Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/245—Stationary reactors without moving elements inside placed in series
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
  • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/06—Solidifying liquids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J4/00—Feed or outlet devices; Feed or outlet control devices
  • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
  • B01J4/002—Nozzle-type elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/005—Separating solid material from the gas/liquid stream
  • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1818—Feeding of the fluidising gas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
  • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/10—Esters
  • C08F120/12—Esters of monohydric alcohols or phenols
  • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00743—Feeding or discharging of solids
  • B01J2208/00761—Discharging
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/18—Details relating to the spatial orientation of the reactor
  • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

Definitions

• the invention is based on a device for producing pulverulent poly (meth) acrylate comprising a droplet polymerization reactor with a device for dropping a monomer solution for the preparation of the poly (meth) acrylate with holes through which the monomer solution is introduced, an addition point for a gas above the device for dripping, at least one gas sampling point at the periphery of the reactor and a fluidized bed, wherein the reactor between the device for dripping and the gas sampling comprises a reactor jacket and above the fluidized bed in the direction of the gas sampling a region of decreasing hydraulic diameter whose maximum hydraulic diameter is greater than the mean hydraulic diameter of the reactor shell, and wherein the reactor shell protrudes into the region of decreasing hydraulic diameter, so that an annular channel between the outer wall of the reactor shell and the wall, by which the region is delimited with decreasing hydraulic diameter, is formed, and the at least one gas sampling point is arranged on the annular channel.
• Poly (meth) acrylates are used in particular as water-absorbing polymers which are used, for example, in the manufacture of diapers, tampons, sanitary napkins and other hygiene articles or else as water-retaining agents in agricultural horticulture.
• the properties of the water-absorbing polymers can be adjusted via the degree of crosslinking. As the degree of crosslinking increases, the gel strength increases and the absorption capacity decreases. This means that with increasing absorption under pressure, the centrifuge retention capacity decreases, and at very high degrees of crosslinking the absorption under pressure also decreases again.
• water-absorbing polymer particles are generally postcrosslinked. As a result, only the degree of crosslinking at the particle surface increases, whereby the absorption under pressure and the centrifuge retention capacity can be at least partially decoupled. This postcrosslinking can be carried out in aqueous gel phase.
• crosslinkers suitable for this purpose are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the hydrophilic polymer.
• Various processes are known for the preparation of the water-absorbing polymer particles.
• the monomers used for the preparation of poly (meth) acrylates and optionally additives can be added to a mixing kneader in which the monomers nomere to react polymer. By rotating shafts with kneading bars in the mixing kneader, the resulting polymer is torn into chunks.
• the polymer removed from the kneader is dried and ground and fed to a post-processing.
• the monomer is introduced into a reactor for droplet polymerization in the form of a monomer solution, which may also contain further additives.
• the monomer solution When the monomer solution is introduced into the reactor, it decomposes into drops.
• the mechanism of droplet formation may be turbulent or laminar jet disintegration or else dripping.
• the mechanism of droplet formation depends on the entry conditions and the material properties of the monomer solution.
• the drops fall down in the reactor, with the monomer reacting to the polymer.
• In the lower part of the reactor there is a fluidized bed into which the polymer particles formed by the reaction from the droplets fall. In the fluidized bed then takes place a post-reaction.
• gas is added at two points.
• a first gas stream is introduced above the device for dripping and a second gas flow from below through the fluidized bed.
• the flow direction of the gas streams is opposite.
• the gas is withdrawn from the reactor via the annular channel, which is formed by the reactor shell projecting into the region of decreasing hydraulic diameter. In this case, the entire amount of gas supplied to the reactor must be removed. This leads to high gas velocities in the region of the annular channel, wherein the gas velocities can be so high that polymer material is entrained with the gas via the annular channel.
• the object of the present invention is therefore to produce a dropwise polymerization reactor for the preparation of pulverulent poly (meth) acrylate in which a droplet or particle nitride in the region of the annular channel is avoided.
• an apparatus for the preparation of powdered poly (meth) acrylate comprising a dropwise polymerization reactor with a device for dropping a monomer solution for the preparation of the poly (meth) acrylate with holes through which the monomer solution is introduced; an addition point for a gas above the device for dripping, at least one gas sampling point at the periphery of the reactor and a fluidized bed, wherein the reactor between the device for dripping and the gas sampling comprises a reactor jacket and above the fluidized bed in the direction of the gas sampling a region of decreasing hydraulic diameter whose maximum hydraulic diameter is greater than the mean hydraulic throughput knife of the reactor shell, and wherein the reactor shell protrudes into the region of decreasing hydraulic diameter, so that an annular channel between the outer wall of the reactor shell and the wall, through which the region is limited with decreasing hydraulic diameter is formed, and the at least one gas sampling point on the annular channel is arranged, wherein the ratio of the horizontal surface of the annular channel to the horizontal surface, which is enclosed by the reactor jacket, in
• the annular channel may be formed in one piece as well as segmented. In a one-piece annular channel this runs without interruption annular around the reactor shell. Alternatively, a one-piece annular channel may also include a dividing wall extending radially between the reactor shell and the wall of the region of decreasing hydraulic diameter. A segmented annular channel is divided by several, that is at least two corresponding radially extending partitions into individual areas. In the case of a segmented annular channel, each segment of the annular channel is connected to at least one gas sampling point, it also being possible for a plurality of gas sampling points to be provided on a segment, depending on the size of the segment.
