WO1997036674A1 PCT/GB1997/000910 GB9700910W WO9736674A1 WO 1997036674 A1 WO1997036674 A1 WO 1997036674A1 GB 9700910 W GB9700910 W GB 9700910W WO 9736674 A1 WO9736674 A1 WO 9736674A1
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WO
WIPO (PCT)
Prior art keywords
membrane
phase
oil
discontinuous phase
size
Prior art date
Application number
PCT/GB1997/000910
Other languages
English (en)
Inventor
Richard Andrew Williams
Derek Alfred Wheeler
Neil Christopher Morley
Original Assignee
Disperse Technologies Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Disperse Technologies Limited filed Critical Disperse Technologies Limited
Priority to BR9708583-9A priority Critical patent/BR9708583A/pt
Priority to JP9535048A priority patent/JP2000507497A/ja
Priority to EP97915560A priority patent/EP0889749A1/fr
Priority to AU22995/97A priority patent/AU2299597A/en
Publication of WO1997036674A1 publication Critical patent/WO1997036674A1/fr

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Classifications

    • 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
    • B01F23/4105—Methods of emulsifying
    • 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
    • B01F23/45—Mixing liquids with liquids; Emulsifying using flow mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/314—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit
    • B01F25/3142—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit the conduit having a plurality of openings in the axial direction or in the circumferential direction
    • B01F25/31421—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit the conduit having a plurality of openings in the axial direction or in the circumferential direction the conduit being porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/50—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle
    • B01F25/51—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle in which the mixture is circulated through a set of tubes, e.g. with gradual introduction of a component into the circulating flow

