EP3370856A1 - Dispositif de mélange de poudres par fluide cryogénique et génération de vibrations - Google Patents
Dispositif de mélange de poudres par fluide cryogénique et génération de vibrationsInfo
- Publication number
- EP3370856A1 EP3370856A1 EP16791566.9A EP16791566A EP3370856A1 EP 3370856 A1 EP3370856 A1 EP 3370856A1 EP 16791566 A EP16791566 A EP 16791566A EP 3370856 A1 EP3370856 A1 EP 3370856A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powders
- cryogenic fluid
- mixing
- mixing chamber
- fluidized bed
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 155
- 238000002156 mixing Methods 0.000 title claims abstract description 90
- 239000012530 fluid Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 19
- 229910052768 actinide Inorganic materials 0.000 claims description 16
- 150000001255 actinides Chemical class 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005243 fluidization Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000010363 phase shift Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000005325 percolation Methods 0.000 claims description 2
- 239000002609 medium Substances 0.000 description 13
- 239000003758 nuclear fuel Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000265 homogenisation Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000014366 other mixer Nutrition 0.000 description 2
- 238000003608 radiolysis reaction Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
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
- B01F23/60—Mixing solids with solids
-
- 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
- B01F23/60—Mixing solids with solids
- B01F23/66—Mixing solids with solids by evaporating or liquefying at least one of the components; using a fluid which is evaporated after mixing
-
- 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
- B01F23/60—Mixing solids with solids
- B01F23/69—Mixing systems, i.e. flow charts or diagrams; Arrangements, e.g. comprising controlling means
-
- 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
- B01F23/80—After-treatment of the mixture
-
- 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
- B01F23/80—After-treatment of the mixture
- B01F23/806—Evaporating a carrier, e.g. liquid carbon dioxide used to dissolve, disperse, emulsify or other components that are difficult to be mixed; Evaporating liquid components
-
- 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
-
- 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
- B01F31/85—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations with a vibrating element inside the receptacle
-
- 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
- B01F33/40—Mixers using gas or liquid agitation, e.g. with air supply tubes
-
- 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
- B01F33/40—Mixers using gas or liquid agitation, e.g. with air supply tubes
- B01F33/406—Mixers using gas or liquid agitation, e.g. with air supply tubes in receptacles with gas supply only at the bottom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/21—Measuring
- B01F35/2132—Concentration, pH, pOH, p(ION) or oxygen-demand
Definitions
- the present invention relates to the field of the preparation of granular media, and more specifically to the mixture of powders, in particular actinide powders, and to their deagglomeration / reagglomeration to obtain a mixture of high homogeneity by means of a cryogenic fluid , also called median cryogenic.
- a cryogenic fluid also called median cryogenic.
- the invention thus preferably has its application for the mixture of actinide powders for the formation of nuclear fuel, in particular nuclear fuel pellets.
- the invention thus proposes a device for mixing powders by cryogenic fluid, as well as a method for mixing powders associated therewith.
- the implementation of the various stages of preparation of a granular medium, in particular from actinide powders, to form nuclear fuel pellets after forming by pressing, is essential because it mainly determines the control of the microstructure of the substrate. final product but also the presence or absence of defects of macroscopic aspects within a fuel pellet.
- the mixture of actinide powders to allow the production of nuclear fuel is a key step in controlling the quality of the fuel pellet obtained, which is most often subject to compliance with stringent requirements in terms of microstructure and impurities.
- the mixer in dry phase without internal media. It may in particular be a Turbula ® type mixer from the company WAB which by more or less complex movements of the tank containing the powders to be mixed, allows more or less uniform homogenization of the granular medium.
- WAB Turbula ® type mixer
- the efficiency of this type of mixer is limited. Indeed, depending on the type of powders to be mixed, there may remain heterogeneous areas, for which mixing does not occur or at least in an incorrect manner and not admissible.