• segmentation by radially extending partitions In addition to a segmentation by radially extending partitions and a segmentation by the reactor jacket at a constant distance circumferential partition is possible.
• a segmentation by radially extending partitions is customary.
• the segmentations can also be partially interrupted or executed only in the edge regions of the annular channel, for example in the form of inner reinforcing ribs.
• it is particularly preferred if the annular channel inside the reactor is not segmented.
• the droplet polymerization reactor By designing the droplet polymerization reactor such that the ratio of the horizontal area of the annular channel to the horizontal area enclosed by the reactor shell is in the range of 0.3 to 5, it is achieved that the amount of gas flow into the annular channel entrained particles is minimized and only very small dust-like particles are entrained. These also generally no longer form caking, since the particles are so small that all of the monomer contained therein has been converted to the polymer and the water has been evaporated.
• a gas stream is formed. speed in the annular channel of 0.25 to 3 m / s, preferably 0.5 to 2.5 m / s and in particular 1, 0 to 1, 8 m / s.
• the ratio of the horizontal area of the annular channel to the horizontal area enclosed by the reactor shell is in the range of 0.4 to 3.5 and in particular in the range of 0.5 to 2.
• a drop polymerization reactor generally comprises a head having a monomer solution dripping device, a central region through which the dripped monomer solution falls and is converted to the polymer, and a fluidized bed into which the polymer droplets fall.
• the fluidized bed closes the region of the reactor with decreasing hydraulic diameter downwards.
• the head of the reactor in the form of a truncated cone and the device for dripping in the frusto-conical head of the reactor to position. Due to the frusto-conical design of the head of the reactor can be saved compared to a cylindrical design material. In addition, a frusto-conically shaped head serves to improve the static stability of the reactor. Another advantage is that the gas introduced at the head of the reactor has to be supplied over a smaller cross section and then flows downwards in the reactor due to the frusto-conical configuration without any strong turbulence.
• the turbulences which can be set in a cylindrical design of the reactor in the head area and a gas supply in the middle of the reactor, have the disadvantage that drops that are entrained with the gas flow can be transported due to the turbulence against the wall of the reactor and so contribute to the formation of deposits.
• the device for dropping the monomer solution is arranged as far up in the frusto-conically shaped head as possible. This means that the device for dropping the monomer solution is disposed at the level of the frustoconical shaped head, in which the diameter of the frustoconical shaped head corresponds approximately to the diameter of the device for dripping.
• the hydraulic diameter of the frustoconical shaped head in the height in 2 to 30%, more preferably 4 to 25% and in particular 5 to 20%, of the device for dripping is greater than the hydraulic see diameter, which belongs to the area enclosed by the shortest line connecting the outermost holes.
• the slightly larger hydraulic diameter of the head also ensures that drops do not bounce early on the reactor wall and stick there even below the reactor head.
• the device for dewatering the monomer solution is an addition point for gas, so that gas and drops flow in direct current from top to bottom through the reactor. Since the fluidized bed is located in the lower part of the reactor, this causes gas to flow in the opposite direction from bottom to top in the lower part of the reactor. Since gas is introduced into the reactor from both above and below, it is necessary to remove the gas between the monomer solution dripping device and the fluidized bed.
• the gas sampling point is positioned at the transition from the reactor jacket to the region with the hydraulic diameter decreasing in the direction of the fluidized bed.
• the region of decreasing hydraulic diameter of the hydraulic diameter decreases from the gas sampling point in the direction of the fluidized bed from top to bottom.
• the decrease in the hydraulic diameter preferably proceeds linearly, so that the region with decreasing hydraulic diameter has the shape of an inverted truncated cone.
• the design of the reactor is independent of the shape of the cross-sectional area. This may be, for example, circular, rectangular, in the form of any polygon, oval or elliptical. However, a circular cross-sectional area is preferred.
• the mean hydraulic diameter in the context of the present invention is understood to be the arithmetic mean.
• the reactor jacket which extends between the head with the device for dripping and the gas sampling point, preferably has a constant hydraulic diameter.
• the reactor jacket is designed cylindrical.
• the reactor jacket is particularly preferably designed with a constant hydraulic diameter, and particularly preferably the reactor jacket is cylindrical.