Definitions

  • This invention relates to an apparatus and method for producing dispersions of two or more immiscible phases, for example in the manufacture of emulsions and encapsulated products wherein the properties of the dispersed phase droplets must be carefully controlled.
  • EP Specification No. 452,140 Al describes a method for the manufacture of emulsions by passing one phase into another through a membrane, particularly in the field of making foodstuff spreads.
  • WO Specification No. 87/04924 is addressed to the manufacture of liposomes and involves the use of a commercially-available asymmetric ceramic filter.
  • a method for preparing a mixture of the emulsion type wherein a discontinuous phase is introduced into a circulating continuous phase by passage through a membrane which is characterised by at least one of the following features:
  • an apparatus so designed as to enable the method of the invention to be carried out, said apparatus comprising a membrane as defined above together with means for providing a circulating continuous phase, means for providing a discontinuous phase and a source of pressure to force the discontinuous phase through the membrane.
  • the membrane itself is preferably formed from a ceramic material, and more particularly it is preferably substantially tubular in shape with the pores passing radially through the material of the tube.
  • the size and size-distribution of the pores of the membrane will be determined by the type of emulsion desired. For example, if oil phase droplets of diameter 1 ⁇ m are desired, a pore size of the order of 0.35 um will be required.
  • the surface chemistry of the membrane may be adapted to provide varying degrees of wettability.
  • the membrane When the membrane is formed of sintered metal it will preferably have a rolled surface finish.
  • the method and apparatus of the invention may be adapted to produce either a single-phase emulsion or an emulsion containing a plurality of discontinuous phases, and it may work in either a batch-process or a continuous production mode.
  • the membrane When a batch-process is desired, the membrane may be formed in the shape of a diverging tube.
  • the continuous aqueous phase is circulated and recirculated through the inside of the tube and the discontinuous oil phase is forced through the tubular membrane wall into the continuous phase.
  • the tube is made divergent in order to maintain constant shear force along the length of the membrane surface, as the total volume and viscosity of the emulsion increase as more oil phase is added to the aqueous phase during passage along the tube.
  • the pore structure of the membrane may be varied, both in terms of individual pore area and number of pores per unit area of the membrane, to ensure that there is uniformity of droplet size along the length of the tube.
  • the circulation of aqueous phase is stopped when the volume of oil phase in the emulsion has reached the desired level.
  • the continuous phase is recirculated via a storage vessel from which the desired emulsion is bled off when the volume of oil phase has reached the desired level.
  • the membrane may consist of a single tubular structure as described above, or it may consist of a plurality of such tubular structures arranged serially, to form a segmented tubular structure.
  • the individual segments of the tubular membrane may be adapted to permit a plurality of different droplet sizes or size distributions of the same oil phase, or to provide a plurality of different oil phases, with droplet sizes or size distributions which may be the same or different.
  • the surface chemistry and geometry of the membrane itself, and the pressure under which the oil phase is forced through the membrane can be varied as desired for each of the individual segments.
  • temperatures of the different oil phases may be individually adjusted to optimise the operation of the invention.
  • a method of preparing a mixture of the emulsion type wherein the discontinuous phase consists of an encapsulated substance which comprises the use of a segmented membrane of the type described above wherein a first segment distributes a discontinuous phase into a continuous phase, and a further segment distributes a further discontinuous phase which coats the first discontinuous phase.
  • the initial emulsion is prepared as generally described above.
  • the encapsulation process may then be carried out, for example, by passing the initial emulsion through a conical tube into a narrower-bore membrane tube incorporating a flov-splitter along its axis to reduce the effective flow area between the splitter and the membrane surface.
  • the further oil phase introduced into the narrower-bore membrane tube by means generally desribed above, then forms a coating on the droplets of the initial oil phase. It must be understood that the surface properties of the further membrane are important in controlling the oleophilicity of the further oil phase and thus improving the coating of the initial oil phase.
  • a method of controlling the start-up of an emulsification process as described above which comprises the use of on-line measurements of the size and size-distribution of the initially-formed discontinuous phase droplets as a feed-back signal to control the cross-flow velocity of the continuous phase and thereby ensure that the desired size and size-distribution of the final discontinuous phase droplets are obtained.
  • the on-line measurements may be obtained by the use of laser scanning microscopy, conductivity measurements and/or other suitable measurement methods. These measurements may separately be used to provide quality assurance of the desired product.
  • Figure 1 shows a schematic diagram of a single module cross-flow membrane unit which comprises:-
  • vessels (2) and (11) are provided with heating means (1) and (12) respectively and vessel (18) is provided with cooling means (19).
