EP0749776A1 - Mixer with tubular housing - Google Patents

Mixer with tubular housing Download PDF

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Publication number
EP0749776A1
EP0749776A1 EP95810418A EP95810418A EP0749776A1 EP 0749776 A1 EP0749776 A1 EP 0749776A1 EP 95810418 A EP95810418 A EP 95810418A EP 95810418 A EP95810418 A EP 95810418A EP 0749776 A1 EP0749776 A1 EP 0749776A1
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EP
European Patent Office
Prior art keywords
mixer according
mixer
mixing
elements
separating webs
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Granted
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EP95810418A
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German (de)
French (fr)
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EP0749776B1 (en
Inventor
Felix Streiff
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Sulzer Chemtech AG
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Sulzer Chemtech AG
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Application filed by Sulzer Chemtech AG filed Critical Sulzer Chemtech AG
Priority to DE59508992T priority Critical patent/DE59508992D1/en
Priority to AT95810418T priority patent/ATE198839T1/en
Priority to EP95810418A priority patent/EP0749776B1/en
Priority to ES95810418T priority patent/ES2155509T3/en
Priority to DE29522199U priority patent/DE29522199U1/en
Priority to TW085105453A priority patent/TW315314B/zh
Priority to CA002178065A priority patent/CA2178065C/en
Priority to US08/660,434 priority patent/US5944419A/en
Priority to KR1019960020691A priority patent/KR100420822B1/en
Priority to CN96111003A priority patent/CN1052171C/en
Priority to BR9602858A priority patent/BR9602858A/en
Priority to JP15997396A priority patent/JP4283901B2/en
Publication of EP0749776A1 publication Critical patent/EP0749776A1/en
Publication of EP0749776B1 publication Critical patent/EP0749776B1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/42Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/432Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction with means for dividing the material flow into separate sub-flows and for repositioning and recombining these sub-flows; Cross-mixing, e.g. conducting the outer layer of the material nearer to the axis of the tube or vice-versa
    • B01F25/4321Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction with means for dividing the material flow into separate sub-flows and for repositioning and recombining these sub-flows; Cross-mixing, e.g. conducting the outer layer of the material nearer to the axis of the tube or vice-versa the subflows consisting of at least two flat layers which are recombined, e.g. using means having restriction or expansion zones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying

