EP4196279A1 - Procédé de concassage de galettes d'engrais dans un broyeur à deux rouleaux - Google Patents

Procédé de concassage de galettes d'engrais dans un broyeur à deux rouleaux

Info

Publication number
EP4196279A1
EP4196279A1 EP21810953.6A EP21810953A EP4196279A1 EP 4196279 A1 EP4196279 A1 EP 4196279A1 EP 21810953 A EP21810953 A EP 21810953A EP 4196279 A1 EP4196279 A1 EP 4196279A1
Authority
EP
European Patent Office
Prior art keywords
roller
slug
cooling
mill
roll
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.)
Pending
Application number
EP21810953.6A
Other languages
German (de)
English (en)
Inventor
Agnes WINTER-PIETRUCK
Eggert De Weldige
Felix HEINICKE
Marcel Pfeifer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maschinenfabrik Koeppern GmbH and Co KG
Original Assignee
Maschinenfabrik Koeppern GmbH and Co KG
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 Maschinenfabrik Koeppern GmbH and Co KG filed Critical Maschinenfabrik Koeppern GmbH and Co KG
Publication of EP4196279A1 publication Critical patent/EP4196279A1/fr
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C4/00Crushing or disintegrating by roller mills
    • B02C4/28Details
    • B02C4/44Cooling or heating rollers or bars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00Disintegrating plant with or without drying of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08Separating or sorting of material, associated with crushing or disintegrating
    • B02C23/10Separating or sorting of material, associated with crushing or disintegrating with separator arranged in discharge path of crushing or disintegrating zone
    • B02C23/12Separating or sorting of material, associated with crushing or disintegrating with separator arranged in discharge path of crushing or disintegrating zone with return of oversize material to crushing or disintegrating zone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C4/00Crushing or disintegrating by roller mills
    • B02C4/02Crushing or disintegrating by roller mills with two or more rollers
    • B02C4/08Crushing or disintegrating by roller mills with two or more rollers with co-operating corrugated or toothed crushing-rollers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C4/00Crushing or disintegrating by roller mills
    • B02C4/28Details
    • B02C4/30Shape or construction of rollers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B30PRESSES
    • B30BPRESSES IN GENERAL
    • B30B15/00Details of, or accessories for, presses; Auxiliary measures in connection with pressing
    • B30B15/30Feeding material to presses
    • B30B15/302Feeding material in particulate or plastic state to moulding presses
    • B30B15/308Feeding material in particulate or plastic state to moulding presses in a continuous manner, e.g. for roller presses, screw extrusion presses