  • Vessel (11) is further provided with filling means (8) and a source of pressure (9). The various pumps, guages and valves which interconnect the vessels will hereinafter be described under the description of the procedure for operation.
  • the membrane unit (10) is shown in more detail in Figure 1(a).
  • the cylindrical membrane itself (25) is supported by a (usually stainless steel) body (22) and a further (usually stainless steel) concentric body (26), separated from (22) by seals (23) and adjustable by clamp means (29), provides a chamber (24) for the oil phase. Entry means are also provided for a gaseous purge (21), for the oil phase (27) and for the aqueous phase (28).
  • vessel (2) is filled to the appropriate level with the aqueous phase through valve (4), valve (17) and sampling valve (15) being closed.
  • Vessel (11) is filled to the appropriate level with the oil phase, suitably emulsified, through funnel and valve (8), purging and pressure valve (9) being open and valve (13) closed.
  • the contents of both vessels are heated to the appropriate temperature by means of the heating tapes (1) and (12).
  • the aqueous phase is then caused to flow through the apparatus by operation of pump (16) and regulation by valve (4) as shown by flowmeter (3) and pressure guages (5) and (14).
  • the oil phase in vessel (11) is brought to the appropriate pressure by means of pressure valve (9), initially air being purged from the chamber (24) by having valves (6) and (13) open, valve (8) closed and relief valve (7) set to safety level.
  • valves (6) and (13) are closed and the oil pressure is brought to and maintained at the appropriate level by means of valve (9).
  • the emulsification process is begun by opening valve (13), the oil phase being forced under pressure through entry (27) and through the membrane (25) into the aqueous phase running through the membrane unit (10).
  • the process is continued until the volume of oil in the emulsion reaches the desired level. This can be determined by noting the volume of oil phase remaining in vessel (11) and by samples of the emulsion removed through sampling valve (15). Small variation in the rate of flow of the aqueous phase can be controlled by valve (4).
  • the process is terminated by closing valve (13) and switching off pressure valve (9).
  • the finished product is transferred to vessel (18) by closing valve (4) and opening valve (17), and may then be cooled to the appropriate temperature by use of jacket (19) and removed from the system through valve (20).
  • Figure 2 shows a sequence of photographs, taken with a high-speed video-camera, of the detachment of an oil droplet from a pore of a membrane.
  • the data shown are for a coarse pore of 98 um diameter and a pressure drop of 2 psi.
  • the double-hatched picture represents the final detchment of the droplet from the pore; it can be seen that increasing the cross-flow velocity of the aqueous phase from 0.19 m/s to 0.40 m/s decreases the droplet formation time from 2380 milliseconds to 420 milliseconds.
  • Figure 3 shows an electron-micrograph of a ceramic membrane surface with a wide range of pore sizes.
  • Figure 4 shows in graphical form the relationship between pore size distribution, cross-flow velocity of the aqueous phase and predicted oil droplet size distribution.
  • the droplet size distribution can be controlled by varying the pore size distribution as well as by varying the cross-flow velocity.
  • Figure 5 shows in graphical form the effect of increasing the cross-flow velocity of the aqueous phase on:-
  • Figure 7 shows in graphical form an example of the evolution of droplets per area ( ⁇ r) of membrane. This example is from a batch production process using a coarse membrane with narrow pore size distribution.
  • Figure 8 shows a schematic diagram of a segmented membrane tube (corresponding to item 10 in Figure 1) which allows for either two sizes of droplets of the same oil phase (in which case the same type of oil phase will be contained in chambers 1 and 2 and the membranes 3 and 4 will differ from each other) or for two different oil phases (in which case two different oil phases will be contained in chambers 1 and 2 and the membranes 3 and 4 may be the same or different).
  • This system may be extended by the use of additional membrane segments to cater for more than two different oil phases and/or oil droplet sizes.
  • Figure 11 shows a schematic diagram of a single module cross-flow membrane unit, similar to that shown in Figure 1, which is adapted to provide continuous emulsion production at room temperature. It comprises a continuous (aqueous) phase tank equipped with a stirrer, a discontinuous (oil) phase tank, a washing tank, a continuous phase circulation pump, a pressure guage and a membrane module, all labelled, and va ves numbered 1 to 6 the functions of which are described below.
  • a continuous (aqueous) phase tank equipped with a stirrer, a discontinuous (oil) phase tank, a washing tank, a continuous phase circulation pump, a pressure guage and a membrane module, all labelled, and va ves numbered 1 to 6 the functions of which are described below.
  • FIG 11(a) shows the membrane module in diagra atic form; it is similar to that described in Figure 1(a) and is appropriately labelled.
  • the ceramic element is 600 mm. in length and has a 5 mm. internal diameter.
  • the inner surface may be coated so as to produce a mean pore size in the range of 0.1 upwards, and typically 0.2um.
  • the two phase tanks are filled with appropriate fluids, the membrane is saturated with aqueous phase and vith all valves closed the pump and stirrer (the latter slowly enough to prevent vortex motion) are switched on.
  • the pump and stirrer the latter slowly enough to prevent vortex motion
  • Valves 3 and 6 are then opened and air allowed into the system to produce the desired pressure of the oil phase.
