EP4088818A1 - Désintégrateur à jet hélicoïdal et procédé de broyage des produits à broyer dans un désintégrateur à jet hélicoïdal - Google Patents
Désintégrateur à jet hélicoïdal et procédé de broyage des produits à broyer dans un désintégrateur à jet hélicoïdal Download PDFInfo
- Publication number
- EP4088818A1 EP4088818A1 EP21173898.4A EP21173898A EP4088818A1 EP 4088818 A1 EP4088818 A1 EP 4088818A1 EP 21173898 A EP21173898 A EP 21173898A EP 4088818 A1 EP4088818 A1 EP 4088818A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- grinding
- grinding gas
- jet mill
- spiral jet
- gas nozzles
- 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- Withdrawn
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
- B02C19/061—Jet mills of the cylindrical type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C25/00—Control arrangements specially adapted for crushing or disintegrating
Definitions
- the invention relates to a spiral jet mill with a grinding chamber which is delimited by a base, a cover and a wall connecting the base and the cover and with a large number of grinding gas nozzles which penetrate the wall and are connected to a grinding gas source.
- the invention also relates to a method for grinding grinding stock in such a spiral jet mill, into which the grinding stock is introduced and subjected to a grinding gas flow from a large number of grinding gas nozzles penetrating the wall.
- Spiral jet mills of the type mentioned at the outset have been known for a long time and are still used very frequently in industry, particularly in the pharmaceuticals and specialty and fine chemicals industries, when particles with diameters of less than about 10 ⁇ m are to be obtained.
- the working principle of the spiral jet mill is based on the fact that the grinding material introduced into the grinding chamber is exposed to the action of a sharp grinding gas stream entering the grinding chamber through the grinding gas nozzles penetrating the wall and accelerated to speeds of several hundred meters per second. Since the grinding gas nozzles are usually directed at an angle approximately tangentially into the grinding chamber, the flow of the incoming grinding gas forms in a spiral shape in the grinding chamber. The supplied regrind is caught and accelerated by the gas jets and crushed by mutual particle collisions.
- the material to be ground in the desired grain size is discharged from the grinding chamber together with the expanded grinding gas in the center of rotation of the spiral flow, while particles that are too coarse are subjected to further grinding stress.
- a spiral jet mill manages without moving built-in elements inside the grinding chamber and enables the production of a particularly fine ground material with a relatively narrow particle size distribution and hardly any mechanical abrasion worth mentioning.
- the object of the invention is therefore to propose a spiral jet mill and a method for grinding bulk materials in a spiral jet mill which, despite improved controllability of the grinding process, results in significantly more efficient grinding with higher output.
- a method according to the invention for solving the problem is the subject of patent claim 8.
- the proposal according to the invention provides an embodiment of a spiral jet mill in which at least some of the existing grinding gas nozzles are assigned a switchable shut-off device, by means of which the connection to the grinding gas source can be opened and closed independently of the other shut-off devices.
- a spiral jet mill in which the built-in grinding gas nozzles can be switched on and off individually by opening or closing the respectively assigned shut-off elements and opening or closing the connection of the assigned grinding gas nozzle to the grinding gas source. It is thus possible with the spiral jet mill according to the invention to regulate the flow of the grinding gas into the grinding chamber exclusively via the number of switched-on nozzles and the nozzle cross-section available for the grinding gas inlet. Regardless of the number of currently open shut-off devices and associated grinding gas nozzles, the optimal maximum operating pressure of the grinding gas source is always present and the grinding gas is fed into the grinding chamber at an optimally high speed via the open grinding gas nozzles.
- all grinding gas nozzles of the spiral jet mill according to the invention can each be equipped with an assigned switchable shut-off element in order to switch them on or off as required.
- shut-off valves ball valves, gate valves and similar shut-off devices come into consideration as shut-off devices within the meaning of the invention, which allow rapid switching between an open and closed state.