Definitions

  • the invention relates to a method for comminuting fertilizer slugs or slug pieces in a two-roller mill in the course of the production of fertilizer granules, the two-roller mill having two rotatingly driven grinding rollers whose roller surfaces are provided with a profile, the slugs or slug pieces being fed onto the two-roller mill and is/are comminuted into granules in the roller gap formed between the grinding rollers and the grinding rollers rotate at a peripheral speed (on the roller surface) of more than 5 m/s.
  • the roller can be designed as a solid roller or have a roller core and a roller jacket fastened to the roller core or a bandage which is provided with the profile.
  • the invention relates to a method and a plant for the production of fertilizer granules from inorganic substances, wherein the starting material inorganic substances such.
  • the starting material inorganic substances such.
  • This type of production of fertilizer granules is also known as press granulation or compaction granulation.
  • the starting material inorganic substances
  • the slug is pressed under high pressure in the (high-pressure) roller press and thereby compacted, resulting in the so-called "slug".
  • This process step is called press agglomeration.
  • This is followed in a further step by granulation by crushing the Schulpe and preferably classification, e.g. B. Screen classification.
  • the flakes emerging from the roller press are not generally fed directly to the two-roller mill, but pre-comminution takes place by first comminuting the flakes in a crusher and/or in a hammer mill to form flake pieces. This is then fed to the two-roll mill, optionally with the interposition of a classification system.
  • fertilizer granules with defined grain sizes are produced by press granulation, which can be handled perfectly.
  • the aim is usually to produce fertilizer granules with a grain size between 1 mm and 5 mm.
  • the inorganic substances that are used in the context of the invention for the production of fertilizer granules are, for. B. mineral substances or substances obtained from the evaporation of salt water, z. B. chlorides or sulfates. So it can preferably be potassium sulfate or potassium chloride.
  • roller press In the processes and systems described, a distinction must therefore be made between a roller press on the one hand and a two-roller mill on the other.
  • the starting material In the roller press, the starting material is compacted under high pressure and with relatively low peripheral speeds of the rollers to form the flakes.
  • the two-roller mill is used to comminute the slugs or slug pieces which, after compaction, e.g. B. using a roller crusher or a hammer mill from the scab. in the In contrast to roller presses, two-roller mills work with a relatively high peripheral speed and the material is scattered loosely as a veil of material into the roller gap.
  • the roll surfaces of the two-roll mill are profiled, ie the roll surfaces are usually structured.
  • the material is pressed under pressure with a screw conveyor into the nip.
  • the material to be pressed is fed in at a temperature greater than 120 °C and the pressing takes place with a high specific pressing force.
  • the rollers rotate at a peripheral speed of 0.55 to 0.75 m/s.
  • the roll surface should be kept at a temperature of less than 80 °C to prevent the material from melting on the press surface and thus creating a slug with a bright-hard surface.
  • This prior art specifically relates to a high pressure roller press.
  • DE 652 349 A describes a device for granulating clod-like products, in particular fertilizers containing ammonium nitrate, Consisting of two counter-rotating rollers, kept at a distance from each other at their outer circumference, the working surface of which is formed by sharp-edged grooves offset against the grooves of the opposite roller.
  • DE 21293 also discloses the grinding of grain on ribbed or smooth rollers.
  • the rollers are cooled to prevent damage to the grain from harmful heating.
  • the cooling of rollers is also described in DE 496543, which deals with the rolling of plastic and soft masses, in particular cocoa and chocolate masses, and alternatively mentions the rolling of rubber, oil paints and other masses containing oil and fat.
  • the cooling also serves to avoid damage to the processed masses.
  • an impairment of the rolling process among other things by burning the mass on the rollers, should be avoided.
  • Plastic materials are also processed with relatively low peripheral speeds and relatively high pressure.
  • DE 635 879 A describes a roller for mills and rolling mills that is provided with cooling.
  • a coolant for the purpose of heat distribution in the roller, the hollow space of the roller is filled with a liquid which is poured in once, after which the inlet opening is closed tightly.
  • chilled rollers in roller presses for hot briquetting or hot compacting of material that is processed temperatures with high Tempe, z. B. in the processing of reduced iron ores or sponge iron with temperatures of over 900 ° C (see e.g. DE 102012 106527 A1).
  • the bandages of the rolls and in particular the pressing tools attached to them are subject to high wear.
  • cooling systems e.g. B. water cooling provided.
  • the invention is based on the technical problem of creating a method for crushing fertilizer slugs or slug pieces in a two-roller mill of the type described above, which is characterized by improved functionality and economy.
  • the invention teaches in a generic method for comminuting fertilizer slugs or slug pieces in a two-roller mill in the course of the production of fertilizer granules that the surfaces of the grinding rollers are cooled during operation and consequently during the comminution of the slugs or slug pieces.
  • cooling of the roller surfaces of the two-roller mill is provided, ie the (preferably hot) Fertilizer slugs or slug pieces are crushed in a two-roller mill with cooled roller surfaces.
  • the invention is based on the surprising finding that in such a two-roller mill when processing fertilizers, despite the low pressures in the roller gap and despite the high peripheral speeds of the roller surfaces and the associated very short contact times of the material with the roller surface, cooling prevents clogging of the profiled roll surfaces can be reliably avoided.