  • the emulsification process is then started by opening valve 2.
  • the droplet-size distribution in the aqueous phase tank was monitored until the desired emulsion had been formed, at which time the process was stopped by closing all valves, releasing the air pressure and stopping the pump and stirrer. The finished product was released from the aqueous phase tank and the system washed out before the next operation.
  • Figure 21 shows a schematic diagram of a single module cross-flow membrane unit which comprises:-
  • vessels (2) and (43) are provided with heating means (4) and (32) respectively and vessel (31) is provided with cooling means (25).
  • Vessel (43) has a removable lid and is further provided with a source of pressure (39). The various pumps, guages and valves which interconnect the vessels will hereinafter be described under the description of the procedure for operation.
  • the membrane unit (14) is shown in more detail in Figure 21(a).
  • the cylindrical membrane itself (46) is supported by a (usually stainless steel) body (52) and a further (usually stainless steel) concentric body (45), separated from (52) by seals (49) and adjustable by clamps (44,48), provides a chamber (50) for the oil phase. Entry means are also provided for a gaseous purge (51), for the oil phase (47) and for the aqueous phase (53).
  • vessel (2) is filled to the appropriate level with the aqueous phase through valve (20).
  • Vessel (43) is filled to the appropriate level with the oil phase, suitably emulsified, through a removable lid.
  • the contents of both vessels are heated to the appropriate temperature by means of the heating tapes (4) and (32).
  • the aqueous phase is then caused to flow through the apparatus by operation of pump (19) and regulation by valve (7), as shown by flowmeter (3) and pressure guages (12) and (17).
  • the oil phase in vessel (43) is brought to the appropriate pressure by means of pressure valve (39) and air regulator (38), initially air being purged from the chamber (50) by having valves (47) and (51) open and relief valve (35) set to safety level.
  • valves (47) and (51) are closed and the oil pressure is brought to and maintained at the appropriate level by means of valve (39) and regulator (38).
  • the emulsification process is begun by opening valves (40, 41), the oil phase being forced under pressure through entry (47) and through the membrane (46) into the aqueous phase running through the membrane unit (14).
  • the process is continued until the volume of oil in the emulsion reaches the desired level. This can be determined by noting the volume of oil phase remaining in vessel (43) and by samples of the emulsion removed through sampling valve (13). Small variation in the rate of flow of the aqueous phase can be controlled by valve (7) or lobe pump (19).
  • the process is terminated by closing valves (40,41) and switching off pressure valve (39), thus releasing the pressure drop.
  • the finished product is transferred to vessel (31) by switching valve (22), and may be cooled to the appropriate temperature by use of jacket (25) and removed from the system through valve (30).
  • Figure 22 shows an accurate representation of the droplets growing at a pore, derived from observations made with a high-speed camera, at given times. The results shown are for a single coarse pore of 98 microns diameter and a pressure drop of 2 psi. It can be seen that increasing the cross-flow velocity of the aqueous phase from 0.19 m/s to 0.40 m/s decreases the droplet formation time from 2380 milliseconds to 420 milliseconds.
  • Figure 23 shows:-
  • Figure 24 shows in graphical form the effect of increasing the cross-flow velocity of the aqueous phase on:-
  • Figure 6 shows in isometric diagrammatical form the relationship between oil droplet size, cross-flow velocity of the aqueous phase and pressure drop across the membrane.
  • Figure 26 shows a schematic diagram of a segmented membrane tube (corresponding to item 14 in Figure 1) which allows for either two sizes of droplets of the same oil phase (in which case the same type of oil phase will be contained in chambers 1 and 2 and the membranes 3 and 4 will differ from each other) or for two different oil phases (in which case two different oil phases will be contained in chambers 1 and 2 and the membranes 3 and 4 may be the same or different).
  • This system may be extended by the use of additional membrane segments to cater for more than two different oil phases and/or oil droplet sizes.
  • Figure 27 shows the droplet size distribution manufactured using a dual membrane assembly (as described in Figure 26) having mean pore diameters of 0.5 microns and 4.0 microns, and operated at 40 psi and 10 psi repectively.
  • An aqueous phase was prepared by adding sorbitol ono-oleate ("Span” 80) (2.5%) to a stirred solution of polyoxyethylenesorbitan mono-oleate (“Tween” 20) (2.5%) and (sodium "Nipastat”) (0.3%) in water (64.7%) and the mixture was loaded into the aqueous phase tank of an apparatus as described in Figure 11.
  • Mineral oil (30.0%) was loaded into the oil phase tank and the emulsification process was carried out for 4.5 hours with an initial crossflow velocity of 5.09 m/sec, to produce a 30% oil-in-water emulsion.
  • the pore size distribution and droplet size distribution are shown in Figure 12; the mean droplet size was 2.03 ⁇ m.
  • the droplet size distribution may be described in terms of a distribution coefficient ⁇ which is defined by the equation:- wherein D* , D ⁇ and ° are the particle sizes obtained when the cumulative frequencies of the emulsion product when measured on a Malvern Instruments Mastersizer are 90%, 50% and 10% respectively. For a perfect monodisperse system ⁇ is zero. In the present Example the emulsions produced give an ⁇ value of not more than 0.6, and at best not more than 0.3. The distribution of pore sizes in the membrane can be defined by the same ⁇ being not more than 0.6 and that no single pore has a size greater the 150% of the mean pore size. The droplet size and size distribution remained unchanged for several weeks, although there was some early phase separation.
