EP0131885B1 - Device to carry out a radical polymerisation, and its use - Google Patents

Device to carry out a radical polymerisation, and its use Download PDF

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Publication number
EP0131885B1
EP0131885B1 EP84108039A EP84108039A EP0131885B1 EP 0131885 B1 EP0131885 B1 EP 0131885B1 EP 84108039 A EP84108039 A EP 84108039A EP 84108039 A EP84108039 A EP 84108039A EP 0131885 B1 EP0131885 B1 EP 0131885B1
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EP
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Prior art keywords
stirrer
diameter
impeller
blades
blade
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EP84108039A
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German (de)
French (fr)
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EP0131885A3 (en
EP0131885A2 (en
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Helmut Klapp
Axel Dr. Dipl.-Ing. Wolf
Otmar Zajicek
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Wacker Chemie AG
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Wacker Chemie AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/112—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B01F27/1123—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades sickle-shaped, i.e. curved in at least one direction

Definitions

  • Radical polymerizations of ethylenically unsaturated monomers are generally carried out with stirring, mostly in stirred tanks, e.g. Stirred autoclaves.
  • stirred tanks e.g. Stirred autoclaves.
  • these containers have stirring devices which usually consist of a stirrer driven via a stirring axis and often additional stators.
  • the stators usually sheets or displacers of various shapes, serve as baffles. This is intended to achieve better mixing.
  • stirrers themselves are usually located on vertical stirrer axes (stirrer shafts) which generally protrude centrally from above or below into the container.
  • Stirrers driven in this way from above generally have the advantage of fewer sealing problems on the passage of the stirrer shaft through the container wall, if such a passage is necessary at all, but due to the greater length of the shaft, vibration (resonance) problems often occur, and the shaft must also have greater torsional rigidity.
  • the lower drive has these disadvantages comparatively to a much lesser extent, since the agitator shaft can be kept shorter for it, but in this embodiment there are greater sealing problems.
  • Stirrers are used in a wide variety of single and multi-stage designs, e.g. Centrifugal stirrer, cone stirrer, stirring rollers, cutting stirrer, bar stirrer, finger stirrer, frame stirrer, blade stirrer, turbine stirrer, propeller stirrer, disk stirrer, anchor stirrer and impeller stirrer.
  • Centrifugal stirrer cone stirrer, stirring rollers, cutting stirrer, bar stirrer, finger stirrer, frame stirrer, blade stirrer, turbine stirrer, propeller stirrer, disk stirrer, anchor stirrer and impeller stirrer.
  • a device consisting of a conventional reaction container, usually a closed container, e.g. an autoclave, with usual supply and discharge lines, which are generally connected to the container via valves, and a special centrically installed impeller stirrer 1, the vertical stirrer shaft 2 of which coincides with the longitudinal axis of the usually cylindrical container and which has a diameter d of 0.2 - Up to 0.9 times, preferably 0.4 to 0.7 times, the container inner diameter D.
  • the container can also be equipped with conventional cooling and / or heating devices, e.g. Cooling or heating jacket, through which a heat transport medium flows, and / or preferably reflux coolers and other conventional internals, e.g. Displacers, baffles, devices for spraying the walls and internals, etc.
  • the special impeller stirrer 1 has, on the stirrer axis 3, a ground clearance of 0.05 to 0.15 times the stirrer diameter d, the impeller blades 11 have an angle of incidence of 0 to 30 ° (upwards) with respect to the horizontal, so that the ground clearance on the wing tips 4 in the same area as on the stirrer axis 3, essentially parallel to the stirrer axis 3, inflow surfaces 5 and essentially triangular to semicircular (semicircular) cross-section 12.
  • the blade height h is 0.1 to 1 times, preferably that 0.1 to 0.5 times, in particular 0.15 to 0.3 times the stirrer diameter d, the blade thickness t of the stirring blades 11 is 0.5 to 5 times, preferably 0.6 bisl times the wing height h.
  • the impeller flaps are usually bent against the direction of rotation 10, the ratio of the stirrer diameter d to the radius r of the wings is 0 to 4, preferably 1 to 3.
  • the modified impeller stirrer 1 used according to the invention can preferably be used in the context of the device according to the invention in a reaction autoclave with an essentially cylindrical shape with dished, basket or flat bottoms.
  • the impeller 1 is installed in the container so that its stirrer shaft 2 coincides with the longitudinal axis or parts of the longitudinal axis of the cylindrical container part.
  • the stirrer 1 can be driven from above or from below.
  • the shape of the blades 11 can differ from the embodiment described above at the inner end 7, e.g. is also shown in Figures 1 and 3. However, this area is preferably kept as small as possible.
  • the cross section of the wings at the attachment point 8 can be circular or elliptical.
  • the device according to the invention can of course be made in all the materials from which the previous devices could be made, e.g. made of stainless steels, the coatings previously used can also be used within the scope of the invention, e.g. Glass and enamel covers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)
  • Polymerisation Methods In General (AREA)