• the height of the annular channel is preferably designed so that the ratio of the distance between the outer wall of the reactor shell and the wall of the region of decreasing hydraulic diameter at the entrance to the annular channel and the height of the annular channel between the entrance into the annular channel and lower edge of the gas sampling in the range of 0.05 to 50 is.
• the ratio of the distance between the outer wall of the reactor shell and the wall of the region of decreasing hydraulic diameter at the entrance to the annular channel and the height of the annular channel between the entrance to the annular channel and the lower edge of the gas sampling is in the range of 0.2 to 25 and in particular in the range of 0.5 to 10.
• entry into the annular channel is understood to mean the surface which is defined perpendicular to the axis of the reactor between the lower end of the reactor jacket and the wall of the region of decreasing hydraulic diameter.
• the at least one gas sampling point is generally positioned either on the outer peripheral surface of the annular channel or alternatively and preferably on the wall which closes the annular channel upwards.
• the wall closing off the annular channel is preferably formed at an angle in the range of 45 to 90 ° to the reactor axis.
• each gas sampling point is connected to a device for the separation of solids.
• the number of devices for separating solids is the same as the number of gas sampling points.
• the solids separation device must be made sufficiently large so that the combined gas streams from the at least two gas sampling points can be passed through the solids separation device.
• the embodiment in which each gas sampling point is connected to a device for the separation of solids is preferred. Suitable devices for separating solids are, for example, filters or centrifugal separators, for example cyclones.
• cyclones are particularly preferred.
• two solids separation devices are provided in parallel and the gas flow is always is passed through a device for separation of solids, while the other is switched off and can be cleaned, for example. This is especially useful when using filters.
• the number of gas tapping points results from the gas quantities flowing through the reactor and the cross-sectional area of the gas tapping points. It is particularly preferred if at least three gas tapping points are provided and in particular at least four gas tapping points. Arranged uniformly over the circumference of the annular channel means that the distance between the centers of two adjacent gas sampling points for each gas sampling points is the same size.
• a ratio of the horizontal cross-sectional area of the annular channel to the total cross-sectional area of all gas sampling points in the range of 1, 5 to 150 is advantageous.
• the horizontal cross-sectional area of the annular channel is the area perpendicular to the reactor axis between the reactor shell and the wall of the area is formed with decreasing hydraulic diameter.
• the total cross-sectional area of all gas sampling points is the sum of the cross-sectional areas of the gas sampling points, wherein the cross-sectional areas of the gas sampling points is the cross-sectional area transverse to the flow direction of the gas and thus perpendicular to the central axis through the gas sampling point.
• the lower end of the reactor shell has a region with a diametric extension, with the diametric extension region entirely within the region forming the annular channel. Due to the diameter enlargement, the formation of deposits by adhering polymer particles can be reduced in the region of the lower end of the reactor shell.
• the diameter extension at the lower end of the reactor shell is preferably conical and has an opening angle in the range of 0 to 10 °.
• the area of decreasing hydraulic diameter may have a decreasing hydraulic diameter over the entire height. In this case, the distance between the outer wall of the annular channel formed by the region of decreasing hydraulic diameter and the inner wall of the annular channel formed by the reactor jacket increases from bottom to top, so that the cross-sectional area of the annular channel increases from bottom to top.
• a region with a constant hydraulic diameter adjoins, so that the outer wall of the annular channel has a constant hydraulic diameter.
• FIG. 1 shows a longitudinal section through a reactor for droplet polymerization
• Figure 2 shows a cross section through the reactor for droplet polymerization in the region of
• FIG. 1 shows a longitudinal section through a reactor designed according to the invention.
• a droplet polymerization reactor 1 comprises a reactor head 3, in which a device for dripping 5 is accommodated, a central region 7, in which the polymerization reaction takes place, and a lower region 9 with a fluidized bed 11, in which the reaction is completed.
• the device for dropping 5 is supplied with a monomer solution via a monomer feed 12. If the device for dripping 5 has multiple channels, it is preferable to supply the monomer solution to each channel via its own monomer feed 12. The monomer solution passes through holes not shown in FIG. 1 in the device for dropping 5 and breaks up into individual drops which fall down in the reactor.
• a gas for example nitrogen or air
• the gas flow thereby supports the disintegration of the monomer solution emerging from the holes of the device for dropping 5 into individual drops.
• the reactor head 3 is preferably conical, as shown here, wherein the device for dripping 5 in FIG conical reactor head 3 is located above the cylindrical portion.
• the reactor also cylindrical in the reactor head 3 with a diameter as in the central region 7.
• a conical design of the reactor head 3 is preferred.
• the position of the dropletizing device 5 is chosen such that a dropping of the droplets between the outermost holes through which the monomer solution is fed and the wall of the reactor is still a sufficiently large distance to prevent the wall.