Definitions

  • the invention relates to a mixer which is arranged in a tube and which comprises at least one mixing element or a mixing body. It also relates to uses of such a mixer.
  • a mixer is known from US Pat. No. 3,051,453, which is composed of a linear arrangement of mixing elements, which are referred to below as "multiflux mixing bodies".
  • This multiflux mixing body the cross section of which is square, has two channels which continuously narrow in the direction of flow up to the center of the mixing body and continuously expand behind the narrowest point in a plane rotated by 90 °.
  • a medium flowing through the mixing body undergoes a deformation by which the number of partial layers doubles.
  • the Multiflux mixing body can be made up of four wedge-shaped partial bodies and two build up triangular plates.
  • the wedges have the shape of a halved cube, which is halved along the diagonal of one side surface. Two of the wedges - one rotated 90 ° relative to the other - each form a coherent part. The two plates form partitions between the two channels of the mixing body.
  • the partial bodies take up a volume that is 25 to 30% of the tube volume assigned to the mixing body.
  • ISG Interfacial Surface Generator
  • the known Multiflux and ISG mixing bodies require a relatively large amount of material for their production, the volume of which takes up at least 25 to 30% of the tube volume.
  • the lengths of the mixing bodies in the direction of flow are relatively long, namely approximately the same size as the pipe diameter.
  • This object is achieved with the features mentioned in claim 1.
  • the empty volume is greater than 80 to 90%; and thus the material requirement is significantly lower.
  • the mixing element of the mixer according to the invention can be considerably shorter, namely at least half as long comparable effect as with the known mixing bodies.
  • a mixer with a plurality of such mixing elements is defined in claim 2.
  • the dependent claims 3 to 18 relate to advantageous embodiments of the mixer according to the invention.
  • Claims 19 and 20 relate to uses of the mixers.
  • the mixer according to the invention has mixing elements with a particularly simple shape. Thanks to this shape, a monolithic mixing body, which comprises a series of several mixing elements connected in series, can be easily produced by injection molding from plastic or investment casting (steel), whereby two-part tools can be used in particular in the simplest embodiment (two-hole variant).
  • the mixing bodies according to the invention can also be produced in a simple manner, for example from sheet metal.
  • the mixer according to the invention is less expensive than the known static mixers: two flowable media of similar viscosity can be homogeneously mixed over a distance (L) of less than ten pipe diameters (D).
  • the mixer according to the invention has no channels with confuser and diffuser-like sections or bores. Trials have shown that simple disks with holes and dividers, which are arranged on the discs, deliver a surprisingly good mixing quality. Effects that were to be expected due to the lack of confuser-like and diffuser-like sections proved to be practically without any disturbing influence with regard to the mixing quality.
  • Pipes of any cross section can be provided for the mixer according to the invention; however, square or circular cross sections are preferred.
  • the Multiflux mixer is surpassed in the specific effects by the tested mixers.
  • the mixing elements 1 and 1 'of FIG. 1 arranged in a tube 10 each consist of two separating webs 2 and 2' and two deflection disks 3 and 3 ', respectively, in a plane 3a and 3a' indicated by dash-dotted lines. lie.
  • the plane 3a lies perpendicular to the pipe axis 5 and parallel to planes 2a and 2b, which touch the upper edge 20 or the lower edge 21 of the separating webs 2.
  • the three levels 2a, 3a and 2b delimit two sections 1a and 1b of the mixing element 1.
  • Each section is assigned a separating web 2 which divides the section.
  • the separating webs 2 of the two sections 1a and 1b intersect at a right angle.
  • the pipe cross section is divided by the separating webs 2 into four parts of the same size, two of these parts being covered by the deflection plates 3.
  • the open partial areas are provided as constrictions and through holes 4 for the medium to be mixed.
  • the two successive mixing elements 1 and 1 ' are constructed essentially the same. But the mixing element 1 represents the mirror image of the mixing element 1 '.
  • the adjacent dividers 2 and 2' intersect; the open partial areas 4 and 4 'are arranged offset from one another.
  • the deflection disks 3 can also form an angle ⁇ with the cross-sectional plane 3a - see FIG. 2. This angle ⁇ is advantageously chosen not to be greater than 30 °.
  • Figures 3 and 4 show further embodiments with inclined surfaces. If the axis 5 is understood as a vertical, the arrow 6 in FIGS. 2 to 4 each represents the falling line of a deflection disk 3. In FIG. 2, this arrow 6 is parallel to the upper one Separator 2. In the exemplary embodiment in FIG. 3, the arrow 6 is tangential to a circular cylinder which is concentric with the axis 5. In the embodiment of Figure 4, the arrow 6 is directed radially outwards.
  • FIGS. 5a and 5b show mixing elements 1 and 1 ', in each of which two separating webs 2 are assigned to a section 1a and 1b (not shown in these figures).
  • Exactly one open partial area 4 is arranged on both sides of each separating web 2.
  • the mixing element 1 'with the open partial areas 4' represents an immediately adjacent element of the mixing element 1.
  • the open partial areas 4 and 4 ' are arranged offset from one another.
  • the shapes of the two mixing elements 1 and 1 ' are identical and are not mirror images as in the two-hole variant (FIG. 1).
  • the elements can be divided into two halves.
  • the boundaries between the half-elements are indicated in FIGS. 5a and 5b as dash-dotted lines 7 and 7 ', respectively.
  • Monolithic partial bodies, each comprising a series of such half-elements, can be produced in a simple manner with two-part tools.
  • the entire mixing body is obtained by joining two monolithic partial bodies.
  • the flow path of the medium to be mixed is additionally indicated by arrows 8, 8 'and 8' '.
  • the arrow 8 ' is perpendicular to the image surface and is directed forward; the arrow 8 '' - also vertical - is directed towards the rear.
  • the reference numeral 9 indicates a point where the generation of two partial flows is indicated by the arrows.
  • the deflection plates 3 are advantageously in a common plane. If there are at least two dividers 2 per section (three-hole variant), several deflection disks 3 can form a common disc or a single disc 30 (four-hole variant): see FIGS. 5a and 5b and the corresponding FIGS. 7a and 7b for the four-hole Variant.
  • FIGS. 7a and 7b only the single and common deflection plate 30 and 30 'is shown.
  • the dash-dotted lines 23 represent the lower edges of the upper dividers.
  • the shapes of adjacent mixing elements are mirror images of one another in the four-hole variant.
  • the mixer according to the invention can also have a cross section with a different shape, for example a square.
  • Sections 1a and 1b can be of different lengths. The length of the sections 1a and 1b is advantageously in the range between D / 8 and D; it is preferably D / 4.
  • FIG. 8 illustrates what deviations from the simple shapes described above are conceivable, for example: connecting elements 35 are arranged between the spaced-apart mixing elements 1, 1 '.
  • the Separators 2 have additional elements 25 for reinforcement or flow control. Separators 2 'and 2''of adjacent mixing elements 1' and 1 '' are inserted into one another at position 29. Individual dividers 2 and deflection plates 3 are not flat.
  • the mixing elements 1 and 1 ' have different numbers of dividers 2 and 2' per section 1a and 1b, namely two and one, respectively.
  • a separating web 2 has a recess 29. 8 is only to be understood as an illustration of individual features; the special combination of all the features listed in the same mixer need not be particularly advantageous.
  • the tube 10 can also be conical (not shown), so that it tapers in the direction of flow; in this case, the mixing bodies 1, 1 'must be of different sizes depending on the changing cross section.
  • Fig. 9 shows how the coefficient of variation s / x ⁇
  • the reference symbols 1 * to 5 * refer to the mixer types listed in the table above.
  • the mixer according to the invention which can be produced monolithically from a small amount of material, is advantageously manufactured from an inexpensive, combustible plastic by injection molding. This mixer is particularly well suited to be used as a disposable item.
  • the mixer according to the invention can also be used for mixing turbulent flowing media.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Food-Manufacturing Devices (AREA)
  • Filling, Topping-Up Batteries (AREA)