  • Figure 12(a) shows a photomicrograph of the product (magnification x 400); the striations in the image are caused by marks on the camera lens.
  • the crossflow velocities are given as a range, because as the concentration of oil in the emulsion increases, it becomes more viscous (as indicated by the reduction in Reynolds number, which is a function of velocity times density divided by viscosity). In practice, the velocity falls by about 10% by the end of the process.
  • the blip on the graph of droplet size distribution at the highest crossflow velocity arises from the inability of the measuring equipment to deal with very small droplet sizes.
  • Figure 14 shows the relationship between initial crossflow velocity and mean droplet size. There is an almost linear decrease of mean droplet size with increasing velocity.
  • Figure 15 shows the relationships between the time progression of the process and:-
  • Figure 16 shows a photomicrograph of the product of Example 2 when the highest exemplified crossflow velocity (5.09 m/sec) is used; the droplets are smaller than those obtained from Example 1 as shown in Figure 12(a).
  • Example 3
  • This example describes by way of illustration the manufacture of a cosmetic-type emulsion at room temperature, and the effect of the cross-flow velocity on the droplets so produced.
  • Curves (2), (3), (4) and (5) show the droplet size distributions of the product, measured by means of a Malvern Mastersizer, for each of the cross-flow velocities 1,12, 2.49, 4.34 and 5.09 m/s respectively.
  • Figure 29 shows a typical photomicrograph of a product manufactured by this process.
  • This example demonstrates how control of droplet size can be achieved by choice of membrane properties, in particular by choice of pore size.
  • Example 4 The process described in Example 4 was repeated (using a ceramic membrane tube of nominal pore size 0.5 micron) except that when the desired oil concentration was reached (after 100 minutes) more aqueous phase was continuously added, and emulsion product was continuously removed, the flow rates being matched to the oil flux rate so that the emulsion concentration in the aqueous phase tank was maintained at that of the final product.
  • Measurements of emulsion concentration, production rate and particle size as a function of time were made using a scanning laser microscope (Type FRBM, Lasentec Corp.). The results are shown in Figure 31; emulsion concentration in Figure 31(a), oil flux rate in Figure 31(b), droplet size number count in Figure 31(c) and droplet size in Figure 31(d).
  • Figure 32 shows the pore size distribution of the membrane (curve 1) and the droplet size distribution (curve 2). It is clear from these results that the use of on-line instrumentation with associated computer control enables continuous production of an emulsion to be achieved.
  • This example demonstrates the production of a cosmetic emulsion at high temperature and low shear.
  • An aqueous phase was prepared by slowly adding 'Carbomer' 934 (0.1%) to well stirred water (88.25%) maintained at 80°C. and then slowly adding triethanolamine (1.0%). The solution was loaded into the aqueous phase tank and maintained at 80°C. by use of the heating tape ( Figure 21, item 4).
  • An oil phase was prepared by heating a mixture of petroleum jelly (6.5%), mineral oil (2.0%), stearic acid (1.5%), glyceryl monostearate (0.4%) and isopropyl isostearate (0.25%) to 80°C. and was loaded into the oil phase tank and maintained at 80°C. by use of the heating tape ( Figure 21, item 32).
  • FIG. 33(a) shows a cryogenic micrograph of the product obtained by the above process
  • Figure 33(b) shows a similar micrograph of an emulsion prepared by a conventional high shear process. It can be seen that the lamallae stearate phase appears to beruptured in the conventional high shear process but is largely intact in the present example, the dispersed oil droplets being otherwise identical.
  • the product of the present process has distinctive application properties from the perspective of the user.
  • aqueous phase in the form of a gel was prepared by adding sodium chloride (2.0%) to a solution of sodium lauryl ether sulphate (40%), cocoamidopropyl betaine (10%), cocadiethanola ide (2.0%) and preservative (0.2%) in water (35.8%) and was loaded into the aqueous phase tank.
  • Silicone oil was loaded into the oil phase tank and the emulsification process was carried out using a stainless steel membrane (Figure 21, item 46; mean pore size 40 microns) until the concentration of silicone oil in the product was 10%.
  • the droplet size distribution of the product which may be used as a shower gel, is shown in Figure 34. It can be seen that the droplet size is comparable with the size of the membrane pore.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Colloid Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Procédé pour préparer un mélange de type émulsion dans lequel une phase discontinue est introduite dans une phase continue circulante par passage à travers une membrane, cette dernière étant de préférence constituée d'un matériau de type céramique ou métal fritté.
PCT/GB1997/000910 1996-03-29 1997-04-01 Dispersion de phases immiscibles WO1997036674A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9708583-9A BR9708583A (pt) 1996-03-29 1997-04-01 Processo para preparar uma mistura do tipo de emulsão, aparelho projetado de forma a permitir a realização do processo, e, método para controlar o inìcio de um processo de emulsificação.
JP9535048A JP2000507497A (ja) 1996-03-29 1997-04-01 非混和相の分散液
EP97915560A EP0889749A1 (fr) 1996-03-29 1997-04-01 Dispersion de phases immiscibles
AU22995/97A AU2299597A (en) 1996-03-29 1997-04-01 Dispersion of immiscible phases