- the grinding gas source communicates with these grinding gas nozzles via separate feed lines each leading to a grinding gas nozzle, the switchable shut-off element being provided in the feed lines. This enables a space-saving arrangement of the shut-off elements and makes it possible to assign an individually controllable supply of grinding gas from the grinding gas source to each individual grinding gas nozzle.
- a particular advantage of the design of the spiral jet mill according to the invention is that, with the exception of the modification of the grinding gas feed to the individual grinding gas nozzles and the integration of associated shut-off devices, the other components of the spiral jet mill, in particular those of a base, a cover and a wall connecting the base and the cover Limited grinding chamber and the corresponding feed and discharge openings for the material to be ground experience no change, so that the configuration according to the invention can also be implemented as part of a modification or retrofitting of existing spiral jet mills.
- the spiral jet mill according to the invention comprises one, but preferably several, grinding gas nozzles distributed around the circumference of the wall.
- grinding gas nozzles distributed around the circumference of the wall.
- 3 to 40 such grinding gas nozzles are provided, which are arranged distributed regularly or together in groups around the circumference of the wall.
- the grinding gas nozzles are designed as Laval nozzles, which cause the grinding gas to exit the grinding chamber at a particularly high speed, which is advantageous for the grinding result.
- Such a design of the grinding gas nozzles as Laval nozzles was previously very difficult to implement, since with the usual regulation of the spiral jet mill via the grinding gas pressure present, the optimal operating point of the Laval nozzles could only be used to a very limited extent.
- the optimal operating point of the Laval nozzles can almost always be used and the grinding gas can be accelerated to a multiple of the speed of sound, which leads to an optimized grinding effect.
- a control device for independently controlling the shut-off devices in order to control the individual shut-off devices and associated grinding gas nozzles in a manner adapted to the respective control task for the purpose of opening or closing.
- the shut-off elements are preferably designed in such a way that they can only be switched over (open/closed) between a complete opening and a complete closure.
- the shut-off devices can be switched over as part of a presetting of the spiral jet mill for an upcoming grinding task before it is put into operation, but also during ongoing operation of the spiral jet mill to regulate individual process parameters.
- Individual grinding gas nozzles of the spiral jet mill according to the invention can be switched on and off, for example based on the desired degree of comminution depending on the type and hardness of the material to be ground and/or the internal pressure in the grinding chamber.
- the spiral jet mill according to the invention can be designed in particular with a cylindrical wall, so that a correspondingly circular-cylindrical grinding chamber is delimited between the base and cover, into which the individual grinding gas nozzles, which can be switched with the associated shut-off devices, open at a predetermined entry angle.
- the base and cover can be either flat or curved in order to give the grinding chamber a cylindrical or lenticular shape.
- a feed opening for feeding the material to be ground into the grinding chamber and also a discharge opening for removing the material to be ground ground in the grinding chamber can be formed in the cover of the spiral jet mill according to the invention.
- the method according to the invention for grinding material to be ground in a spiral jet mill is based on the fact that the spiral jet mill has a grinding chamber delimited by a base, cover and wall, into which the material to be ground is introduced and a grinding gas flow from a large number of grinding gas nozzles penetrating the wall is applied.
- the number of grinding gas nozzles to which the grinding gas flow is applied is varied in order to regulate the grinding gas flow.
- the invention is provided in particular to open the grinding gas nozzles separately and independently of the other grinding gas nozzles and to apply them to the grinding gas flow or to close them and separate them from the grinding gas flow.
- This opening or closing can be effected in particular by means of switchable shut-off elements which are assigned to the grinding gas nozzles and are arranged in the supply lines for the grinding gas which lead separately to each individual grinding gas nozzle.
- the flow of the grinding gas per unit of time into the grinding chamber is regulated by changing the number of grinding gas nozzles to which the grinding gas flow is applied, so that the method according to the invention enables a particularly efficient and variable adjustment of the grinding process in the spiral jet mill to the specific characteristics of the material to be ground and the respective grinding task permitted.
- individual grinding gas nozzles can be charged with the grinding gas flow or switched off in almost any configuration.