Abstract

A mixer assembly incorporated within a pipe (10) consists of one or more elements (1, 1') disrupting the laminar fluid flow. Each element (1, 1') is formed by a disc less two opposing radial sectors, with a baffle edge (5) along one sector face of one diametrical axis, and a second baffle edge (2) along the opposite sector face of the other diametrical axis. The baffles on each element (1, 1') form a cross and act as supports and spacers from the next element (1, 1'). Part-discs and vanes guide the fluid flow at the boundaries (3, 3') between elements (1, 1'). An open gap (4, 4') is maintained on both sides of each baffle (2, 2'). The mixer elements are assembled as a battery in series, each element (1, 1') being slightly rotated during assembly with respect to the adjacent element (1, 1').

Description

Die Erfindung betrifft einen Mischer, der in einem Rohr angeordnet ist und der mindestens ein Mischelement oder einen Mischkörper umfasst. Sie bezieht sich auch auf Verwendungen eines derartigen Mischers.The invention relates to a mixer which is arranged in a tube and which comprises at least one mixing element or a mixing body. It also relates to uses of such a mixer.

Aus der US-PS 3 051 453 ist ein Mischer bekannt, der sich aus einer linearen Anordnung von Mischelementen zusammensetzt, die nachfolgend als "Multiflux-Mischkörper" bezeichnet werden. Dieser Multiflux-Mischkörper, dessen Querschnitt quadratisch ist, weist zwei Kanäle auf, die sich in Strömungsrichtung bis zur Mitte des Mischkörpers kontinuierlich verengen und hinter der engsten Stelle in einer um 90° gedrehten Ebene wieder kontinuierlich erweitern. Ein durch den Mischkörper fliessendes Medium erfährt eine Umformung, durch die sich die Anzahl der Teilschichten verdoppelt.A mixer is known from US Pat. No. 3,051,453, which is composed of a linear arrangement of mixing elements, which are referred to below as "multiflux mixing bodies". This multiflux mixing body, the cross section of which is square, has two channels which continuously narrow in the direction of flow up to the center of the mixing body and continuously expand behind the narrowest point in a plane rotated by 90 °. A medium flowing through the mixing body undergoes a deformation by which the number of partial layers doubles.

Der Multiflux-Mischkörper lässt sich - geometrisch gesehen - aus vier keilförmigen Teilkörpern und zwei dreieckigen Platten aufbauen. In einer besonderen Ausführungsform haben die Keile die Form eines halbierten Würfels, der längs der Diagonale einer Seitenfläche halbiert ist. Je zwei der Keile - der eine gegenüber dem andern um 90° gedreht - bilden jeweils einen zusammenhängenden Teilkörper. Die beiden Platten bilden Trennwände zwischen den beiden Kanälen des Mischkörpers. Die Teilkörper nehmen ein Volumen ein, das 25 bis 30 % des dem Mischkörper zugeordneten Rohrvolumens beträgt.Geometrically speaking, the Multiflux mixing body can be made up of four wedge-shaped partial bodies and two build up triangular plates. In a particular embodiment, the wedges have the shape of a halved cube, which is halved along the diagonal of one side surface. Two of the wedges - one rotated 90 ° relative to the other - each form a coherent part. The two plates form partitions between the two channels of the mixing body. The partial bodies take up a volume that is 25 to 30% of the tube volume assigned to the mixing body.

Es sind analoge Mischkörper mit vier Kanälen - sogenannte ISG-Mischkörper (ISG = Interfacial Surface Generator) - bekannt (siehe H.Brünemann, G.John "Mischgüte und Druckverlust statischer Mischer mit verschiedenen Bauformen", Chemie-Ing.-Techn. 43. Jahrg. 1971, S.348). Die ISG-Mischkörper weisen kreisförmige Querschnitte auf. In einem Mischer mit ISG-Mischkörpern werden in einem zu mischenden und aus zwei Komponenten bestehenden Medium acht Teilschichten erzeugt.Analog mixing bodies with four channels - so-called ISG mixing bodies (ISG = Interfacial Surface Generator) - are known (see H.Brünemann, G.John "Mixing quality and pressure loss of static mixers with different designs", Chemical Engineering Techn. 43. Year 1971, p.348). The ISG mixing bodies have circular cross sections. In a mixer with ISG mixing bodies, eight partial layers are produced in a medium to be mixed and consisting of two components.

Die bekannten Multiflux- und ISG-Mischkörper benötigen zu ihrer Herstellung relativ viel Material, dessen Volumen nämlich mindestens 25 bis 30 % des Rohrvolumens einnimmt. Die Längen der Mischkörper in Strömungsrichtung sind relativ lang, nämlich ungefähr gleich gross wie der Rohrdurchmesser.The known Multiflux and ISG mixing bodies require a relatively large amount of material for their production, the volume of which takes up at least 25 to 30% of the tube volume. The lengths of the mixing bodies in the direction of flow are relatively long, namely approximately the same size as the pipe diameter.