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9606738.4A GB9606738D0 (en) 1996-03-29 1996-03-29 Dispersion of immiscible phases
GB9606738.4 1996-03-29

Publications (1)

Publication Number Publication Date
WO1997036674A1 true WO1997036674A1 (fr) 1997-10-09

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PCT/GB1997/000910 WO1997036674A1 (fr) 1996-03-29 1997-04-01 Dispersion de phases immiscibles

Country Status (8)

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EP (1) EP0889749A1 (fr)
JP (1) JP2000507497A (fr)
CN (1) CN1219889A (fr)
AU (1) AU2299597A (fr)
BR (1) BR9708583A (fr)
CA (1) CA2250366A1 (fr)
GB (1) GB9606738D0 (fr)
WO (1) WO1997036674A1 (fr)

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US6200937B1 (en) 1998-06-09 2001-03-13 Neutrogena Corporation Anti-residue shampoo and liquid toiletry production method
WO2003014196A1 (fr) * 2001-08-03 2003-02-20 Akzo Nobel N.V. Procede de preparation de dispersions
WO2005056169A1 (fr) * 2003-12-10 2005-06-23 Rwth Aachen Procede et dispositif de production d'emulsions monodispersees
US8133441B2 (en) * 2006-07-19 2012-03-13 Beijing University Of Technology Apparatus and process for metal oxides and metal nanoparticles synthesis
WO2019092461A1 (fr) * 2017-11-13 2019-05-16 Micropore Technologies Ltd Ensemble à écoulement transversal pour production de gouttelettes commandée par émulsification par membrane
US10835877B2 (en) * 2016-03-15 2020-11-17 Arcolor Ag Method for producing dispersions of a defined particle size
EP4112158A4 (fr) * 2020-02-27 2024-04-10 Nitto Denko Corporation Procédé et appareil de production d'émulsion