- the kinematics of this type of mixer is generally not complex enough to induce a thorough mixture, that is to say a mixture that is satisfactory in terms of homogeneity, without focusing itself, or a penalizing mixing time. at the industrial level.
- the energy transmitted to the granular medium in this type of mixer does not allow deagglomeration to be sufficient to reach sufficient degrees of homogeneity in the case where the size of these agglomerates is too large (in particular to be compensated during the sintering step).
- the principle of the media mixer is also known. According to this principle and to promote the mixing operation, one or more mobile can be used within the tank containing the powder to be mixed. These mobiles can be blades, turbines, shares, ribbons, worms, among others. To improve the mixing, the tank can itself be mobile. This type of mixer may be more efficient than the previous category but is still insufficient and suffers limitations. In fact, the stirring induces a modification of the granular medium by agglomeration or disagglomeration difficult to control, which induces a proliferation of powders and / or degradation of the flowability of the granular medium.
- the use of mobile (media) for mixing causes pollution (contaminations) when it comes to mixing abrasive powders such as those to be implemented for the realization of nuclear fuel.
- the mobiles implemented induce retentions that generate very high dose rates in the case of the development of nuclear fuel.
- the aforementioned mixers are not fully satisfactory for mixing certain powders, such as actinide powders, and it is necessary to carry out a granulation step in order to obtain a flowable granular medium.
- mixers are also known, implementing a multiphasic medium, namely fluid-solid phases. These mixers can be classified in two main categories described below.
- the mixture is most often not effective or requires significant stirring speeds. Indeed, the take-off speed of a particle from the bottom of the agitator is directly related to the density difference between the particles constituting the powders and that of the liquid for suspending.
- the so-called non-dimensional number of Archimedes must be greater than 10 (ie the viscosity forces are lower than the forces of gravity and inertia). Knowing that the constituent particles of the powders to be mixed have relatively small diameters, typically less than 10 ⁇ , it is not conceivable to make homogeneous and complete suspensions with this type of device without using complementary mixing means. In this sense, technologies, such as that described in patent application CA 2 882 302 A1, have been proposed but remain nonetheless ineffective for a mixture of actinide powders, the vibration means used not allowing sufficient homogenization in view of the homogenization objectives to be achieved and the peculiarities of the actinide powders.
- the volume of the mixer must be limited, to prevent any risk of double loading that could lead to exceeding the critical mass allowable.
- the particle density per volume of The tank can not be large unless it exceeds a stirring power that is too high, or undergoes slow mixing kinetics.
- liquid phase powder mixers in particular of the type described in patent applications CA 2,882,302 A1, WO 2006/0111266 A1 and WO 1999/010092 A1, are not suitable for the problematics of a mixture of powders of actinide powders type, since they would require stirring speeds too high to hope to take off the powders from the bottom of the stirring tank and achieve homogeneity levels consistent with those sought in the industry nuclear.
- the object of the invention is to at least partially remedy the needs mentioned above and the drawbacks relating to the embodiments of the prior art.
- the subject of the invention is a device for mixing powders, in particular actinide powders, by cryogenic fluid, characterized in that it comprises:
- a powder mixing chamber comprising a cryogenic fluid, provided with means for forming a bed of fluidized powders;
- a powder supply chamber to allow the introduction of powders into the mixing chamber, a chamber for supplying cryogenic fluid to allow the introduction of the cryogenic fluid into the mixing chamber;
- the powders are subjected to fluidization through the cryogenic fluid to obtain the fluidized bed of powders.
- this bed of fluidized powders is subjected to the vibrations of the vibration generating system to preferentially obtain a major disorder in the suspension of powders and cryogenic fluid, these vibrations being controlled by means of the control system to optimize the mixed.
- a cryogenic fluid here designates a liquefied gas kept in the liquid state at low temperature.
- This liquefied gas is chemically inert under the conditions of implementation of the invention for the powders to be mixed and deagglomerated.
- the powder mixing device according to the invention may further comprise one or more of the following characteristics taken separately or in any possible technical combinations.