Es ist Aufgabe der Erfindung, einen Mischer vom Multiflux- oder ISG-Typ zu schaffen, dessen Mischkörper oder Mischelemente aus weniger Material herstellbar sind. Diese Aufgabe wird mit den in Anspruch 1 genannten Merkmalen gelöst. Der Leervolumenanteil ist grösser als 80 bis 90 %; und somit ist der Materialbedarf wesentlich geringer. Dank seiner besonderen Form kann das Mischelement des erfindungsgemässen Mischers wesentlich kürzer, nämlich mindestens halb so lang - bei vergleichbarer Wirkung wie bei den bekannten Mischkörpern - gemacht werden. Ein Mischer mit einer Mehrzahl derartiger Mischelemente ist in Anspruch 2 definiert.It is an object of the invention to provide a mixer of the Multiflux or ISG type, the mixing body or mixing elements of which can be produced from less material. This object is achieved with the features mentioned in claim 1. The empty volume is greater than 80 to 90%; and thus the material requirement is significantly lower. Thanks to its special shape, the mixing element of the mixer according to the invention can be considerably shorter, namely at least half as long comparable effect as with the known mixing bodies. A mixer with a plurality of such mixing elements is defined in claim 2.

Die abhängigen Ansprüche 3 bis 18 beziehen sich auf vorteilhafte Ausführungsformen des erfindungsgemässen Mischers. Die Ansprüche 19 und 20 betreffen Verwendungen der Mischer.The dependent claims 3 to 18 relate to advantageous embodiments of the mixer according to the invention. Claims 19 and 20 relate to uses of the mixers.

Der erfindungsgemässe Mischer weist Mischelemente mit einer besonders einfachen Form auf. Dank dieser Form lässt sich ein monolithischer Mischkörper, der eine Serie von mehreren hintereinander geschalteten Mischelementen umfasst, gut durch Spritzgiessen aus Kunststoff oder Feinguss (Stahl) herstellen, wobei insbesondere bei der einfachsten Ausführungsform (Zweilöcher-Variante) zweiteilige Werkzeuge verwendbar sind. Die erfindungsgemässen Mischkörper lassen sich auch beispielsweise aus Blech auf einfache Weise herstellen.The mixer according to the invention has mixing elements with a particularly simple shape. Thanks to this shape, a monolithic mixing body, which comprises a series of several mixing elements connected in series, can be easily produced by injection molding from plastic or investment casting (steel), whereby two-part tools can be used in particular in the simplest embodiment (two-hole variant). The mixing bodies according to the invention can also be produced in a simple manner, for example from sheet metal.

Der erfindungsgemässe Mischer eignet sich besonders für zähe Medien wie beispielsweise Kunststoffe, Harze oder Klebstoffe (wobei die Reynolds-Zahl Re = v·D·ρ/η

Figure imgb0001
kleiner als 1 ist; v: Geschwindigkeit des fliessenden Mediums, D: Rohrdurchmesser, ρ: Dichte des Mediums, η: Viskosität). Bezüglich Mischgüte und Druckverlust (= NeReD, Ne: Newton-Zahl) ist der erfindungsgemässe Mischer günstiger als die bekannten statischen Mischer: Zwei fliessfähige Medien ähnlicher Viskosität können über eine Strecke (L) von weniger als zehn Rohrdurchmessern (D) homogen vermischt werden.The mixer according to the invention is particularly suitable for viscous media such as plastics, resins or adhesives (with the Reynolds number Re = v · D · ρ / η
Figure imgb0001
is less than 1; v: velocity of the flowing medium, D: tube diameter, ρ: density of the medium, η: viscosity). In terms of mixing quality and pressure loss (= NeReD, Ne: Newton number), the mixer according to the invention is less expensive than the known static mixers: two flowable media of similar viscosity can be homogeneously mixed over a distance (L) of less than ten pipe diameters (D).

Im Gegensatz zu den bekannten Multiflux- oder ISG-Mischern weist der erfindungsgemässe Mischer keine Kanäle mit konfusor- und diffusorartigen Abschnitten oder Bohrungen auf. Versuche ergaben, dass einfache Scheiben mit Löchern und Trennstegen, die auf den Scheiben angeordnet sind, eine überraschend gute Mischgüte liefern. Effekte, die aufgrund fehlender konfusor- und diffusorartigen Abschnitten zu erwarten waren, erwiesen sich in Bezug auf die Mischgüte als praktisch ohne störenden Einfluss.In contrast to the known Multiflux or ISG mixers, the mixer according to the invention has no channels with confuser and diffuser-like sections or bores. Trials have shown that simple disks with holes and dividers, which are arranged on the discs, deliver a surprisingly good mixing quality. Effects that were to be expected due to the lack of confuser-like and diffuser-like sections proved to be practically without any disturbing influence with regard to the mixing quality.

Für den erfindungsgemässen Mischer können Rohre mit beliebigm Querschnitt vorgesehen werden; bevorzugt sind jedoch quadratische oder kreisförmige Querschnitte.Pipes of any cross section can be provided for the mixer according to the invention; however, square or circular cross sections are preferred.

