EP3589398A1 - Dispositif et procédé pour produire des polymères pulvérulents - Google Patents

Dispositif et procédé pour produire des polymères pulvérulents

Info

Publication number
EP3589398A1
EP3589398A1 EP18708946.1A EP18708946A EP3589398A1 EP 3589398 A1 EP3589398 A1 EP 3589398A1 EP 18708946 A EP18708946 A EP 18708946A EP 3589398 A1 EP3589398 A1 EP 3589398A1
Authority
EP
European Patent Office
Prior art keywords
gas
turbulence
nozzles
reactor
flow
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
EP18708946.1A
Other languages
German (de)
English (en)
Inventor
Stephan Bauer
Markus Toennessen
Christophe Bauduin
Katrin Baumann
Marco Krueger
Andreas Daiss
Markus Muehl
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP3589398A1 publication Critical patent/EP3589398A1/fr
Pending legal-status Critical Current

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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
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
    • 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
    • B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • 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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/0092—Perforated plates
    • 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
    • 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
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical

Definitions

  • the invention is based on a device for the production of pulverulent polymers comprising a droplet polymerization reactor with a device for dropping a monomer solution for the production of the polymer with holes through which the monomer solution is introduced, a point of addition for a gas above the device for dripping , at least one gas sampling point on the circumference of the reactor and a fluidized bed.
  • the invention further relates to a process for the preparation of pulverulent polymers in such a device.
  • the apparatus used and the process are suitable, for example, for producing water-absorbing polymers, in particular poly (meth) acrylates, which are used in the production of diapers, tampons, sanitary napkins and other hygiene articles or as water-retaining agents in agricultural horticulture.
  • water-absorbing polymers in particular poly (meth) acrylates, which are used in the production of diapers, tampons, sanitary napkins and other hygiene articles or 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 may be added to a mixing kneader in which the monomers react to form the 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 dripping may be to act turbulent or laminar jet decay or even dripping.
  • the mechanism of droplet formation depends on the entry conditions and the material properties of the monomer solution.
  • the drops fall down 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.
  • the object of the present invention is therefore to provide an apparatus and a method for the production of pulverulent polymers in which an improved mixing of the drying gas and the dripped-in monomer solution is ensured and, moreover, that the droplets are distributed more homogeneously over the reactor cross section.
  • a device for the production of powdery polymers comprising a dropwise polymerization reactor with a device for dropping a monomer solution for the preparation of the polymer, wherein the device for dropping (5) has holes through which the monomer solution is introduced, a Loading 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 at least one of the following features is fulfilled:
  • a device for turbulence increase in the gas flow is arranged,
  • a device for turbulence increase in the gas flow is arranged,
  • the gas addition point is designed to produce increased turbulence.
  • step (a) dripping a monomer solution in the device for dripping, wherein the generated monomer droplets fall through the reactor and the monomer at least partially reacts with the polymer to form particles, (b) supplying gas via the gas addition point above the dropper to produce gas flow in the reactor from top to bottom; (c) collecting the particles produced in step (a) in the fluidized bed, wherein in the fluidized bed the reaction to the polymer in the individual particles is completed and optionally a post-crosslinking takes place,
  • the gas flow generated from top to bottom in the reactor is also referred to as the drying gas flow and the gas supplied via the gas addition point is also referred to as the drying gas.
  • the drops produced are already distributed relatively homogeneously over the reactor cross-section and thus also mixed with the drying gas. Nevertheless, variations in the droplet concentration and the gas temperature, which lead to incomplete utilization of the drying gas, generally result locally above the reactor cross section.
  • the drying gas is understood here as the water absorption and heat emission of the gas, which sets a fully homogeneous temperature and a largely homogeneous water concentration in the gas in a full utilization of the drying gas over the reactor cross-section.
  • the temperature distribution and the water concentration are not homogeneous over the reactor cross-section.
  • a defined flow turbulence is generated in the gas phase, which increases the homogeneity of the distribution of the droplets over the reactor cross section and thus ensures an even better mixing of the drying gas with the droplets from the monomer solution.
  • the flow turbulence must neither be too small, because the homogenizing effect is otherwise negligible, nor too large, because otherwise drops or Particles can get too fast to the reactor wall and lead there to a deposit formation.
  • any device can be used with which the turbulence of the gas flow can be increased.