- the cryogenic fluid may comprise a weakly hydrogenated liquid, ie a liquid comprising at most one hydrogen atom per molecule of liquid, having a boiling point lower than that of water.
- the device may further comprise an analysis system, in particular a system for measuring the solid concentration (ie powders) of the suspension of powders and of cryogenic fluid in the mixing chamber, the operation of which is in particular controlled by the system. piloting.
- an analysis system in particular a system for measuring the solid concentration (ie powders) of the suspension of powders and of cryogenic fluid in the mixing chamber, the operation of which is in particular controlled by the system. piloting.
- the mixing chamber may be configured in such a way that the introduction of cryogenic fluid into it allows fluidization of the powders to be mixed by percolating the cryogenic fluid through the thus fluidized bed of powders.
- the mixing chamber may comprise a distribution system, in particular a sintered grid or part, cryogenic fluid through the fluidized bed of powders to allow a homogeneous distribution of the cryogenic fluid in the fluidized bed.
- the vibration generating system may be at least partially located in the fluidized bed of powders.
- the vibration generating system may comprise sonotrodes introduced into the fluidized bed of powders.
- the sonotrodes can be controlled independently by the control system to induce a periodic phase shift of the phases between the sonotrodes to introduce unsteady interference improving mixing within the fluidized bed of powders.
- the sonotrodes can still be configured to generate pseudo-chaotic oscillations, potentially for example by means of a Van der Pol type oscillation generator.
- the mixing device may further comprise stirring means in the mixing chamber to promote the mixing of the powders placed in suspension in the cryogenic fluid, including in particular grinding means, for example of the balls, pebbles, among others .
- the mixing device may also include a system for electrostatically charging the powders intended to be introduced into the mixing chamber.
- Part of the powders may in particular be brought into contact with one part of the electrostatic charge system to be electrostatically charged in a positive manner and the other part of the powders may be brought into contact with the other part of the electrostatic charge system to be charged. Electrostatically negative, to allow differentiated local agglomeration. When mixing more than two types of powders, some powders may be either positively charged, or negatively charged, or without charge.
- the cryogenic fluid may also be of any type, in particular being liquefied nitrogen or argon. It should be noted that the use of nitrogen is relevant because of its low price, but also because the glove boxes and processes used for the development of plutonium-based nuclear fuel are inerted with nitrogen and liquid nitrogen is itself fuel operations (BET measurement, ). The use of this type of cryogenic fluid does not therefore induce any additional particular risk in the production process.
- another aspect of the invention relates to a process for mixing powders, in particular actinide powders, by cryogenic fluid, characterized in that it is implemented by means of a device as defined above, and in that it comprises the following steps:
- the powders can advantageously be electrostatically charged in a different manner, in particular in an opposite manner in the presence of at least two types of powders, to promote differentiated local agglomeration.
- the method may also include the step of controlling the vibration generating system through the control system, in particular according to the particle concentration of the suspension.
- the device and method for mixing powders according to the invention may comprise any of the features set forth in the description, taken alone or in any technically possible combination with other characteristics.
- FIG. 1 represents a diagram illustrating the general principle of a device for mixing powders by cryogenic fluid according to the invention
- FIG. 2 partially represents an example of a device according to the invention
- FIG. 3 illustrates a representation of interference lines induced by two vibratory sources having the same pulse frequency
- FIGS. 4A and 4B illustrate the generation of stable oscillations induced by a Van der Pol type oscillator after convergence
- FIGS. 5A and 5B illustrate the generation of quasi-chaotic oscillations of a Van der Pol type oscillator when its driving parameters are adapted
- FIGS. 6, 7 and 8 respectively represent photographs of a first type of powders before mixing, of a second type of powders before mixing, and of the mixture obtained of the first and second types of powders after mixing by means of a device and a method according to the invention.
- the P powders considered are actinide powders for the manufacture of nuclear fuel pellets.
- the cryogenic fluid considered here is liquefied nitrogen.