Es wurden Versuche mit erfindungsgemässen Mischern durchgeführt, deren Mischelemente jeweils 2, 3 oder 4 Löcher aufwiesen. Die Länge der Elemente war in allen Fällen gleich dem halben Rohrdurchmesser. Die Versuche ergaben eine Homogenisierung (Variationskoeffizient s/ x ¯ ≦ 0,01

Figure imgb0002
) über Strecken von 8, 7 bzw. 8 Rohrdurchmessern. Der Druckverlust war wesentlich geringer als bei den bekannten Multiplex- und ISG-Mischern.Experiments were carried out with mixers according to the invention, the mixing elements of which each had 2, 3 or 4 holes. The length of the elements was half the pipe diameter in all cases. The tests showed homogenization (coefficient of variation s / x ¯ ≦ 0.01
Figure imgb0002
) over distances of 8, 7 or 8 pipe diameters. The pressure loss was much lower than with the known multiplex and ISG mixers.

In der folgenden Tabelle sind Messresultate zusammengefasst. Die Definitionen der Grössen WLV, WLD 1/3 und WLL 1/3 sind beispielsweise aus folgender Publikation bekannt: "Mischen beim Herstellen und Verarbeiten von Kunststoffen", Reihe "Kunststofftechnik", VDI-Verlag, Düsseldorf, 1991 (Auch die Definition des Variationskoeffizienten s / x ¯

Figure imgb0003
, siehe oben, findet man dort). Diese Grössen, die als spezifische Wirkungen bezeichnet werden, machen relative Angaben über das Volumen des Mischers, seinen Durchmesser bzw. die Mischerlänge; sie beziehen sich auf den bekannten SMX-Mischer, der beispielsweise aus der DE-PS 28 08 854 (= P.5473) bekannt ist. Die Homogenisierungslänge (L/D)h ist bei s/ x ¯ = 0.01
Figure imgb0004
abgelesen worden (vgl. Fig.9). Mischertyp NeRe D (L/D) h W LV W LD 1/3 W LL 1/3 1* SMX 1200 10 1 1 1 2* 2-Loch 500 8 0.27 0.69 0.55 3* 3-Loch 1000 7 0.41 0.84 0.58 4* 4-Loch 2070 8 1.10 1.11 0.89 5* Multiflux 920 15 1.73 1.05 1.57 The results of the measurements are summarized in the following table. The definitions of the sizes W LV , W LD 1/3 and W LL 1/3 are known, for example, from the following publication: "Mixing in the manufacture and processing of plastics", "Plastics technology" series, VDI-Verlag, Düsseldorf, 1991 (also the Definition of the coefficient of variation s / x ¯
Figure imgb0003
, see above, can be found there). These quantities, which are referred to as specific effects, give relative information about the volume of the mixer, its diameter or the mixer length; they relate to the known SMX mixer, which is known for example from DE-PS 28 08 854 (= P.5473). The homogenization length (L / D) h is at s / x ¯ = 0.01
Figure imgb0004
been read (see Fig. 9). Mixer type NeRe D (L / D) h W LV W LD 1/3 W LL 1/3 1* SMX 1200 10th 1 1 1 2 * 2 holes 500 8th 0.27 0.69 0.55 3 * 3 holes 1000 7 0.41 0.84 0.58 4 * 4 holes 2070 8th 1.10 1.11 0.89 5 * Multiflux 920 15 1.73 1.05 1.57

Der Multiflux-Mischer wird bezüglich den spezifischen Wirkungen durch die getesteten Mischer übertroffen.The Multiflux mixer is surpassed in the specific effects by the tested mixers.

Nachfolgend wird die Erfindung anhand der Zeichnungen näher erläutert. Es zeigen:

Fig. 1
eine Explosionszeichnung eines statischen Mischers gemäss der Erfindung mit zwei Mischelementen (Zweilöcher-Variante),
Fig.2-4
Varianten zum Mischelement der Fig.1,
Fig.5a,b
Mischelemente mit zwei Trennstegen pro Abschnitt (Dreilöcher-Variante),
Fig. 6
einen Längsschnitt durch einen Mischer mit Elementen gemäss Fig.5,
Fig.7a,b
Umlenkscheiben zu Mischelementen mit drei Trennstegen (Vierlöcher-Variante),
Fig. 8
Mischelemente zu einem quadratischen Rohr und
Fig. 9
ein Diagramm mit Messresultaten für die Variationskoeffizienten s / x ¯
Figure imgb0005
(mit x = 0.5).
The invention is explained in more detail below with reference to the drawings. Show it:
Fig. 1
an exploded view of a static mixer according to the invention with two mixing elements (two-hole variant),
Fig. 2-4
Variants of the mixing element of Fig.1,
Fig.5a, b
Mixing elements with two dividers per section (three-hole variant),
Fig. 6
2 shows a longitudinal section through a mixer with elements according to FIG. 5,
Fig.7a, b
Deflection disks to mixing elements with three dividers (four-hole variant),
Fig. 8
Mixing elements to form a square tube and
Fig. 9
a diagram with measurement results for the variation coefficients s / x ¯
Figure imgb0005
(with x = 0.5).