Description

Radikalische Polymerisationen ethylenisch ungesättigter MOnomeren werden im allgemeinen unter Rührung durchgeführt, meist in Rührbehältern, z.B. Rührautoklaven. Diese Behälter besitzen dafür neben Kühl- und Heizeinrichtungen sowie Zu- und Ableitungen, auf die hier nicht weiter eingegangen werden muß, da sie dem Fachmann geläufig sind, Rührvorrichtungen, die meist aus einem über eine Rührachse angetriebenen Rührer und vielfach zusätzlichen Statoren bestehen. Die Statoren, meist Bleche oder Verdrängerkörper verschiedenster Formen dienen dabei als Stromstörer. Damit soll eine bessere Durchmischung erreicht werden.Radical polymerizations of ethylenically unsaturated monomers are generally carried out with stirring, mostly in stirred tanks, e.g. Stirred autoclaves. For this purpose, in addition to cooling and heating devices as well as supply and discharge lines, which need not be discussed further here since they are familiar to the person skilled in the art, these containers have stirring devices which usually consist of a stirrer driven via a stirring axis and often additional stators. The stators, usually sheets or displacers of various shapes, serve as baffles. This is intended to achieve better mixing.

Die Rührer selbst sitzen meist an senkrechten Rührachsen (Rührerschäften), die entweder von oben oder unten im allgemeinen zentrisch in den Behälter hineinragen. Auf solche Weise von oben angetriebene Rührer besitzen im allgemeinen den Vorteil geringerer Dichtungsprobleme an der Durchführung des Rührerschaftes durch die Behälterwandung, sofern eine solche Durchführung überhaupt notwendig ist, jedoch treten aufgrund der größeren Länge des Schaftes vielfach Schwingungs-(Resonanz-) Probleme auf, und der Schaft muß überdies größere Verwindungssteifigkeit besitzen. Diese Nachteile besitzt der Unterantrieb vergleichsweise in weitaus geringerem Ausmaß, da bei ihm der Rührerschaft kürzer gehalten werden kann, jedoch treten bei dieser Ausführungsform dafür größere Abdichtungsprobleme auf.The stirrers themselves are usually located on vertical stirrer axes (stirrer shafts) which generally protrude centrally from above or below into the container. Stirrers driven in this way from above generally have the advantage of fewer sealing problems on the passage of the stirrer shaft through the container wall, if such a passage is necessary at all, but due to the greater length of the shaft, vibration (resonance) problems often occur, and the shaft must also have greater torsional rigidity. The lower drive has these disadvantages comparatively to a much lesser extent, since the agitator shaft can be kept shorter for it, but in this embodiment there are greater sealing problems.

Für den Erfolg der im folgenden beschriebenen Erfindung sind beide Ausführungsformen geeignet, so daß der Fachmann die ihm für die Lösung seines speziellen Problems geeigneter erscheinende Ausführungsform auswählen kann.Both embodiments are suitable for the success of the invention described below, so that the person skilled in the art can select the embodiment which appears to him to be suitable for solving his specific problem.

Rührer werden in en verschiedensten ein- und mehrstufigen Bauformen eingesetzt, z.B. Kreiselrührer, Konusrührer, Rührwalzen, Schneidrührer, Balkenrührer, Fingerrührer, Rahmenrührer, Blattrührer, Turbinenrührer, Propellerrührer, Scheibenrührer, Ankerrührer und Impellerrührer.Stirrers are used in a wide variety of single and multi-stage designs, e.g. Centrifugal stirrer, cone stirrer, stirring rollers, cutting stirrer, bar stirrer, finger stirrer, frame stirrer, blade stirrer, turbine stirrer, propeller stirrer, disk stirrer, anchor stirrer and impeller stirrer.