- the invention is not limited to these choices. Referring to Figure 1, there is shown a diagram illustrating the general principle of a device 1 for mixing powders P by cryogenic fluid according to the invention.
- the device 1 comprises a mixing chamber E1, preferably heat-insulated, powders P provided with means for forming a bed of fluidized powders Lf, visible in Figure 2 described below.
- the device 1 comprises a feed enclosure A1 in powders P to allow the introduction of powders P into the mixing chamber E1, and a feed chamber B1 in cryogenic fluid FC to allow the introduction of the fluid In this way, it is possible to obtain a suspension of powders P and cryogenic fluid FC in the mixing chamber E 1 forming a fluidized bed Lf.
- the feed chamber B 1 in cryogenic fluid FC may correspond to a distribution chamber or an enclosure for recirculating cryogenic fluid FC.
- This supply chamber B1 can allow the distribution and / or recycling of cryogenic fluid FC. It can in particular partly rely on a pressurization of a liquefied gas supply tank.
- the device 1 also comprises a vibration generation system Vb in the fluidized bed of powders Lf, a control system Sp of this vibration generation system Vb, and a concentration analysis system Ac of the suspension of powders P and cryogenic fluid FC in the mixing chamber E1, the operation of which is controlled by the control system Sp.
- the control system Sp can in particular make it possible to control the operation of the device 1 and the data processing, in particular in terms of powder supply conditions P, FC cryogenic fluid and / or in terms of amplitude of the vibrations.
- the mixing chamber E1 is configured such that the introduction of cryogenic fluid FC into the latter makes it possible to fluidize the powders P with mixing by percolation of the cryogenic fluid FC through the bed of powders and fluidized Lf.
- FIG. 2 precisely, there is shown partially and schematically an example of mixing device 1 according to the invention.
- This mixing device 1 comprises a mixing chamber E1 forming a vertical main axis reservoir advantageously having a symmetry of revolution, in particular in the form of a cylinder, and being advantageously insulated to minimize thermal losses as its purpose is to receive a phase of circulating liquefied gas.
- cryogenic fluid FC (liquefied gas) is introduced into the lower part of the mixing chamber E1, at the inlet of the fluidized bed Lf of powders P, by means of a distribution system Sd, in particular in the form of gate or sintered part, for distributing the cryogenic fluid FC homogeneously on the passage section of the fluidized bed Lf.
- the mixing chamber E1 can be equipped with a diverging zone so as to disengage the smaller powder particles P and allow them to remain in the zone of the fluidized bed Lf.
- a system for analyzing the concentration Ac of the suspension of powders P and cryogenic fluid FC in the mixing chamber E1 comprising in particular an optical sensor Co making it possible to observe the fluidized bed Lf powder P through a viewing port H.
- the Ac system is thus interfaced through the fluidized bed Lf.
- the concentration analysis system Ac equipped with the optical sensor Co, can make it possible to analyze the concentration of the powders P, or even to analyze the granulometry of the granular medium formed in the mixing chamber E1.
- the concentration analysis system Ac may comprise an optical fiber of emitting type (light source illuminating the fluidized bed Lf) and receiver (sensor). It can still include a camera. It should be noted that the concentration of the particles is a function of the distance between the emitting fiber and the receiving fiber, the particle size distribution, the refractive index of the granular medium, and the wavelength of the incident beam in the dispersion medium.
- the device 1 comprises the vibration generation system Vb.
- This system advantageously comprises sonotrodes So.
- Vb is introduced to the right of the fluidized bed Lf closest to the introduction of cryogenic fluid FC.
- the sonotrodes So can dive within the fluidized bed Lf.
- FIG. 3 illustrates a representation of the interference lines induced by two vibratory sources S1 and S2 having the same pulse frequency.
- the interferences can move a distance equivalent to the order of magnitude of the wavelength of the vibrations injected into the fluidized bed Lf. This then allows an additional degree of mixing.