Die in einem Rohr 10 angeordneten Mischelemente 1 und 1' der Fig.1 bestehen jeweils aus zwei Trennstegen 2 bzw. 2' und zwei Umlenkscheiben 3 bzw. 3', die in einer mit strichpunktierten Linien angedeuteten Ebene 3a bzw. 3a'. liegen. Die Ebene 3a liegt senkrecht zur Rohrachse 5 und parallel zu Ebenen 2a und 2b, die die obere Kante 20 bzw. die untere Kante 21 der Trennstege 2 berühren. Die drei Ebenen 2a, 3a und 2b begrenzen zwei Abschnitte 1a und 1b des Mischelements 1. Jedem Abschnitt ist ein den Abschnitt unterteilender Trennsteg 2 zugeordnet. Die Trennstege 2 der beiden Abschnitte 1a und 1b kreuzen sich unter einem rechten Winkel. Der Rohrquerschnitt ist durch die Trennstege 2 in vier gleich grosse Teilflächen unterteilt, wobei zwei dieser Teilflächen durch die Umlenkscheiben 3 abgedeckt sind. Die offenen Teilflächen sind als Einschnürungen und Durchtrittslöcher 4 für das zu mischende Medium vorgesehen.The mixing elements 1 and 1 'of FIG. 1 arranged in a tube 10 each consist of two separating webs 2 and 2' and two deflection disks 3 and 3 ', respectively, in a plane 3a and 3a' indicated by dash-dotted lines. lie. The plane 3a lies perpendicular to the pipe axis 5 and parallel to planes 2a and 2b, which touch the upper edge 20 or the lower edge 21 of the separating webs 2. The three levels 2a, 3a and 2b delimit two sections 1a and 1b of the mixing element 1. Each section is assigned a separating web 2 which divides the section. The separating webs 2 of the two sections 1a and 1b intersect at a right angle. The pipe cross section is divided by the separating webs 2 into four parts of the same size, two of these parts being covered by the deflection plates 3. The open partial areas are provided as constrictions and through holes 4 for the medium to be mixed.

Die beiden aufeinander folgenden Mischelemente 1 und 1' sind im wesentlichen gleich aufgebaut. Aber das Mischelement 1 stellt die zum Mischelement 1' spiegelbildliche Form dar. Die benachbarten Trennstege 2 und 2' kreuzen sich; die offenen Teilflächen 4 und 4' sind gegeneinander versetzt angeordnet.The two successive mixing elements 1 and 1 'are constructed essentially the same. But the mixing element 1 represents the mirror image of the mixing element 1 '. The adjacent dividers 2 and 2' intersect; the open partial areas 4 and 4 'are arranged offset from one another.

Die Umlenkscheiben 3 können auch einen Winkel α mit der Querschnittsebene 3a - siehe Fig.2 - einschliessen. Dieser Winkel α wird mit Vorteil nicht grösser als 30° gewählt. Die Figuren 3 und 4 zeigen weitere Ausführungsformen mit geneigten Flächen. Wird die Achse 5 als Vertikale verstanden, so stellt der Pfeil 6 in den Figuren 2 bis 4 jeweils die Falllinie einer Umlenkscheibe 3 dar. In Fig.2 ist dieser Pfeil 6 parallel zum oberen Trennsteg 2. Bei dem Ausführungsbeispiel der Fig.3 ist der Pfeil 6 tangential zu einem zur Achse 5 konzentrischen Kreiszylinder. Bei dem Ausführungsbeispiel der Fig.4 ist der Pfeil 6 radial nach aussen gerichtet.The deflection disks 3 can also form an angle α with the cross-sectional plane 3a - see FIG. 2. This angle α is advantageously chosen not to be greater than 30 °. Figures 3 and 4 show further embodiments with inclined surfaces. If the axis 5 is understood as a vertical, the arrow 6 in FIGS. 2 to 4 each represents the falling line of a deflection disk 3. In FIG. 2, this arrow 6 is parallel to the upper one Separator 2. In the exemplary embodiment in FIG. 3, the arrow 6 is tangential to a circular cylinder which is concentric with the axis 5. In the embodiment of Figure 4, the arrow 6 is directed radially outwards.

Die Figuren 5a und 5b zeigen Mischelemente 1 und 1', bei denen jeweils zwei Trennstege 2 einem Abschnitt 1a bzw. 1b (in diesen Figuren nicht dargestellt) zugeordnet sind. Auf beiden Seiten jedes Trennstegs 2 ist genau eine offene Teilfläche 4 angeordnet. Das Mischelement 1' mit den offenen Teilflächen 4' stellt ein unmittelbar benachbartes Element des Mischelements 1 dar. Die offenen Teilflächen 4 und 4' sind gegeneinander versetzt angeordnet. Bei der Dreilöcher-Variante (Fig.5) sind die Formen der beiden Mischelemente 1 und 1' identisch und nicht spiegelbildlich wie bei der Zweilöcher-Variante (Fig.1).FIGS. 5a and 5b show mixing elements 1 and 1 ', in each of which two separating webs 2 are assigned to a section 1a and 1b (not shown in these figures). Exactly one open partial area 4 is arranged on both sides of each separating web 2. The mixing element 1 'with the open partial areas 4' represents an immediately adjacent element of the mixing element 1. The open partial areas 4 and 4 'are arranged offset from one another. In the three-hole variant (FIG. 5), the shapes of the two mixing elements 1 and 1 'are identical and are not mirror images as in the two-hole variant (FIG. 1).