- a regular sequence of grinding gas nozzles is alternately opened or closed all around the circumference of the wall, for example alternately open-closed-closed etc separate, for example to open two or more adjacent grinding gas nozzles and to close the subsequent number of adjacent grinding gas nozzles accordingly.
- the method according to the invention is thus distinguished by an extremely large control bandwidth.
- it is essential that the feed of the grinding gas is not subject to any energy-inefficient throttling, but rather the highest possible operating pressure of the grinding gas source is present at each individual grinding gas nozzle, regardless of whether the respective grinding gas nozzle is open and also charged with the grinding gas flow or closed and separated from the grinding gas flow.
- the comminution effect and comminution intensity that can be achieved in the spiral jet mill according to the invention is therefore not adjusted by regulating the grinding gas source, but rather by switching individual grinding gas nozzles on and off and applying the grinding gas to them.
- the total grinding gas flow that is introduced into the grinding chamber is adjusted, although the pressure of the grinding gas in front of each individual grinding gas nozzle remains as high as possible, so that the achievable exit speeds of the grinding gas exceed those with the Grinding gas stream acted upon grinding gas nozzles remain accordingly high in the grinding chamber, which leads to an efficient use of the kinetic energy of the grinding gas.
- the grinding gas nozzles used can have cylindrical or conical nozzle cross sections. In a further development of the invention, however, they can also be designed as Laval nozzles and the exiting Accelerate grinding gas to a speed in the one to several times supersonic range.
- the grinding gas nozzles are also opened or closed while the grinding chamber is being subjected to the grinding gas flow, so that the spiral jet mill can also be controlled without any problems during operation, for example to check for changes in other to react to influencing parameters or disturbance variables.
- the grinding gas nozzles are preferably opened or closed as a function of the desired grain size, the hardness of the material to be ground and/or the pressure of the grinding chamber and must be selected by the person skilled in the art according to the requirements.
- the figures show a highly simplified schematic representation of a spiral jet mill 1 for grinding material to be ground, such as is used in the pharmaceutical, specialty and fine chemical industries, for example for grinding particulate solids.
- Particulate solids are used in this context for example iron oxides, in particular ⁇ -, ⁇ -, ⁇ - and/or ⁇ -FeOOH phases and/or Fe(OH) 2 phases, ferrihydrite and mixed and intermediate phases thereof, particularly preferably hematite of the modification ⁇ -Fe 2 O 3 , ⁇ -Fe 2 O 3 maghemite, magnetite, manganese or zinc ferrites, titanium dioxides, for example in rutile, anatase modification or as rutile mixed-phase pigments, chromium oxides, zinc oxides, zinc sulfides, ultramarine, nickel or chromium antimony titanium dioxides, cobalt blue, cobalt green , chromium oxides, or forms of carbon such as carbon black, graphite or graphene.
- Inorganic pigments from the aforementioned group are particularly preferred.
- the spiral jet mill 1 comprises a circular-cylindrical grinding chamber 10, which is delimited by a base 11, a cover 12 and a wall 13 connecting the base 11 and the cover 12 at a distance.
- the wall 13 is accordingly also circular-cylindrical.
- a corresponding curvature of the base 11 and/or cover 12 can also result in a lens-shaped design of the grinding chamber 10 .
- the wall 13 is penetrated by a plurality of grinding gas nozzles 14, in the example shown here a total of four, which open out approximately tangentially into the grinding chamber 10 at a predetermined entry angle.
- the grinding gas nozzles 14 communicate with a grinding gas source (not shown), for example a compressor, via feed lines 16 that are only indicated, and are acted upon by this with a corresponding grinding gas flow, for example compressed air.
- the grinding gas enters the grinding chamber 10 approximately tangentially via the grinding gas nozzles and, in the exemplary embodiment shown, generates a counter-clockwise spiral grinding gas flow inside the grinding chamber 10.
- the material to be ground is fed via a funnel 121 from a corresponding storage container and via a gas stream emerging from an injector nozzle 122 in a Injector tube 123 accelerated and introduced into the grinding chamber 10.