• the distance should be at least in the range of 50 to 1500 mm, preferably in the range of 100 to 1250 mm and in particular in the range of 200 to 750 mm.
• a greater distance to the wall of the reactor is possible. However, this has the disadvantage that with a greater distance is associated with a poorer utilization of the reactor cross-section.
• the lower region 9 terminates with a fluidized bed 11 into which the polymer particles formed during the fall from the monomer droplets fall.
• the post-reaction to the desired product takes place in the fluidized bed.
• the outermost holes through which the monomer solution is dripped are positioned such that a drop falling vertically downwards falls into the fluidized bed 1 1.
• This can be realized, for example, in that the hydraulic diameter of the fluidized bed is at least as large as the hydraulic diameter of the area enclosed by a line connecting the outermost holes in the device 5, the cross-sectional area of the fluidized bed and that of the surface forming the outermost holes has the same shape and the centers of the two surfaces are in a perpendicular projection at the same position.
• the outermost position of the outer holes with respect to the position of the fluidized bed 1 1 is shown in Figure 1 by means of a dashed line 15.
• the hydraulic diameter at the level of the middle between the device for dripping and the gas sampling point is at least 10% greater than the hydraulic diameter of the fluidized bed.
• the reactor 1 can have any desired cross-sectional shape.
• the cross section of the reactor 1 is preferably circular.
• the hydraulic diameter corresponds to the diameter of the reactor 1.
• the diameter of the reactor 1 increases in the embodiment shown here, so that the reactor 1 widens conically in the lower region 9 from bottom to top.
• This has the advantage that in the reactor 1 resulting polymer particles that hit the wall, can slide down the wall in the fluidized bed 1 1.
• knockers not shown here can be provided nusförmigen part of the reactor, with which the wall of the reactor is caused to oscillate, thereby dissolving adhering polymer particles and slip into the fluidized bed 1 1.
• a gas distributor 17 through which the gas is injected into the fluidized bed 1 1.
• At least one gas sampling point 19 is arranged at the transition from the middle region 7 with a constant cross-section to the lower region 9 which widens conically from the bottom to the top.
• the cylindrical central region 7 protrudes with its wall into the upwardly conically widening lower region 9, whereby the diameter of the conical lower region 9 at this position is greater than the diameter of the central region 7
• Area 7 circumferential annular channel 21 is formed, in which the gas flows in and through which at least one gas sampling point 19 which is connected to the annular channel 21, can be deducted.
• the post-reacted polymer particles of the fluidized bed 11 are removed via at least one product removal point 23 in the area of the fluidized bed.
• the gas sampling point 19 is connected via a gas channel 25 to at least one device for solids separation 27, for example a filter or a cyclone, preferably a cyclone.
• the solid particles removed from the gas can then be removed from the cyclone via a removal of solids, and the gas purified from solids can be removed via a gas outlet 31.
• each gas sampling point 19 is connected to a device for solids separation 27 or, alternatively, a plurality of gas sampling points 19 are in each case directed into a device for solids separation 27.
• a design is preferred such that each gas sampling point 19 is connected to a separate device for solids separation 27.
• FIG. 2 shows a cross-section of the reactor in the region of the annular channel.
• the reactor 1 preferably has a circular cross-section so that it is symmetrical to a reactor axis 33 running vertically from top to bottom and shown in FIG.
• the central region 7 preferably has, as shown in Figure 1, a constant hydraulic diameter, so that the reactor shell 35, which surrounds the central region 7, has a cylindrical shape in a circular cross-section.
• the lower portion 9 has a decreasing hydraulic diameter, so that the hydraulic diameter in the region immediately above the fluidized bed at the smallest and at the upper end of the lower portion 9 with the decreasing hydraulic diameter is greatest.
• a region of constant volume closes as the hydraulic diameter decreases
• Diameter 37 so that the outer wall formed by the lower portion 9 of the annular channel 21 is parallel to the reactor axis and the annular channel thus below the annular channel upwardly wall 39 has a constant cross-sectional area 39.
• the ratio of the cross-sectional area 39 of the annular channel 21, which corresponds to the horizontal surface of the annular channel 21, to the surface 41 enclosed by the reactor jacket 35 is in the range of 0.3 to 5.

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• 2016
  • 2016-11-16 WO PCT/EP2016/077806 patent/WO2017085093A1/de active Application Filing
  • 2016-11-16 US US15/774,620 patent/US20180326392A1/en not_active Abandoned
  • 2016-11-16 CN CN201680065721.8A patent/CN108348883A/zh active Pending
  • 2016-11-16 JP JP2018544420A patent/JP2018535305A/ja active Pending
  • 2016-11-16 EP EP16797861.8A patent/EP3377212A1/de not_active Withdrawn

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