Verglichen mit normalem Rührverfahren, z.B. dem Herstellen und Homogenisieren von Lösungen, treten bei radikalischen Polymerisationen zusätzliche Schwierigkeiten auf.Compared to normal stirring methods, e.g. the preparation and homogenization of solutions, additional difficulties arise in radical polymerizations.

Eines der größten Probleme bei der Herstellung von Polymerdispersionen, -suspensionen und -emulsionen ist die Gewährleistung der gleichmäßigen Rührung im gesamten Reaktionsgemisch, so daß sich keine Ruhezonen mit Monomernestern bilden können. In solchen Ruhezonen bilden sich ansonsten Polymer beläge an den Wandungen und Einbauten, bzw. zumindest bildet sich dort nicht spezifikationsgerechtes Polymer, das das restliche Produkt verunreinigt und ggf. mühsam, sofern überhaupt möglich, abgetrennt und verworfen werden muß. Die gleichmäßige Rührung über den gesamten Polymerisationsverlauf zu gewährleisten, stellt aufgrund der sich ständig ändernden Zusammensetzung des Reaktionsgemisches und des damit sich ändernden Viskositätsverhaltens den Fachmann vor große Probleme. Bekanntermaßen können das vielfach auftretende und sich zeitlich ändernde "nicht-newton'sche" Fließverhalten der flüssigen Phase solcher Polymerisationsgemische nicht so durch an sich übliche Rührversuche mit Wasser oder mit wäßrigen Lösungen nachgestellt werden, daß sich daraus für die eigentliche Verwendung der Rührsysteme bei der Polymerisation verläßliche Daten sammeln lassen.One of the biggest problems in the production of polymer dispersions, suspensions and emulsions is ensuring uniform stirring throughout the reaction mixture, so that no quiet zones can form with monomer esters. In such quiet zones, polymer deposits otherwise form on the walls and internals, or at least polymer that does not meet specifications is formed there, which contaminates the rest of the product and, if at all possible, has to be laboriously separated and discarded if at all possible. Ensuring uniform stirring over the entire course of the polymerization poses great problems for the person skilled in the art owing to the constantly changing composition of the reaction mixture and the viscosity behavior that changes as a result. As is known, the frequently occurring and changing "non-Newtonian" flow behavior of the liquid phase of such polymerization mixtures cannot be simulated by conventional stirring tests with water or with aqueous solutions in such a way that this results in the actual use of the stirring systems in the polymerization Have reliable data collected.

So lassen sich beispielsweise kaum verläßliche Daten über die Spitzen der Leistungsaufnahme der Rührer gewinnen, mit der Folge, daß aus Sicherheitsgründen die Polymerisationen mit größerer Verdünnung gefahren werden müssen.For example, it is difficult to obtain reliable data on the peak power consumption of the stirrer, with the result that the polymerizations have to be run at a higher dilution for safety reasons.

Eine dringliche Aufgabe bestand daher darin, die bisherigen Vorrichtungen zur radikalischen Polymerisation ethylenisch ungesättigter Monomeren in wäßrigem Medium so zu verbessern, daß die Polymerisationsreaktionen mit höheren Monomerkonzentrationen durchgeführt werden können, ohne daß für die Rührung die oben angesprochenen Sicherheitsrisiken auftreten, und ohne daß sich die üblichen Qualitätsschwankungen der Monomeren sofort negativ auf die Produktqualität auswirken.An urgent task was therefore to improve the existing devices for the radical polymerization of ethylenically unsaturated monomers in an aqueous medium so that the polymerization reactions can be carried out with higher monomer concentrations, without the above-mentioned safety risks for stirring, and without the usual Fluctuations in the quality of the monomers have an immediate negative impact on product quality.