Für eine Herstellung des Dreilöcher-Mischkörpers mittels Spritzgusses kann man die Elemente in zwei Hälften teilen. Die Grenzen zwischen den Halbelementen sind in den Figuren 5a und 5b als strichpunktierte Linien 7 bzw. 7' angegeben. Monolithische Teilkörper, die jeweils eine Serie solcher Halbelemente umfassen, können auf einfache Weise mit zweitteiligen Werkzeugen hergestellt werden. Den gesamten Mischkörper erhält man durch Zusammenfügen zweier monolithischer Teilkörper.For the production of the three-hole mixing body by means of injection molding, the elements can be divided into two halves. The boundaries between the half-elements are indicated in FIGS. 5a and 5b as dash-dotted lines 7 and 7 ', respectively. Monolithic partial bodies, each comprising a series of such half-elements, can be produced in a simple manner with two-part tools. The entire mixing body is obtained by joining two monolithic partial bodies.

Im Längsschnitt der Fig.6 ist gezeigt, dass die einzelnen Mischelemente 1 und 1' dicht aufeinander folgen. Es können allerdings auch Abstände zwischen einzelnen benachbarten Elementen oder auch zwischen allen Elementen vorgesehen sein. Beabstandet eingebaute Mischelemente können durch Verbindungsstücke zu einem monolithischen Mischer verbunden werden.6 shows that the individual mixing elements 1 and 1 'follow one another closely. However, distances can also be provided between individual neighboring elements or between all elements. Mixing elements installed at a distance can be connected to a monolithic mixer by connecting pieces.

In Fig.6 ist zusätzlich mit Pfeilen 8, 8' und 8'' der Strömungsverlauf des zu mischenden Mediums angedeutet. Der Pfeil 8' steht senkrecht zur Bildfläche und ist nach vorn gerichtet; der Pfeil 8'' - ebenfalls senkrecht - ist nach hinten gerichtet. Das Bezugszeichen 9 weist auf eine Stelle hin, wo durch die Pfeile eine Erzeugung zweier Teilströme angedeutet ist.In FIG. 6, the flow path of the medium to be mixed is additionally indicated by arrows 8, 8 'and 8' '. The arrow 8 'is perpendicular to the image surface and is directed forward; the arrow 8 '' - also vertical - is directed towards the rear. The reference numeral 9 indicates a point where the generation of two partial flows is indicated by the arrows.

Die Umlenkscheiben 3 liegen mit Vorteil in einer gemeinsamen Ebene. Bei Vorliegen von mindestens zwei Trennstegen 2 pro Abschnitt (Dreilöcher-Variante) können mehrere Umlenkscheiben 3 eine gemeinsame Scheibe oder eine einzige Scheibe 30 (Vierlöcher-Variante) bilden: siehe die Figuren 5a und 5b und die entsprechenden Figuren 7a und 7b für die Vierlöcher-Variante.The deflection plates 3 are advantageously in a common plane. If there are at least two dividers 2 per section (three-hole variant), several deflection disks 3 can form a common disc or a single disc 30 (four-hole variant): see FIGS. 5a and 5b and the corresponding FIGS. 7a and 7b for the four-hole Variant.

In den Figuren 7a und 7b ist jeweils nur die einzige und gemeinsame Umlenkscheibe 30 bzw. 30' gezeigt. Die strichpunktierten Linien 23 stellen die unteren Kanten der oberen Trennstege dar. Wie schon bei der Zweilöcher-Variante sind bei der Vierlöcher-Variante die Formen benachbarter Mischelemente zueinander spiegelbildlich.In FIGS. 7a and 7b only the single and common deflection plate 30 and 30 'is shown. The dash-dotted lines 23 represent the lower edges of the upper dividers. As with the two-hole variant, the shapes of adjacent mixing elements are mirror images of one another in the four-hole variant.

Der erfindungsgemässe Mischer kann statt eines kreisförmigen Querschnitts auch einen Querschnitt mit einer anderen Form, beispielsweise einem Quadrat, haben. Die Winkel zwischen den sich kreuzenden Trennstegen 2, 2' können auch von 90° abweichen. Die Abschnitte 1a und 1b können verschieden lang sein. Die Länge der Abschnitte 1a und 1b liegt mit Vorteil im Bereich zwischen D/8 und D; sie beträgt vorzugsweise D/4.Instead of a circular cross section, the mixer according to the invention can also have a cross section with a different shape, for example a square. The angles between the crossing dividers 2, 2 'can also deviate from 90 °. Sections 1a and 1b can be of different lengths. The length of the sections 1a and 1b is advantageously in the range between D / 8 and D; it is preferably D / 4.