  • an apparatus for turbulence increase for example, flow obstacles can be used, which are arranged above or below the device for dropping.
  • gas nozzles, gas / liquid nozzles or liquid nozzles it is also possible to use gas nozzles, gas / liquid nozzles or liquid nozzles to increase turbulence.
  • the circulation of the flow obstacles swirls the drying gas and in this way increases the turbulence.
  • the flow obstacles are preferably placed so that they are always at a gap between the individual when placed below the device for dripping in an imaginary vertical projection Vertropfer adopteden the device for dripping sitting and are not taken directly from the droplets formed at the Vertropfer wornen. By size and number of flow obstacles, the degree of flow turbulence can be adjusted.
  • Suitable flow obstacles are, for example, arbitrarily shaped, vertically or substantially perpendicular to the vertical plates arranged, for example, round, rectangular or polygonal plates, or any other body that cause a significant separation of the flow and thus generation of flow turbulence.
  • flow obstacles also perforated plates can be used or the Vertropfer wornen can be modified in their geometry so that thereby an additional increase in turbulence takes place.
  • the flow obstructions may also include a perforated bottom having holes with a hydraulic diameter of 5 to 200 cm, preferably 10 to 100 cm.
  • the holes may be arbitrarily shaped, for example, be circular, polygonal or elliptical. Preferably, the holes are circular.
  • the size of the holes in the hole bottom prevents - unlike very fine free jets, which emerge from small holes with a few millimeters in diameter, as they are formed in conventional hole bottoms, the induced flow turbulence is immediately dissipated by friction. The turbulence thus generated leads, as with the flow obstacles, to a homogenization of the gas phase temperature and of the particle concentration.
  • the gas addition point may for example have one or more perforated plates and is usually designed so that a sufficient uniform distribution of the in the reactor inflowing drying gas is achieved.
  • the gas addition site may also include one or more gas nozzles that generate flow turbulence.
  • Increased turbulence in the context of the present invention means that the local turbulence of the gas flow in the area of the dropletizing devices or below the dropletizing devices is greater than the mean turbulence which the incoming gas would have solely due to the mean gas velocity in the reactor.
  • the parts of the device for dropping in which the droplets are generated.
  • Vertropfer- devices such as spray nozzles can be used.
  • the dropletizing devices each comprise a dropletizing channel which has holes on its underside through which the monomer solution is dripped.
  • the holes are particularly preferably formed in perforated plates which form the underside of the Vertropferkanals.
  • nozzles can also be used to increase the turbulence.
  • the device for turbulence increase gas nozzles
  • Gas / liquid nozzles or liquid nozzles are gas / liquid nozzles or liquid nozzles, in one embodiment they are part of the device for dropping the monomer solution.
  • an increased turbulence can be achieved, for example, by increasing the entry momentum of the droplet jets of the dropletizing devices or by using spray nozzles to produce the droplets.
  • spray nozzles or increasing the droplet jet velocity also entail the risk that droplets reach the reactor wall at an early stage and as a result deposit formation occurs.
  • gas nozzles as nozzles for increasing the turbulence.
  • Gas nozzles induce turbulence downstream of the nozzle free jet depending on nozzle diameter and gas exit velocity.
  • the nozzles can at the height of the droppers or slightly below or above the droppers.
  • the nozzles preferably also sit on the gap between the Vertropfer adopteden to avoid that drop jets hit the nozzles and lead to a rapid deposit formation on the nozzles.
  • the turbulence induced by the nozzles is essentially determined by the pulse current I D introduced by the nozzles.
  • the momentum flow is the product of mass flow and gas velocity of the free jet at the outlet of the nozzles:
  • v D Mean flow velocity of the free jet at the nozzle outlet [m / s]
  • the pulse stream of the drying gas is here
  • the ratio r TG is preferably in the range of 0.1 to 50, more preferably in the range of 0.2 to 20 and particularly preferably in the range of 0.5 to 10.
  • the ratio r r is preferably in the range of 0.1 to 100, more preferably in the range of 0.2 to 50, and particularly preferably in the range of 0.5 to 20.
  • the desired pulse I D of the turbulence-generating nozzles can be adapted both by the mass flow and by the nozzle exit speed.
  • the locally generated turbulence is very high, but this is very fine-scale and is immediately dissipated by friction, so that it is no advantage to choose particularly high exit velocities.
  • very high exit velocities result in high noise loading and higher power required to produce nozzle flow.