Diese Aufgabe wurde gelöst durch eine solche Vorrichtung, bestehend aus einem üblichen Reaktionsbehälter, meist geschlossenem Behälter, z.B. einem Autoklaven, mit üblichen Zu- und Ableitungen, die im allgemeinen über Ventile mit dem Behälter verbunden sind, und einem speziellen zentrisch eingebauten Impellerrührer 1, dessen senkrechter Rührerschaft 2 mit der Längsachse des üblicherweise zylindrischen Behälters zusammenfällt und der einen Durchmesser d vom 0,2- bis 0,9- fachen, vorzugsweise 0,4- bis 0,7-fachen, des Behälterinnendurchmessers D besitzt. Der Behälter kann außerdem mit üblichen Kühl- und/oder Heizvorrichtungen, z.B. Kühl- bzw. Heizmantel, der von einem Wärmetransportmedium durchflossen wird, und/oder vorzugsweise Rückflußkühler und weiteren üblichen Einbauten versehen sein, z.B. Verdrängerkörpern, Stromstörern, Vorrichtungen zum Besprühen der Wandungen und Einbauten etc.This object was achieved by such a device, consisting of a conventional reaction container, usually a closed container, e.g. an autoclave, with usual supply and discharge lines, which are generally connected to the container via valves, and a special centrically installed impeller stirrer 1, the vertical stirrer shaft 2 of which coincides with the longitudinal axis of the usually cylindrical container and which has a diameter d of 0.2 - Up to 0.9 times, preferably 0.4 to 0.7 times, the container inner diameter D. The container can also be equipped with conventional cooling and / or heating devices, e.g. Cooling or heating jacket, through which a heat transport medium flows, and / or preferably reflux coolers and other conventional internals, e.g. Displacers, baffles, devices for spraying the walls and internals, etc.

Der spezielle Impellerrührer 1 besitzt, an der Rührerachse 3 einen Bodenabstand vom 0,05- bis 0,15- fachen des Rührerdurchmessers d, die Impellerflügel 11 besitzen einen Anstellwinkel von 0 bis 30° (nach oben) gegenüber der Horizontalen, so daß der Bodenabstand an den Flügelspitzen 4 im selben Bereich liegt wie an der Rührerachse 3, im wesentlichen zur Rührerachse 3 parallele Anströmflächen 5 und im wesentlichen dreieckigen bis halbkreisähnlichen (halbrunden) Querschnitt 12. Die Blatthöhe h beträgt das 0,1- bis 1-fache, vorzugsweise das 0,1- bis 0,5-fache, insbesondere das 0,15- bis 0,3-fache des Rührerdurchmessers d, die Blattdicke t der Rührflügel 11 beträgt das 0,5- bis 5-fache, vorzugsweise das 0,6- bisl-fachederFlügelhöheh.Dielmpellerflügeill sind meist entgegen der Drehrichtung 10 gebogen, das Verhältnis des Rührerdurchmessers d zum Radius r der Flügel beträgt 0 bis 4, vorzugsweise 1 bis 3.The special impeller stirrer 1 has, on the stirrer axis 3, a ground clearance of 0.05 to 0.15 times the stirrer diameter d, the impeller blades 11 have an angle of incidence of 0 to 30 ° (upwards) with respect to the horizontal, so that the ground clearance on the wing tips 4 in the same area as on the stirrer axis 3, essentially parallel to the stirrer axis 3, inflow surfaces 5 and essentially triangular to semicircular (semicircular) cross-section 12. The blade height h is 0.1 to 1 times, preferably that 0.1 to 0.5 times, in particular 0.15 to 0.3 times the stirrer diameter d, the blade thickness t of the stirring blades 11 is 0.5 to 5 times, preferably 0.6 bisl times the wing height h. The impeller flaps are usually bent against the direction of rotation 10, the ratio of the stirrer diameter d to the radius r of the wings is 0 to 4, preferably 1 to 3.

Vielfach ist es bevorzugt, die Vorderkanten 6 der Rührflügel 11 abzurunden. Als besonders zweckmäßig hat sich ein Verhältnis des zugehörigen Krümmungsradius k zur Blatthöhe h von k/h=0,01 bis 0,3 erwiesen.In many cases it is preferred to round off the leading edges 6 of the impeller 11. To be particularly useful in a ratio of the associated radius of curvature has k to the blade height h k / h = 0, proved 01 to 0.3.