  • the cooling prevents caking or sticking of the salts or slugs on the roll surfaces and consequently in the roll profiles.
  • the granular and preferably hot material ie the scab or the pre-comminuted scab pieces (e.g. with a size/fraction of 4 to 10 mm) is scattered loosely into the roller gap as a veil of material without compaction, e.g . B. via a arranged above the nip vibrating material chute and a following or arranged below the chute chute, which extend over the entire width of the roller.
  • the roller width can B. 1000 mm to 3000 mm, e.g. B. be 1500 mm to 2500 mm.
  • a typical roll width is z. B. 1800mm to 2000mm.
  • the material is scattered as a veil of material into the chute located above the roller gap via the vibrating chute or similar means.
  • the speed of the two rollers is more than 5 m/s, preferably more than 6 m/s. At different speeds, the slower roller is more than 5 m/s, preferably more than 6 m/s.
  • the peripheral speeds can be 5 to 25 m/s, e.g. B. 5 to 20 m/s, preferably 7 to 15 m/s.
  • the diameter of the grinding rollers is, in a known manner, about 200 mm to 1000 mm, preferably 400 mm to 800 mm, e.g. B. 500mm to 700mm.
  • the speed (for both rolls or for the slower roll) may be 80 to 2400 rpm, eg 100 to 1000 rpm, preferably 200 to 600 rpm, e.g. 200 to 500 rpm.
  • the respective peripheral speed then results from the roll diameter and the speed.
  • the grinding rollers are driven in opposite directions.
  • the nip is z. 0.5 to 10 mm, e.g. B. 1 to 5 mm.
  • the nip can be structurally fixed.
  • the roll gap can be variably set to a specific value in the specified range.
  • the nip is preferably fixed so that -. B. in contrast to grain paktierpressen - is not worked with a changing during operation roller gap.
  • the surface of the grinding rollers is preferably provided with corrugations (as profiling), these corrugations z. B. can be formed by a variety of channel-shaped depressions and projections. This Ver depressions and projections can be z. B. extend across the roll width and z. B. be oriented straight (parallel) or obliquely to the roll axis, spirally or arcuately. It is also possible to use two rolls in one press with different profiles, e.g. B. one with straight and one with not straight oriented corrugation can be combined with each other.
  • the profiling of the grinding rollers of the two-roller mill is to be distinguished from the individual crushing elements realized in roller crushers.
  • the flake (or the flake parts) is preferably introduced dry into the two-roller mill, with the flake or the particles preferably having a maximum moisture content of 1.5% by weight.
  • the material i.e. H. the slug or slug pieces are usually made in a warm state, e.g. B. at a temperature of at least 100 ° C on the two-roll mill.
  • the temperature is 100°C to 200°C, e.g. B. 120 °C to 150 °C.
  • the cooling according to the invention prevents the (granular and hot) material from sticking to the roll surfaces.
  • the cooling can be implemented with the proviso that the temperature of the roll surfaces is 100 °C, e.g. B. 90 ° C, preferably does not exceed 80 ° C.
  • the cooling of the roll surfaces is essential and for this purpose the rolls can be provided with internal cooling, e.g. B. in the rolls one or more cooling devices are integrated. These cooling devices can, for. B. be designed as liquid cooling, which have one or more arranged within the roller cooling channels for a cooling medium. As a cooling medium z. B. water can be used.
  • the invention also relates to a two-roller mill of the type described for comminuting such flakes of fertilizer, this two-roller mill being set up to carry out the method described and consequently being provided with a cooling system.
  • the roller of such a two-roller mill can be designed as a solid roller or, in a manner known in principle, as one roll core and on the other hand a roll shell arranged on the roll core or a ring bandage, this roll shell or the ring bandage being provided with the described profiling.
  • the roller shell which can also be made in several parts from several segments, or the ring bandage can consequently be exchanged as wearing elements and fastened detachably on the roller core.
  • the cooling is preferably implemented by one or more cooling channels that are set up to cool the roll surface.
  • Cooling channels in the roll core, in the bandage (or the roll shell) and / or between the roll core and bandage / shell can be arranged. Such channels can e.g. B. as holes in the roll core and / or in the bandage.
  • a possible embodiment is characterized in that the cooling channels or a ring-shaped circumferential or spiral-shaped circumferential cooling channel is formed between the roll core and the bandage. This can be constructive z.
  • a spiral-shaped circumferential annular groove is introduced into the roll core on the outer circumference, which is closed by the attached bandage and thus forms a circumferential, spiral-shaped annular channel as a cooling channel on the inside of the bandage.
  • annular groove can also be introduced into the bandage on the inner circumference. It is always expedient to feed the cooling medium into the roller body via a central or axis-parallel feed channel. From there, the cooling medium z. B. via radial feed channels in the area of the surface, z. B. in the spiral cooling channel.
  • the invention also relates to a process for the production of fertilizer granules from inorganic substances, in which the starting material is first compacted into a flake in a (high-pressure) roller press and the flake or the flake pieces produced from the flake are then processed in a two-roller mill in the described Kind is crushed or are crushed, wherein the rolls of the two-roll mill are cooled during the crushing.
  • the focus is on the processing of granular, hot material.
  • the starting material is fed to the roller press as feed material, preferably at a temperature of at least 100 °C. Consequently, hot material is processed, so that the slugs or slug pieces, as preferably granular material, are also fed to the two-roller mill in a hot state, specifically preferably at a temperature of at least 100°C.