  • the nozzle exit velocity is therefore preferably selected in a range between 5 and 1000 m / s, more preferably between 10 and 500 m / s and particularly preferably between 20 and 300 m / s. From the desired pulse current is then obtained when selecting the speed of the required mass flow. This finally results in the required nozzle cross-section.
  • the shape of the nozzle cross-section is of minor importance. Can be used round, slot-like, elliptical or optionally also nozzles with multiple openings.
  • the reactor cross-sectional area per turbulence generation nozzle in the region of the reactor having a constant hydraulic diameter is preferably between 0.5 and 50 m 2 , preferably between 1 and 25 m 2 and particularly preferably between 2 and 10 m 2 .
  • gas nozzles used for turbulence increase, gas / liquid nozzles or liquid nozzles, in particular gas nozzles, in the range of 0.02 to 2 per square meter reactor cross-sectional area, more preferably 0.04 to 1 and in particular 0.1 to 0.5.
  • the dropwise polymerization reactor comprises a central region of constant hydraulic diameter, a conically shaped reactor head of downward increasing hydraulic diameter, and a lower region which is also conical, in which case the hydraulic diameter decreases from top to bottom, and the device for Dropper and the device for turbulence increase are arranged in the reactor head
  • the above sizes refer to the reactor cross-sectional area in the central region with a constant hydraulic diameter.
  • the turbulence increasing device is located in the area of the monomer solution dripping device, the turbulence increasing device is preferably arranged in a range between 2 m above and 2 m below the dripping device.
  • the device for turbulence increase is 1 m above to 1 m below arranged the device for Vertropfung. If the device for dripping comprises drip devices at different heights, the height of the device for dripping, which is used to determine the distance of the device for turbulence increase, the middle level, in which the Vertropfer sensibleen are arranged, is used.
  • the turbulence increasing device When the turbulence increasing device is located in the vicinity of the gas addition point, the turbulence increasing device is located up to 2 m below the gas addition point, and more preferably in a range between 10 cm and 1 m below the gas addition point.
  • the devices for turbulence increase that is, the gas nozzles, gas / liquid nozzles or liquid nozzles or the flow obstacles can be arranged at different heights. This is particularly advantageous when the Vertropfer wornen are arranged at different heights or when mounting reasons make a different height required.
  • all flow obstacles, gas nozzles, gas / liquid nozzles or liquid nozzles of the device for turbulence increase can be arranged at a height in the reactor. This is particularly advantageous when the Vertropfer wornen are also arranged at a height.
  • the orientation of the nozzles can take place vertically downwards or vertically upwards, other orientations are conceivable. For example, a slight adjustment of the nozzles can take place in the direction of the reactor axis or also to the outside. Likewise, the nozzles may also have a partial tangential orientation. However, it must always be borne in mind that, as in the case of a tangential orientation, for example, there is the danger that particles will be entrained by the nozzle streams, reach the reactor wall at an early stage and lead to deposit formation. It is particularly preferred if the nozzles are aligned vertically upwards, that is, that the gas flow exiting through the gas nozzles is directed counter to the flow of the drying gas. Such an orientation causes the largest turbulence increase.
  • the distribution of the nozzles used as a device for turbulence increase over the reactor cross section depends on the arrangement of the Vertropfer wornen. In principle, it is advantageous to distribute the nozzles as uniformly as possible over the reactor cross-section in order to produce the most uniform flow turbulence possible. It is also advantageous to gap the nozzles with respect to the horizontal position of the dropletizers so as not to cause direct jet-to-droplet jet interaction. Likewise, it is advantageous to arrange the nozzles as symmetrically as possible relative to the dropletizing devices.
  • the ratio of that of the device the area covered by dripping in the reactor, based on the area enclosed by the line connecting the outermost holes, is less than 50% and preferably in the range between 3 and 30%.
  • the device according to the invention and the method according to the invention are preferably used for the production of water-absorbing polymers, in particular for the preparation of poly (meth) acrylates.
  • poly (meth) acrylates are understood as meaning polyacrylates, polymethacrylates and any desired mixture of polyacrylates and polymethacrylates.