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KR100932418B1 (ko) * 2003-06-11 2009-12-17 아사히 가라스 가부시키가이샤 무기질 구상체의 제조 방법 및 제조 장치
JP5037781B2 (ja) * 2003-06-11 2012-10-03 旭硝子株式会社 無機質球状体の製造方法及び製造装置
JP4767504B2 (ja) * 2003-06-18 2011-09-07 旭硝子株式会社 無機質球状体の製造方法及び製造装置
US8221882B2 (en) 2003-06-18 2012-07-17 Asahi Glass Company, Limited Process and apparatus for producing inorganic spheres
JPWO2012133736A1 (ja) * 2011-03-31 2014-07-28 国立大学法人九州大学 連続相中に分散相が微分散した組成物の製造方法およびその装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3748277A (en) * 1965-10-14 1973-07-24 Ncr Co Process of forming minute capsules
US4147551A (en) * 1972-08-14 1979-04-03 E. I. Du Pont De Nemours And Company Process for photographic emulsion precipitation in a recycle stream
EP0452140A1 (fr) * 1990-04-11 1991-10-16 Morinaga Milk Industry Co., Ltd. Procédé pour la préparation des émulsions, de produit à tartiner à basse teneur en graisse et de produit à tartiner de type huile/eau/huile
EP0481892A1 (fr) * 1990-10-16 1992-04-22 Sugiura, Satoshi Procédé de production des particules inorganiques comprenants des spheres fines de dimension uniforme
EP0546174A1 (fr) * 1991-06-29 1993-06-16 Miyazaki-Ken Emulsions monodispersees simples et doubles et procede de production
EP0564738A1 (fr) * 1992-04-06 1993-10-13 Morinaga Milk Industry Co., Ltd. Produit à tartiner et procédé pour sa fabrication

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3748277A (en) * 1965-10-14 1973-07-24 Ncr Co Process of forming minute capsules
US4147551A (en) * 1972-08-14 1979-04-03 E. I. Du Pont De Nemours And Company Process for photographic emulsion precipitation in a recycle stream
EP0452140A1 (fr) * 1990-04-11 1991-10-16 Morinaga Milk Industry Co., Ltd. Procédé pour la préparation des émulsions, de produit à tartiner à basse teneur en graisse et de produit à tartiner de type huile/eau/huile
EP0481892A1 (fr) * 1990-10-16 1992-04-22 Sugiura, Satoshi Procédé de production des particules inorganiques comprenants des spheres fines de dimension uniforme
EP0546174A1 (fr) * 1991-06-29 1993-06-16 Miyazaki-Ken Emulsions monodispersees simples et doubles et procede de production
EP0564738A1 (fr) * 1992-04-06 1993-10-13 Morinaga Milk Industry Co., Ltd. Produit à tartiner et procédé pour sa fabrication

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6200937B1 (en) 1998-06-09 2001-03-13 Neutrogena Corporation Anti-residue shampoo and liquid toiletry production method
WO2003014196A1 (fr) * 2001-08-03 2003-02-20 Akzo Nobel N.V. Procede de preparation de dispersions
WO2005056169A1 (fr) * 2003-12-10 2005-06-23 Rwth Aachen Procede et dispositif de production d'emulsions monodispersees
US8133441B2 (en) * 2006-07-19 2012-03-13 Beijing University Of Technology Apparatus and process for metal oxides and metal nanoparticles synthesis
US10835877B2 (en) * 2016-03-15 2020-11-17 Arcolor Ag Method for producing dispersions of a defined particle size
WO2019092461A1 (fr) * 2017-11-13 2019-05-16 Micropore Technologies Ltd Ensemble à écoulement transversal pour production de gouttelettes commandée par émulsification par membrane
JP2021502249A (ja) * 2017-11-13 2021-01-28 マイクロポア テクノロジーズ リミテッド 制御された膜乳化液滴生成のためのクロスフロー組立体
US12011695B2 (en) 2017-11-13 2024-06-18 Micropore Technologies Limited Cross-flow assembly and method for membrane emulsification controlled droplet production
EP4112158A4 (fr) * 2020-02-27 2024-04-10 Nitto Denko Corporation Procédé et appareil de production d'émulsion

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JP2000507497A (ja) 2000-06-20
EP0889749A1 (fr) 1999-01-13
AU2299597A (en) 1997-10-22
GB9606738D0 (en) 1996-06-05
CN1219889A (zh) 1999-06-16
CA2250366A1 (fr) 1997-10-09
BR9708583A (pt) 2000-01-04

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