- the feed enclosure Al of the powders P can allow gravity feeding, or even a worm-type device, or even by way of a vibrating bed, for example.
- the powders P can be electrostatically charged with opposite charges to allow during the suspension to obtain a differentiated reagglomeration.
- Table 1 below also gives an example of sizing of a device 1 according to the invention.
- FIGS. 6, 7 and 8 respectively represent photographs of a first type of powders before mixing, of a second type of powders before mixing, and of the mixture obtained of the first and second types of powders after mixing through a device 1 and a method according to the invention.
- FIG. 6 represents aggregates of cerium dioxide powders C0 2
- FIG. 7 represents aggregates of alumina powders AI 2 O 3
- FIG. 8 represents the mixture of these powders obtained with a mixing time of about 30 seconds.
- the invention thus exploits various technical effects that make it possible in particular to reach the desired level of homogenization, such as those described below:
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1560571A FR3042986B1 (fr) | 2015-11-04 | 2015-11-04 | Dispositif de melange de poudres par fluide cryogenique et generation de vibrations |
PCT/EP2016/076508 WO2017076945A1 (fr) | 2015-11-04 | 2016-11-03 | Dispositif de mélange de poudres par fluide cryogénique et génération de vibrations |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3370856A1 true EP3370856A1 (fr) | 2018-09-12 |
EP3370856B1 EP3370856B1 (fr) | 2019-12-04 |
Family
ID=55806428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16791566.9A Active EP3370856B1 (fr) | 2015-11-04 | 2016-11-03 | Dispositif de mélange de poudres par fluide cryogénique et génération de vibrations et procédé |
Country Status (7)
Country | Link |
---|---|
US (1) | US10688459B2 (fr) |
EP (1) | EP3370856B1 (fr) |
JP (1) | JP6929280B2 (fr) |
CN (1) | CN108348873B (fr) |
FR (1) | FR3042986B1 (fr) |
RU (1) | RU2718717C2 (fr) |
WO (1) | WO2017076945A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3072378B1 (fr) * | 2017-10-12 | 2019-11-08 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Dispositif et procede de fabrication de pieces en ceramique par voie cryogenique |
EP4008452A1 (fr) * | 2020-12-02 | 2022-06-08 | Linde GmbH, Linde Engineering | Procédé de traitement de la poudre |
FR3121365A1 (fr) | 2021-04-02 | 2022-10-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé pour transporter des poudres |
FR3137590A1 (fr) | 2022-07-11 | 2024-01-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de dosage de poudres |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE758901A (fr) * | 1969-05-19 | 1971-04-16 | Anderson Robert Neil | Reacteur nucleaire a combustible comprenant une masse critique de nitrure d'actinide et procede de conduite de ce |
US4474905A (en) * | 1982-09-30 | 1984-10-02 | General Technology Applications, Inc. | Freeze blending of reactive liquids and solids |
US4571086A (en) * | 1984-09-26 | 1986-02-18 | Rockwell International Corporation | Mixing of ceramic powders |
SU1393464A1 (ru) * | 1986-09-18 | 1988-05-07 | Специальное Конструкторское Бюро По Подземному Самоходному Горному Оборудованию | Вибросмеситель |
US4917834A (en) * | 1988-11-16 | 1990-04-17 | General Technology Applications, Inc. | Method for forming homogeneous blends of particulate materials |
SU1713632A1 (ru) * | 1990-01-05 | 1992-02-23 | Ленинградский Технологический Институт Им.Ленсовета | Смеситель сыпучих материалов |