  • FIG. 1 shows a longitudinal section through a droplet polymerization reactor with a device for turbulence elevation below the device for dripping, a longitudinal section through a droplet polymerization reactor with a device for turbulence elevation above the device for dripping, an arrangement of radially extending droplet channels of different lengths and between the droplets Channels arranged turbulence increasing device, an arrangement of star-shaped Vertropferkanälen and arranged between the channels turbulence increasing devices, an array of Vertropferkanälen in rectangular pitch and arranged between the channels devices for turbulence increase,
  • FIG. 6 shows an arrangement of dropletizing channels in triangular division and turbulence-increasing devices arranged between the channels.
  • FIG. 7 shows an upper section of a drop polymerization reactor in which the gas addition point is designed to generate increased turbulence.
  • FIG. 8 shows an upper section of a drop polymerization reactor with gas nozzles pointing upwards as a device for turbulence increase,
  • FIG. 10 shows a profile of the total temperature as a function of the particle residence time with and without the use of a device for turbulence increase, wherein the dashed curve represents the case with and the solid curve represents the case without turbulence increase.
  • Figure 1 shows a longitudinal section through a reactor for droplet polymerization, as it is preferably used for the preparation of poly (meth) acrylate particles.
  • 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 a plurality of channels, it is preferable to supply the monomer solution to each channel via its own monomer feed 12.
  • the monomer solution exits through holes, not shown in FIG. 1, in the dropletizing device 5 and breaks down into individual drops which fall downwards in the reactor.
  • a gas for example nitrogen or air, is introduced into the reactor 1. The gas flow thereby supports the disintegration of the monomer solution emerging from the holes of the device for dropping 5 into individual drops. In addition, the gas flow assists that the individual drops do not touch each other and coalesce into larger 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 in the reactor head 3 cylindrical with a diameter as in the central region 7.
  • a conical configuration of the reactor head 3 is preferred. The position of the dropletizing device 5 is selected so that a collision occurs between the outermost holes, through which the monomer solution is supplied and the wall of the reactor, is still a sufficiently large distance to prevent the drop to 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.
  • this has the disadvantage that with a greater distance is associated with a poorer utilization of the reactor cross-section.
  • a device for increasing the turbulence 31 is used in the region of the device 5 for dripping the monomer solution.
  • the device for turbulence increase the turbulence of the gas is increased, so that a better mixing of gas and drops generated with the device for dropletizing 5 is realized. This allows the drops to deliver even water to the gas.
  • a more uniform temperature distribution over the residence time of the droplets is obtained in the reactor.
  • the turbulence generated by the device for turbulence increase 31 is shown here by arrows 33.
  • flow obstructions or nozzles in particular gas nozzles, gas / liquid nozzles or liquid nozzles can be used as the device for turbulence increase 31.
  • 31 gas nozzles 35 are used as the device for increasing turbulence. These are arranged in the embodiment shown in Figure 1 below, preferably at most 2 m below the device for dropping 5.
  • the gas jet 37 emerging from the gas nozzles 35 the gas supplied via the gas injection point 10 is accelerated.
  • the gas emerging from the gas nozzles 35 is decelerated, whereby the gas jet 37 is deflected and deformed, so that an additional turbulence is induced.
  • the difference in velocity between the gas added by the gas addition point 13 and the gas added through the gas nozzles 35 is not too great, so that the generated turbulence is not dissipated by the friction that occurs.
  • 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 is at the level of the middle between the device. dripping and the gas sampling point 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 may be provided, with which the wall of the reactor is vibrated, thereby dissolving adhering polymer particles and slip into the fluidized bed 1 1.
  • a gas distributor 17 For gas supply for the operation of the fluidized bed 1 1, located below 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 central region 7 with a constant cross-section to the conically extending from bottom to top lower portion 9.
  • the cylindrical central portion 7 protrudes with its wall in the upwardly conically widening lower portion 9, wherein the diameter of the conical lower portion 9 at this position is greater than the diameter of the central region 7.
  • the wall of the middle Area 7 circumferential annular chamber 21 is formed, into which the gas flows and can be withdrawn through the at least one gas sampling point 19 which is connected to the annular chamber 21.
  • the post-reacted polymer particles of the fluidized bed 1 1 are removed via a product removal point 23 in the fluidized bed.
  • Figure 2 shows a reactor for drop polymerization in an alternative embodiment.
  • the device for turbulence elevation 31 is positioned above the device 5 for dropletizing the monomer solution.
  • FIG. 2 also shows, by way of example, gas nozzles 35 for increasing the turbulence.
  • gas nozzles 35 for increasing the turbulence.