  • the scab that emerges from the high-pressure roller press is not fed directly to the two-roller mill, but is first pre-comminuted in a pre-comminution device.
  • the crushing device can be z. B. be a roll crusher and / or a hammer mill. As a result, flake pieces or flake particles are first produced from the flake and these are fed to the roller mill for granulation.
  • the slug pieces are classified between the pre-crushing device and the two-roller mill, e.g. B. with one or more screening devices.
  • pre-crushing device e.g. B.
  • two-roller mill e.g. B. with one or more screening devices.
  • the invention also relates to a plant for the production of fertilizer granules with such a method, the plant having at least one roller press (high-pressure roller press) and a two-roller mill, the two-roller mill being provided with cooling of the roller surfaces according to the invention.
  • at least one pre-comminution device and/or one classification device are preferably provided.
  • FIG. 1 a greatly simplified flow chart for a plant or a
  • FIG. 2 shows a two-roller mill for comminuting fertilizer flakes within such a method
  • Fig. 3 shows a detail from the two-roller mill according to Fig. 2.
  • a plant for the production of fertilizer granules from inorganic substances, with a temperature of, for example, at least 100° C. is shown schematically and in a highly simplified manner.
  • the system has a roller press 1, which is designed as a braiding pressure roller press.
  • the starting material A namely inorganic substances
  • This slug S is then granulated, with optional pre-comminution initially being provided in at least one pre-comminution device 2a, 2b.
  • This pre-crushing device can, for. B. be designed as a roll crusher 2a.
  • flake pieces or flake particles P are produced in this way from the flake S, which are comminuted in a next process step and consequently granulated.
  • the slug pieces P which, for example, have a temperature of at least 100 °C have, a two-roll mill 3 abandoned and crushed into granules G in the two-roll mill.
  • classification takes place between the pre-crushing and the comminution, and for this purpose a screening device 4 with a plurality of screening stages 4a, 4b, 4c is arranged between the pre-crushing device 2 and the two-roller mill 3.
  • the slug pieces or particles P are fed to the screening device and in the first screening stage 4a very coarse particles with a size of more than 10 mm are screened off as coarse fraction a.
  • This coarse fraction a z. B. a further crushing device 2c, z. B. a hammer mill, and from there the crushed particles are fed to the screening device 4 again.
  • a middle fraction b with a particle size of, for example, greater than 4 mm to 10 mm is screened off and this middle fraction b is fed as feed material to the two-roller mill 3, where it is crushed in the manner described.
  • the comminuted material is circulated and consequently fed back to the screening device 4 .
  • a material with a grain size of 2 mm to 4 mm and consequently the desired granules G are screened and discharged as product G.
  • the finest material F that has passed through all the sieve passes is fed back to the compaction-granulation process and consequently fed back to the roller press 1 for compaction.
  • Fig. 2 shows a simplified schematic of a two-roller mill 3 with two counter-rotating grinding rollers 7, the roller surfaces are provided with a profiling tion 8, z. B. is formed as a corrugation with a plurality of trough-shaped depressions and projections. This channel-shaped depressions and projections extend over the entire width of the roll and z. B. oriented obliquely to the roll axis.
  • each of the rollers 7 consists of a rotatingly driven roller core 9 and a ring bandage 10 mounted on the roller core, which in turn is provided with the profile 8 .
  • the rolls 7 are each equipped with a cooling device with which the roll surfaces are cooled.
  • cooling channels 11 are integrated into the rollers.
  • these cooling channels 11 are each designed as cooling channels 11 running around in a spiral shape. Structurally, these can be realized in that the roller core 9 is provided with an annular circumferential spiral groove on the outside, which is closed by the mounted bandage 10, so that a spirally circumferential cooling channel 11 is formed between the roller core 9 and bandage 10.
  • the cooling medium is supplied via a central supply channel 12 which is arranged axially in the roller core. The cooling medium can be supplied to and removed from the cooling channel 11 via radial channels 13 .
  • the two-roller mill 3 is provided with a housing 14 which forms an enclosure. Furthermore, a feed chute 15 is provided, via which the material is fed, wherein this chute 15 can be part of the housing or enclosure 14 . The material is scattered loosely in the form of a material veil without pressure in the roller gap.
  • a vibrating channel or vibrating platform (not shown) can be provided, via which the material enters the chute 15 above the nip and is guided from there into the nip.
  • the cooling of the two-roller mill described is of particular importance, since clogging of the profiling or corrugation can surprisingly be avoided by the cooling in this method.
  • This is of essential importance, because clogging of the profile means that the shearing effect in the gap is reduced and the material breaks into finer pieces. Furthermore, the open, central nip is reduced and this also leads to more fines being produced. After the next pass through the screen, both are returned to the roller press as fine returns and run through the process again. This unwanted fine material increases the circulating load in the plant and thus the output of product is reduced. Overall, clogging of the profiling consequently leads to a reduction in efficiency and thus to a reduction in the cost-effectiveness of the system. According to the invention, these disadvantages are avoided in a surprisingly simple manner by the described cooling of the rolls, specifically in a two-roll mill within the described method.