Bei der bevorzugten Verwendung der erfindungsgemäßen Vorrichtung zur Herstellung von Vinylchlorid-Polymerisaten im wäßrigen Medium nach dem Suspensionspolymerisationsverfahren haben sich überraschenderweise folgende Vorteile ergeben:

  • 1. Der Rührer 1 kann mit niedrigerer Drehzahl betrieben werden, seine Leistungsaufnahme während der Polymerisation ist gleichmäßiger under geringer als bei herkömmlichen Vorrichtungen.
  • 2. Die Dispergierleistung ist größer, so daß gegebenenfalls das Monomer/Wasser-Verhältnis gesteigert werden kann.
  • 3. Der Einfluß von Schwankungen der Qualität der Monomeren auf das Produkt ist deutlich vermindert. Schwankungen der Produktqualität können verkleinert werden.
  • 4. Die Stippenbildung ist deutlich herabgesetzt.
  • 5. Aufgrund fehlender oder zumindest geringerer Bildung von Wandbelag können die Reaktionszeiten herabgesetzt werden.
The preferred advantages of the device according to the invention for the production of vinyl chloride polymers in the aqueous medium by the suspension polymerization process have surprisingly resulted in the following advantages:
  • 1. The stirrer 1 can be operated at a lower speed, its power consumption during the polymerization is more uniform and less than in conventional devices.
  • 2. The dispersing power is greater, so that the monomer / water ratio can be increased if necessary.
  • 3. The influence of fluctuations in the quality of the monomers on the product is significantly reduced. Fluctuations in product quality can be reduced.
  • 4. The formation of specks is significantly reduced.
  • 5. Because of the lack of or at least less formation of wall covering, the reaction times can be reduced.

Der erfindungsgemäß eingesetzte modifizierte lmpellerrührer 1 kann im Rahmen der erfindungsgemäßen Vorrichtung bevorzugt im Reaktionsautoklaven mit im wesentlichen zylindrischer Form mit Klöpper-, Korb- oder Flachböden eingesetzt werden. Das Verhältnis der lichten Höhe zum Innendurchmesser beträgt vorzugsweise H/D=1-3.The modified impeller stirrer 1 used according to the invention can preferably be used in the context of the device according to the invention in a reaction autoclave with an essentially cylindrical shape with dished, basket or flat bottoms. The ratio of the clear height to the inner diameter is preferably H / D = 1-3.

Der Impeller 1 ist in den Behälter so eingebaut, daß sein Rührerschaft 2 mit der Längsachse oder Teilen der Längsachse des zylindrischen Behälterteils zusammenfällt. Der Rührer 1 kann von oben oder von unten angetrieben werden.The impeller 1 is installed in the container so that its stirrer shaft 2 coincides with the longitudinal axis or parts of the longitudinal axis of the cylindrical container part. The stirrer 1 can be driven from above or from below.

In den beiliegenden Figuren 1-3 wird eine bevorzugte Ausführungsform des Rührers 1 schematisch dargestellt.

  • Fig. 1 stellt eine Aufsicht auf den Rührer 1 dar (längs des Rührerschaftes 2),
  • Fig. 2 stellt einen Querschnitt durch einen Rührerflügel 11 (entlang der Markierung A-A von Fig. 1) dar, und
  • Fig. 3 stellt eine Seitenansicht des Rührers 1 dar.
In the accompanying Figures 1-3, a preferred embodiment of the stirrer 1 is shown schematically.
  • 1 shows a top view of the stirrer 1 (along the stirrer shaft 2),
  • FIG. 2 shows a cross section through a stirrer blade 11 (along the marking AA from FIG. 1), and
  • 3 shows a side view of the stirrer 1.

Zur Erleichterung der Befestigung der Impellerflügel 11 am Schaft 2 kann die Form der Flügel 11 von der oben beschriebenen Ausführungsform am inneren Ende 7 abweichen, wie z.B. auch in den Figuren 1 und 3 dargestellt ist. Vorzugsweise wird dieser Bereich allerdings möglichst klein gehalten. Z.B. kann der Querschnitt der Flügel an der Befestigungsstelle 8 kreisförmig oder elliptisch sein.In order to facilitate the attachment of the impeller blades 11 to the shaft 2, the shape of the blades 11 can differ from the embodiment described above at the inner end 7, e.g. is also shown in Figures 1 and 3. However, this area is preferably kept as small as possible. E.g. the cross section of the wings at the attachment point 8 can be circular or elliptical.

Auch ist es möglich, die Kanten der äußeren Flügelenden 9 abzurunden, z.B. hat sich auch dort bewährt, eine Rundung mit dem Radius k vorzusehen.It is also possible to round off the edges of the outer wing ends 9, e.g. has also proven itself there to provide a radius k.