  • the turbulence can be adjusted in a simple manner by changing the velocity of the gas leaving the gas nozzles 35.
  • the individual flow obstacles or nozzles of the device for turbulence-increasing 31 are positioned such that they are interposed between the individual dropletizing devices.
  • FIG. 3 shows an arrangement of radially extending droplet channels of different lengths.
  • the device for dripping has radially extending channels 25.
  • a portion of the channels 25 extends into the middle of the reactor 1.
  • Another portion of channels 24 projects less far into the reactor 1, so that in particular in the outer regions of the reactor, where the distance between the radially extending to the center the reactor 1 protruding channels 25 is large, further channels 24 are provided, can be introduced through the monomer solution in the reactor 1. This allows a more uniform distribution of the drops over the entire reactor cross-section.
  • the individual gas nozzles 35 which are used to increase the turbulence, are positioned between the channels 24, 25.
  • the gas nozzles 25 are evenly distributed over the reactor cross-section for a uniform turbulence and thus a uniform gas flow in the reactor.
  • FIG. 25 A corresponding star-shaped arrangement of the channels 25 is shown in FIG.
  • FIGS. 5 and 6 Further possible arrangements of the channels are shown in FIGS. 5 and 6. In these, however, an arrangement having an angle ⁇ to the horizontal is difficult to realize, so that in this case the channels 25 preferably extend horizontally.
  • Figure 5 shows an arrangement in rectangular division, in which the individual channels 25 are each arranged at an angle of 90 ° to each other, so that each rectangles, preferably squares are formed by the intersections 27 of the channels.
  • FIG. 6 shows an arrangement in triangular division.
  • the channels 25 are each arranged at an angle of 60 ° to each other, so that 25 each equilateral triangles are formed by the intersections 27 of the channels.
  • this also requires that the respective parallel channels always have the same distance.
  • the flow obstacles or nozzles are evenly distributed over the reactor cross-section between the dropletizers.
  • the position of the flow obstacles or nozzles is preferably in each case in the center of the rectangles or triangles formed by the channels 25.
  • the necessary supply of gas and / or liquid preferably takes place via lines 39, which in an arrangement as shown in FIGS. 3 and 4 extend between the channels 24, 25 or in the case of an arrangement as shown in FIGS 5 or 6, above the channels 25 run to prevent drops generated in the device 5 drops fall on the lines 39 and lead there to a deposit formation.
  • FIGS. 3 and 4 are preferred.
  • the number of channels may vary depending on the size of the reactor.
  • a rotationally symmetrical arrangement is always preferred.
  • the number of channels 24, 25 is chosen such that the ratio of the area covered by the channels 24, 25 or the droplet head in the reactor relative to the area defined by the circumference of a line along the outermost holes is smaller than 50%. This ensures that sufficient gas can flow past the channels 24, 25 and a sufficient contact between the gas and the channels 24, 25 leaving drops is realized.
  • FIG. Another possibility for generating an increased turbulence in the gas flow is shown in FIG.
  • the addition point for gas 13 is designed so that an increased turbulence is generated.
  • the addition point for gas 13 comprises at least one perforated bottom 41, through which the gas is passed.
  • the hole bottom has holes that have a hydraulic diameter of 5 to 200 cm, preferably from 10 to 100 cm. It is particularly advantageous if a plurality of perforated plates are arranged one above the other and at least the last hole bottom in the flow direction of the gas as described above has holes with a hydraulic diameter of 5 to 200 cm.
  • the arrangement of the perforated plates is preferably carried out so that the holes of the individual perforated plates are not exactly on top of each other. This means that the centers of superimposed holes are not on a vertical axis.
  • the shape of the holes can be chosen arbitrarily. However, preferred are circular holes.
  • the gas addition point 13 such that increased turbulence is generated, the gas flow already above the device 5 for dropletizing turbulence 33, which leads to a more homogeneous distribution of drops generated in the device 5 for droplet over the reactor cross-section .
  • the turbulence increase should be localized and preferably act only in the region or below the dropletizing units. As a result, the desired improved mixing of the drying gas with the dripped monomer solution is ensured and the droplets are distributed more homogeneously over the reactor cross-section, without resulting in undesirable effects such as scale formation on the reactor wall.
  • FIG. 1 A preferred embodiment of the device for turbulence increase is shown in FIG.
  • the gas nozzles 35 are oriented vertically upwards.