GB9313442D0 (en) * | 1993-06-30 | 1993-08-11 | Bp Chem Int Ltd | Method of mixing heterogegeous systems |
SE9400335D0 (sv) * | 1994-02-02 | 1994-02-02 | Astra Ab | Powder mixing |
FR2767720B1 (fr) | 1997-08-27 | 1999-11-19 | Denis | Melangeur liquide(s)/solide(s) rotatif, en continu, a oeil ouvert |
US6916389B2 (en) * | 2002-08-13 | 2005-07-12 | Nanotechnologies, Inc. | Process for mixing particulates |
US7090391B2 (en) * | 2002-09-25 | 2006-08-15 | Reika Kogyo Kabushiki Kaisha | Apparatus and method for mixing by agitation in a multichambered mixing apparatus including a pre-agitation mixing chamber |
FR2870841B1 (fr) * | 2004-05-28 | 2007-02-09 | Commissariat Energie Atomique | Procede de coprecipitation d'actinides a des etats d'oxydation distincts et procede de preparation de composes mixtes d'actinides |
US7473405B2 (en) * | 2004-10-13 | 2009-01-06 | Chevron U.S.A. Inc. | Fluid distribution apparatus for downflow multibed poly-phase catalytic reactor |
WO2006104227A1 (fr) * | 2005-03-29 | 2006-10-05 | Kajima Corporation | Procédé consistant à ajuster la teneur en eau d'une matière |
US20090061059A1 (en) | 2005-04-21 | 2009-03-05 | Daniel Anthony Jarvis | Method for moulding a food product |
US7703698B2 (en) * | 2006-09-08 | 2010-04-27 | Kimberly-Clark Worldwide, Inc. | Ultrasonic liquid treatment chamber and continuous flow mixing system |
CN101432063B (zh) * | 2006-05-02 | 2013-02-13 | 尼罗有限公司 | 凝聚装置及用于制造凝聚颗粒的方法 |
RU2353424C1 (ru) * | 2007-12-03 | 2009-04-27 | Государственное Учреждение Институт металлургии Уральского отделения Российской Академии Наук (ГУ ИМЕТ УрО РАН) | Способ смешивания сыпучих материалов |
FI122098B (fi) * | 2010-03-18 | 2011-08-31 | Outotec Oyj | Reaktori ja menetelmä prosessiliuoksen puhdistamiseksi |
WO2014031425A1 (fr) | 2012-08-20 | 2014-02-27 | Banus Christopher T | Appareil à vibrations pour le mélange de liquides non miscibles et pour le mélange de poudres avec des liquides ou d'autres poudres |
FR3029002B1 (fr) | 2014-11-25 | 2019-08-30 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Dispositif de transfert de poudre a ecoulement ameliore |
FR3030500B1 (fr) | 2014-12-18 | 2019-07-05 | Areva Nc | Procede de fabrication d'une pastille d'au moins un oxyde metallique, son utilisation comme combustible nucleaire |
-
2015
- 2015-11-04 FR FR1560571A patent/FR3042986B1/fr not_active Expired - Fee Related
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2016
- 2016-11-03 EP EP16791566.9A patent/EP3370856B1/fr active Active
- 2016-11-03 WO PCT/EP2016/076508 patent/WO2017076945A1/fr active Application Filing
- 2016-11-03 CN CN201680064415.2A patent/CN108348873B/zh active Active
- 2016-11-03 JP JP2018522552A patent/JP6929280B2/ja active Active
- 2016-11-03 US US15/772,327 patent/US10688459B2/en active Active
- 2016-11-03 RU RU2018120108A patent/RU2718717C2/ru active
Also Published As
Publication number | Publication date |
---|---|
US10688459B2 (en) | 2020-06-23 |
RU2018120108A3 (fr) | 2020-02-07 |
EP3370856B1 (fr) | 2019-12-04 |
RU2018120108A (ru) | 2019-12-04 |
CN108348873A (zh) | 2018-07-31 |
FR3042986A1 (fr) | 2017-05-05 |
CN108348873B (zh) | 2020-11-10 |
RU2718717C2 (ru) | 2020-04-14 |
FR3042986B1 (fr) | 2017-12-15 |
JP6929280B2 (ja) | 2021-09-01 |
US20180318779A1 (en) | 2018-11-08 |
WO2017076945A1 (fr) | 2017-05-11 |
JP2018533474A (ja) | 2018-11-15 |
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