- the material to be ground is caught and entrained by the spirally circulating flow of grinding gas, with the acceleration forces occurring and collisions of the individual parts of the material to be ground causing the desired comminution and grinding of the material to be ground.
- each individual grinding gas nozzle 14 is provided in the area of its feed 16 for the grinding gas with a separate and independently controllable shut-off device 15, which makes it possible to shut off the individual grinding gas nozzles 14 to be acted upon by the milling gas flow and to activate it accordingly, or to separate it from the milling gas flow and to deactivate it accordingly.
- a shut-off device 15 is opened, the corresponding grinding gas nozzle 14 is subjected to the grinding gas from the grinding gas source and, conversely, separated from the grinding gas as soon as the associated shut-off device 15 is closed.
- the shut-off devices 15 can be formed, for example, by shut-off valves that can be switched between the open and closed positions.
- the comminution effect and intensity of the spiral jet mill 1 can be adjusted by changing the total milling gas flow into the milling chamber 10 without reducing the exit velocity of the milling gas into the milling chamber 10. This leads to the most efficient possible utilization of the grinding gas and a significantly more energy-efficient mode of operation of the spiral jet mill 1.
- the number of open or closed shut-off devices 15 and associated grinding gas nozzles 14 can be changed as desired before and during operation of the spiral jet mill.
- every second grinding gas nozzle 14 can be subjected to the grinding gas flow by opening the associated shut-off elements 15, but only a single grinding gas nozzle 14 can also be opened or three adjacent grinding gas nozzles 14 or all grinding gas nozzles 14 can be opened.
- spiral jet mills 1 with a higher or also lower number of grinding gas nozzles, with numbers of 3 to 40 such grinding gas nozzles 10 being considered suitable in the context of the invention.
- the control of the individual shut-off elements 15 that is currently desired can expediently be carried out by a corresponding control device, for example in accordance with an electronic system control.
- each individual grinding gas nozzle 14 is provided with a separate feed line 16, in which an independently switchable shut-off device 15 is provided.
- previously customary pre-distributors and pressure control devices for the grinding gas fed in can be omitted.
- the embodiment explained above achieves an ideally constant high pressure at the inlet of the grinding gas nozzles.
- This makes it possible to not only form the grinding gas nozzles cylindrically or conically, but also in the form of form Laval nozzles.
- the pressure in the grinding chamber 10 can be adjusted by switching individual grinding gas nozzles on or off as explained above, if necessary with adjustment of the grinding stock feed flow, with constant high pressure being applied to the open grinding gas nozzles, however.
- the individual open grinding gas nozzles can therefore always be operated in the range of the optimum operating point, which ensures energy-efficient operation, especially when designed as a Laval nozzle, since the highest outflow speeds of the grinding gas can be achieved up to a multiple of the speed of sound with low jet divergence. This is reflected in a significantly more energy-efficient grinding effect.
- the outflow speed of the grinding gas into the grinding chamber 10 can be increased up to the speed of sound by limiting the number of active or open grinding gas nozzles 14 for a predetermined flow of grinding material, which also enables energy-efficient grinding.
- spiral jet mill explained above and the method can not only be implemented in newly constructed spiral jet mills, but can also be implemented in existing spiral jet mills according to the prior art within the scope of a comparatively simple conversion.