  • the gas nozzles 35 thus each leaves a gas jet 37 which is directed against the flow direction of the drying gas supplied via the point of addition of the gas 13. Due to the gas emerging from the gas nozzles 35 in the opposite direction to the flow direction of the drying gas, the turbulence 33 is generated in the region of the dropletizing device 5. Since the drying gas is the main gas flow, the total gas flow is directed downwards and the drying gas flow remains turbulent in the flow direction of the drying gas as it flows past the device 5 for dripping.
  • the flow turbulence in the drying gas stream up to the device for dropping 5 can spread better across and thus more effectively and uniformly affect the exiting from the device for dropping 5 monomer solution.
  • the flow obstructions or nozzles of the turbulence-increasing device 31 are always positioned so that no droplets are present. can fall on the flow obstacles or nozzles. Furthermore, the flow obstacles or nozzles are evenly distributed over the reactor cross-section to obtain a uniform gas flow and turbulence throughout the reactor cross-section to produce a uniform product.
  • the diameter of the reactor at the level of the Vertropfer wornen is 7.2 m.
  • the gas volume flow, which is fed in via the addition point for gas 13, is 175,000 Nm 3 / h.
  • FIG. 9 shows the course of the standard deviation of the particle temperature as a function of the particle residence time for the two calculated cases, wherein the course for the first case with gas nozzles for turbulence increase is shown with a dashed line and the profile for the second case without turbulence increase with a solid line.
  • the particle dwell time in seconds and the ordinate the standard deviation are shown on the abscissa. The higher the standard deviation, the more heterogeneous is the particle heating up.
  • the residence time range of 0 to 6 s the standard deviation in the case of operation with turbulence nozzles is up to 5 K lower than in the case without turbulence nozzles.
  • the residence time of 6 seconds corresponds to the time it takes for the particles to reach the fluidized bed at the lower end of the reactor.
  • FIG. 10 shows the gas temperature of the gas surrounding the particles along their trajectory as a function of the particle residence time. Again, the particle residence time is shown in seconds on the abscissa. The ordinate shows the temperature of the gas surrounding the particles in ° C. Again, the first case with gas nozzles for turbulence increase with a dashed line and the second case without additional turbulence increase with a solid line shown. In the case of operation with gas nozzles for turbulence increase, the gas temperature decreases faster, which means that the particles are heated on average faster.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Polymerisation Methods In General (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un dispositif pour produire des polymères pulvérulents, comprenant un réacteur (1) pour réaliser une polymérisation par pulvérisation, comportant un dispositif de génération de gouttes (5) d'une solution monomère pour la production du polymère, le dispositif de génération de gouttes (5) étant pourvu de trous à travers lesquels la solution monomère est introduite, un point d'addition (13) pour un gaz situé en amont du dispositif de génération de gouttes (5), au moins un point de prélèvement de gaz (19) situé sur la périphérie du réacteur (1) et un lit fluidisé (11), au moins une des caractéristiques suivantes étant présente : dans la zone du dispositif de génération de gouttes (5) de la solution monomère est agencé un dispositif d'augmentation de turbulence (31) de l'écoulement gazeux, dans la zone du point d'addition (13) de gaz est agencé un dispositif d'augmentation de turbulence de l'écoulement gazeux, le point d'addition (13) de gaz est conçu de manière qu'une turbulence accrue soit générée. Cette invention concerne en outre un procédé pour produire des polymères pulvérulents, la turbulence de l'écoulement gazeux étant augmentée dans la zone du dispositif de génération de gouttes (5).
EP18708946.1A 2017-03-01 2018-02-26 Dispositif et procédé pour produire des polymères pulvérulents Pending EP3589398A1 (fr)

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PCT/EP2018/054657 WO2018158191A1 (fr) 2017-03-01 2018-02-26 Dispositif et procédé pour produire des polymères pulvérulents

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US11332550B2 (en) 2017-03-01 2022-05-17 Basf Se Device and method for producing powdered polymers
US11376559B2 (en) * 2019-06-28 2022-07-05 eJoule, Inc. Processing system and method for producing a particulate material

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JP2020509130A (ja) 2020-03-26
JP7143315B2 (ja) 2022-09-28
US20200231711A1 (en) 2020-07-23
CN110352092B (zh) 2022-10-21
US11332550B2 (en) 2022-05-17
WO2018158191A1 (fr) 2018-09-07
CN110352092A (zh) 2019-10-18

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