Landscapes

  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Crushing And Grinding (AREA)
  • Fertilizers (AREA)

Abstract

L'invention concerne un procédé de concassage de galettes ou de morceaux de galette d'engrais dans un broyeur à deux rouleaux (3) au cours de la production d'un matériau d'engrais granulaire, le broyeur à deux rouleaux (3) comprenant deux rouleaux de broyage entraînés en rotation, dont les surfaces de rouleau sont pourvues d'un profilage, la galette ou les morceaux de galette étant placés sur le broyeur à deux rouleaux (3) et concassés en matériau granulaire dans l'espacement de rouleaux formé entre les rouleaux de broyage, les rouleaux de broyage tournant à une vitesse circonférentielle supérieure à 5 m/s. Ce procédé est caractérisé en ce que les surfaces des rouleaux de broyage sont refroidies pendant le fonctionnement.
EP21810953.6A 2020-11-30 2021-11-09 Procédé de concassage de galettes d'engrais dans un broyeur à deux rouleaux Pending EP4196279A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020131638.0A DE102020131638B4 (de) 2020-11-30 2020-11-30 Verfahren zur Zerkleinerung von Düngemittelschülpen in einer Zweiwalzenmühle
PCT/EP2021/081126 WO2022111990A1 (fr) 2020-11-30 2021-11-09 Procédé de concassage de galettes d'engrais dans un broyeur à deux rouleaux

Publications (1)

Publication Number Publication Date
EP4196279A1 true EP4196279A1 (fr) 2023-06-21

Family

ID=78709406

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21810953.6A Pending EP4196279A1 (fr) 2020-11-30 2021-11-09 Procédé de concassage de galettes d'engrais dans un broyeur à deux rouleaux

Country Status (7)

Country Link
US (1) US20230347356A1 (fr)
EP (1) EP4196279A1 (fr)
BR (1) BR112023010458A2 (fr)
CA (1) CA3199451A1 (fr)
DE (1) DE102020131638B4 (fr)
IL (1) IL302684A (fr)
WO (1) WO2022111990A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115069351A (zh) * 2022-08-05 2022-09-20 成都建筑材料工业设计研究院有限公司 一种复合水冷式辊式破碎设备
DE102023106787B3 (de) 2023-03-17 2024-05-08 Maschinenfabrik Köppern Gmbh & Co. Kg Anlage und Verfahren zur Herstellung von Düngemittelgranulat

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE21293C (de) F. KRAUS in Neufs, Rhein Neuerung an Walzenmühlen
DE496543C (de) 1927-08-25 1930-04-25 Bauermeister Hermann Maschf Zylindrische, mittels Kuehlfluessigkeit zu temperierende Walze
DE652349C (de) 1934-04-14 1937-10-29 Ruhrchemie Akt Ges Vorrichtung zur Koernung schollenartiger Produkte, insbesondere ammonnitrathaltiger Duengemittel
DE635879C (de) 1936-02-02 1936-09-25 Ind Akt Ges Walze fuer Muehlen und Walzwerke
DE1758978A1 (de) 1968-09-11 1971-04-08 Koeppern & Co Kg Maschf Verfahren zum Kompaktieren von durch Flotation gewonnenen Kalisalzen auf Walzenpressen
DE2824827B2 (de) 1978-06-06 1980-09-11 Maschinenfabrik Koeppern Gmbh & Co Kg, 4320 Hattingen Verfahren zum Verpressen von Salzen auf Walzenpressen
US4439384A (en) * 1981-12-16 1984-03-27 Maschinenfabrick Koppern Gmbh & Co. Kg Method for manufacturing graules from potassium chloride fines
DE3802173C1 (fr) 1988-01-26 1988-09-08 Maschinenfabrik Koeppern Gmbh & Co Kg, 4320 Hattingen, De
US20060065770A1 (en) * 2003-12-31 2006-03-30 Armex, Inc. Material processing apparatus and methods
US20130193245A1 (en) * 2012-01-27 2013-08-01 David M. Futa Apparatus and method for producing crumb rubber
DE102012106527B4 (de) 2012-07-18 2016-01-21 Maschinenfabrik Köppern GmbH & Co KG Presswalze für eine Walzenpresse

Also Published As

Publication number Publication date
DE102020131638B4 (de) 2024-03-28
DE102020131638A1 (de) 2022-06-02
WO2022111990A1 (fr) 2022-06-02
BR112023010458A2 (pt) 2024-02-06
IL302684A (en) 2023-07-01
CA3199451A1 (fr) 2022-06-02
US20230347356A1 (en) 2023-11-02

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