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- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Disintegrating Or Milling (AREA)
- Crushing And Grinding (AREA)
- Milling Processes (AREA)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21173898.4A EP4088818A1 (fr) | 2021-05-14 | 2021-05-14 | Désintégrateur à jet hélicoïdal et procédé de broyage des produits à broyer dans un désintégrateur à jet hélicoïdal |
| US18/289,848 US20240238797A1 (en) | 2021-05-14 | 2022-05-13 | Spiral jet mill and method for grinding materials to be ground in a spiral jet mill |
| AU2022274163A AU2022274163A1 (en) | 2021-05-14 | 2022-05-13 | Spiral jet mill and method for grinding materials to be ground in a spiral jet mill |
| CA3216964A CA3216964A1 (fr) | 2021-05-14 | 2022-05-13 | Broyeur a jet en spirale et procede pour broyer des matieres a broyer dans un broyeur a jet en spirale |
| PCT/EP2022/063088 WO2022238573A1 (fr) | 2021-05-14 | 2022-05-13 | Broyeur à jet en spirale et procédé pour broyer des matières à broyer dans un broyeur à jet en spirale |
| KR1020237042361A KR20240006624A (ko) | 2021-05-14 | 2022-05-13 | 나선형 제트밀 및 나선형 제트밀에서 분쇄될 재료를 분쇄하는 방법 |
| EP22728914.7A EP4337385A1 (fr) | 2021-05-14 | 2022-05-13 | Broyeur à jet en spirale et procédé pour broyer des matières à broyer dans un broyeur à jet en spirale |
| CN202280034782.3A CN117295555A (zh) | 2021-05-14 | 2022-05-13 | 螺旋喷射研磨机和在螺旋喷射研磨机中研磨研磨材料的方法 |
| BR112023022828A BR112023022828A2 (pt) | 2021-05-14 | 2022-05-13 | Moinho de jato espiral e método de moagem de materiais a serem moídos em um moinho de jato espiral |
| JP2023569927A JP2024520923A (ja) | 2021-05-14 | 2022-05-13 | 螺旋状ジェットミル及び螺旋状ジェットミル内で粉砕される材料の粉砕方法 |
| CONC2023/0015301A CO2023015301A2 (es) | 2021-05-14 | 2023-11-14 | Molino de chorro en espiral y método para moler materiales en un molino de chorro en espiral |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21173898.4A EP4088818A1 (fr) | 2021-05-14 | 2021-05-14 | Désintégrateur à jet hélicoïdal et procédé de broyage des produits à broyer dans un désintégrateur à jet hélicoïdal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4088818A1 true EP4088818A1 (fr) | 2022-11-16 |
Family
ID=75936762
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21173898.4A Withdrawn EP4088818A1 (fr) | 2021-05-14 | 2021-05-14 | Désintégrateur à jet hélicoïdal et procédé de broyage des produits à broyer dans un désintégrateur à jet hélicoïdal |
| EP22728914.7A Pending EP4337385A1 (fr) | 2021-05-14 | 2022-05-13 | Broyeur à jet en spirale et procédé pour broyer des matières à broyer dans un broyeur à jet en spirale |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22728914.7A Pending EP4337385A1 (fr) | 2021-05-14 | 2022-05-13 | Broyeur à jet en spirale et procédé pour broyer des matières à broyer dans un broyeur à jet en spirale |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20240238797A1 (fr) |
| EP (2) | EP4088818A1 (fr) |
| JP (1) | JP2024520923A (fr) |
| KR (1) | KR20240006624A (fr) |
| CN (1) | CN117295555A (fr) |
| AU (1) | AU2022274163A1 (fr) |
| BR (1) | BR112023022828A2 (fr) |
| CA (1) | CA3216964A1 (fr) |
| CO (1) | CO2023015301A2 (fr) |
| WO (1) | WO2022238573A1 (fr) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040211849A1 (en) * | 2001-09-03 | 2004-10-28 | Hitoshi Itoh | Raw feed feeding device of jet mill |