Die erfindungsgemäße Vorrichtung kann selbstverständlich in all den Materialien ausgeführt sein, aus denen die bisherigen Vorrichtungen gefertigt werden konnten, z.B. aus rostfreien Stählen, auch können die bisher verwendeten Beschichtungen im Rahmen der Erfindung verwendet werden, z.B. Glas- und Emailüberzüge.The device according to the invention can of course be made in all the materials from which the previous devices could be made, e.g. made of stainless steels, the coatings previously used can also be used within the scope of the invention, e.g. Glass and enamel covers.

Die folgenden Beispiele und Vergleichsversuche dienen lediglich der weiteren Erläuterung der Erfindung, sie besitzen keinen beschränkenden Charakter.The following examples and comparative experiments serve only to further explain the invention and are not restrictive in nature.

Ausführungsform 1-normaler ImpellerrührerEmbodiment 1-normal impeller stirrer

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Ausführungsform 2-erfindungsgemäßer ImpellerrührerEmbodiment 2-impeller stirrer according to the invention

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Beispiel 1:Example 1: PVC-Type A Ausführungsform 1PVC type A embodiment 1

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Beispiel 2:Example 2: PVC-Type A Ausführungsform 2PVC type A embodiment 2

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Beispiel 3:Example 3: PVC-Type B Ausführungsform 1PVC type B embodiment 1

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Beispiel 4:Example 4: PVC-Type B Ausführungsform 2PVC type B embodiment 2

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Claims (4)

1. Device for carrying out a free-radical polymerisation of ethylenically unsaturated monomers in an aqueous medium, consisting of a conventional reaction vessel with conventional feed and discharge lines, of a centrally installed impeller stirrer having a vertical stirrer shaft and a diameter d of 0.2 to 0.9 times the internal vessel diameter D, and, if appropriate, having cooling and/or heating devices and, if appropriate, further conventional internals, wherein the impeller stirrer has, at the stirrer axle, a distance from the bottom of 0.05 to 0.15 times the stirrer diameter d, the impeller blades have a setting angle a of 0 to 30° to the horizontal so that the distance from the bottom at the blade tips is within the same range as that at the stirrer axle, i.e. between 0.05 and 0.15 times the stirrer diameter d, the blades have flow impingement surfaces essentially parallel to the stirrer axle and an essentially triangular to semicircle-like cross-section, the blade height h is 0.1 to 1 times the stirrer diameter d, and the ratio of the stirrer diameter d to the radius r of the blades, which may be curved against the direction of rotation, is 0 to 4 and that of the blade thickness t to the blade height h is 0.5 to 5.
2. Device according to Claim 1, characterized in that the leading edges of the impeller blades are rounded off and the radius of curvature k is 0.01 to 0.3 times the blade height h.
3. Device according to Claim 1, characterized by the ratios:
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4. Use of the device according to one of the preceding claims for the production of vinyl chloride polymers in an aqueous medium by the suspension polymerisation process.
EP84108039A 1983-07-12 1984-07-10 Device to carry out a radical polymerisation, and its use Expired - Lifetime EP0131885B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833325095 DE3325095A1 (en) 1983-07-12 1983-07-12 DEVICE FOR CARRYING OUT A RADICAL POLYMERIZATION AND ITS USE
DE3325095 1983-07-12

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EP0131885A2 EP0131885A2 (en) 1985-01-23
EP0131885A3 EP0131885A3 (en) 1987-10-14
EP0131885B1 true EP0131885B1 (en) 1990-11-28

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NO177415C (en) * 1994-11-03 1995-09-13 Geir Nordahl Mixes with double curved blades
US5984520A (en) * 1994-11-03 1999-11-16 Nordahl; Geir Blade for a mixing device
CN103341336B (en) * 2013-06-17 2015-09-16 济南卡博唐生物科技有限公司 The agitator of stirred tank
DE102019124886A1 (en) * 2019-09-16 2021-03-18 EKATO Rühr- und Mischtechnik GmbH Agitator device
CN110980935B (en) * 2019-12-14 2022-03-15 浙江永续环境工程有限公司 Biofilm reactor

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Publication number Priority date Publication date Assignee Title
US2301204A (en) * 1939-07-28 1942-11-10 Du Pont Apparatus for polymerization processes
GB863055A (en) * 1958-01-21 1961-03-15 Union Carbide Corp Suspension polymerization and apparatus therefor
GB1053572A (en) * 1963-05-14

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EP0131885A3 (en) 1987-10-14
DE3325095A1 (en) 1985-01-24
DE3483668D1 (en) 1991-01-10
EP0131885A2 (en) 1985-01-23

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