| WO2013156465A1 (fr) | 2012-04-17 | 2013-10-24 | Micro-Macinazione S.A. | Broyeur à jet en spirale destiné à la micronisation d'une matière en poudre ou d'une matière contenant des particules en général, doté d'un nouveau système d'alimentation et de distribution de la matière en po0udre à microniser, et processus correspondant pour la micronisation d'un produit en poudre |
| CN203990833U (zh) * | 2014-08-05 | 2014-12-10 | 四川极速动力超微粉体设备制造有限公司 | 粉碎腔内无残留物料堆集的超微粉碎气流磨 |
| WO2017042341A1 (fr) | 2015-09-09 | 2017-03-16 | Vectura Limited | Procédé de broyage à jet |
| WO2019155038A1 (fr) | 2018-02-12 | 2019-08-15 | Micro-Macinazione Sa | Broyeur hélicoïdal modulaire et instrumenté pour effectuer des tests visant à définir, étudier et optimiser la micronisation d'un matériau en poudre |
| EP3613508A1 (fr) | 2018-08-23 | 2020-02-26 | NETZSCH Trockenmahltechnik GmbH | Procédé et dispositif de décharge des particules difficilement broyables d'un désintégrateur à jet hélicoïdal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5828885B2 (ja) * | 2011-02-28 | 2015-12-09 | 日清エンジニアリング株式会社 | 粉体の粉砕方法 |
| CN108982342B (zh) * | 2018-07-20 | 2021-11-09 | 中海石油(中国)有限公司湛江分公司 | 一种高温高压气藏水平井防砂筛管抗冲蚀性能评价装置及评价方法与应用 |
| CN109356674A (zh) * | 2018-12-25 | 2019-02-19 | 大庆特博科技发展有限公司 | 一种可调喷嘴数量的有机工质透平 |
-
2021
- 2021-05-14 EP EP21173898.4A patent/EP4088818A1/fr not_active Withdrawn
-
2022
- 2022-05-13 KR KR1020237042361A patent/KR20240006624A/ko active Pending
- 2022-05-13 WO PCT/EP2022/063088 patent/WO2022238573A1/fr not_active Ceased
- 2022-05-13 BR BR112023022828A patent/BR112023022828A2/pt unknown
- 2022-05-13 US US18/289,848 patent/US20240238797A1/en active Pending
- 2022-05-13 CN CN202280034782.3A patent/CN117295555A/zh active Pending
- 2022-05-13 EP EP22728914.7A patent/EP4337385A1/fr active Pending
- 2022-05-13 CA CA3216964A patent/CA3216964A1/fr active Pending
- 2022-05-13 JP JP2023569927A patent/JP2024520923A/ja active Pending
- 2022-05-13 AU AU2022274163A patent/AU2022274163A1/en active Pending
-
2023
- 2023-11-14 CO CONC2023/0015301A patent/CO2023015301A2/es unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040211849A1 (en) * | 2001-09-03 | 2004-10-28 | Hitoshi Itoh | Raw feed feeding device of jet mill |
| WO2013156465A1 (fr) | 2012-04-17 | 2013-10-24 | Micro-Macinazione S.A. | Broyeur à jet en spirale destiné à la micronisation d'une matière en poudre ou d'une matière contenant des particules en général, doté d'un nouveau système d'alimentation et de distribution de la matière en po0udre à microniser, et processus correspondant pour la micronisation d'un produit en poudre |
| CN203990833U (zh) * | 2014-08-05 | 2014-12-10 | 四川极速动力超微粉体设备制造有限公司 | 粉碎腔内无残留物料堆集的超微粉碎气流磨 |
| WO2017042341A1 (fr) | 2015-09-09 | 2017-03-16 | Vectura Limited | Procédé de broyage à jet |
| WO2019155038A1 (fr) | 2018-02-12 | 2019-08-15 | Micro-Macinazione Sa | Broyeur hélicoïdal modulaire et instrumenté pour effectuer des tests visant à définir, étudier et optimiser la micronisation d'un matériau en poudre |
| EP3613508A1 (fr) | 2018-08-23 | 2020-02-26 | NETZSCH Trockenmahltechnik GmbH | Procédé et dispositif de décharge des particules difficilement broyables d'un désintégrateur à jet hélicoïdal |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2022274163A1 (en) | 2023-11-16 |
| CA3216964A1 (fr) | 2022-11-17 |
| JP2024520923A (ja) | 2024-05-27 |
| CN117295555A (zh) | 2023-12-26 |
| EP4337385A1 (fr) | 2024-03-20 |
| US20240238797A1 (en) | 2024-07-18 |
| CO2023015301A2 (es) | 2023-11-30 |
| BR112023022828A2 (pt) | 2024-01-16 |
| KR20240006624A (ko) | 2024-01-15 |
| WO2022238573A1 (fr) | 2022-11-17 |
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