In Fig.8 ist illustriert, was für Abweichungen von den einfachen, oben beschriebenen Formen beispielsweise denkbar sind: Zwischen den beabstandeten Mischelementen 1, 1' sind Verbindungselemente 35 angeordnet. Die Trennstege 2 weisen zusätzliche Elemente 25 zur Verstärkung oder Strömungslenkung auf. Trennstege 2' und 2'' benachbarter Mischelemente 1' und 1'' sind an der Stelle 29 ineinander gesteckt. Einzelne Trennstege 2 und Umlenkscheiben 3 sind nicht eben. Die Mischelemente 1 und 1' weisen verschieden viele Trennstege 2 und 2' pro Abschnitt 1a bzw. 1b auf, nämlich zwei bzw. einen. Ein Trennsteg 2 weist eine Aussparung 29 auf. Die Fig.8 ist lediglich als Veranschaulichung einzelner Merkmale zu verstehen; die besondere Kombination aller aufgeführter Merkmale im gleichen Mischer braucht nicht besonders vorteilhaft zu sein.FIG. 8 illustrates what deviations from the simple shapes described above are conceivable, for example: connecting elements 35 are arranged between the spaced-apart mixing elements 1, 1 '. The Separators 2 have additional elements 25 for reinforcement or flow control. Separators 2 'and 2''of adjacent mixing elements 1' and 1 '' are inserted into one another at position 29. Individual dividers 2 and deflection plates 3 are not flat. The mixing elements 1 and 1 'have different numbers of dividers 2 and 2' per section 1a and 1b, namely two and one, respectively. A separating web 2 has a recess 29. 8 is only to be understood as an illustration of individual features; the special combination of all the features listed in the same mixer need not be particularly advantageous.

Das Rohr 10 kann auch konisch ausgebildet sein (nicht dargestellt), so dass es sich in Fliessrichtung verjüngt; die Mischkörper 1, 1' müssen in diesem Fall dem ändernden Querschnitt entsprechend verschieden gross ausgebildet sein.The tube 10 can also be conical (not shown), so that it tapers in the direction of flow; in this case, the mixing bodies 1, 1 'must be of different sizes depending on the changing cross section.

Das Diagramm in Fig.9 zeigt wie der Variationskoeffizient s/ x ¯

Figure imgb0006
für x ¯
Figure imgb0007
= 0.5 gemäss den oben erwähnten Versuchen von L/D abhängt. x ¯
Figure imgb0008
= 0.5 bedeutet, dass die Anteile der beiden zu mischenden Komponenten gleich gross sind. Die Bezugszeichen 1* bis 5* beziehen sich auf die Mischertypen, die in der oben stehenden Tabelle aufgeführt sind.The diagram in Fig. 9 shows how the coefficient of variation s / x ¯
Figure imgb0006
For x ¯
Figure imgb0007
= 0.5 depends on L / D according to the experiments mentioned above. x ¯
Figure imgb0008
= 0.5 means that the proportions of the two components to be mixed are of the same size. The reference symbols 1 * to 5 * refer to the mixer types listed in the table above.

Der erfindungsgemässe Mischer, der sich aus wenig Material monolithisch herstellen lässt, wird mit Vorteil aus einem kostengünstigen, verbrennbaren Kunststoff durch Spritzgiessen gefertigt. Dieser Mischer eignet sich besonders gut dazu, als Einwegartikel verwendet zu werden.The mixer according to the invention, which can be produced monolithically from a small amount of material, is advantageously manufactured from an inexpensive, combustible plastic by injection molding. This mixer is particularly well suited to be used as a disposable item.

Der erfindungsgemässe Mischer kann auch zum Mischen turbulent strömender Medien verwendet werden.The mixer according to the invention can also be used for mixing turbulent flowing media.

Claims (20)

In einem Rohr (10) angeordneter Mischer mit mindestens einem Mischelement (1, 1'), das zwei axiale Abschnitte (1a, 1b) umfasst, wobei jedem Abschnitt mindestens ein den Abschnitt unterteilender Trennsteg (2, 2') zugeordnet ist, die Trennstege der beiden Abschnitte sich kreuzen und der Rohrquerschnitt durch die Trennstege in Teilflächen unterteilt ist, wobei ferner bei der Grenze (3a, 3a') zwischen den Abschnitten offene sowie durch Umlenkscheiben (3, 3') abgedeckte Teilfächen vorgesehen sind und auf beiden Seiten jedes Trennstegs genau eine offene Teilfläche (4, 4') angeordnet ist.Mixer arranged in a tube (10) with at least one mixing element (1, 1 ') which comprises two axial sections (1a, 1b), each section being assigned at least one separating web (2, 2') dividing the section, the separating webs of the two sections intersect and the pipe cross-section is divided into partial areas by the separating webs, further open areas being provided at the border (3a, 3a ') between the sections and covered by deflection disks (3, 3') and on both sides of each separating web exactly one open partial area (4, 4 ') is arranged. Mischer nach Anspruch 1, dadurch gekennzeichnet, dass eine Mehrzahl von Mischelementen (1, 1') vorliegt und dass bezüglich aufeinander folgender Mischelemente einerseits benachbarte Trennstege (2, 2') sich kreuzen und andererseits die offenen Teilflächen (4, 4') gegeneinander versetzt angeordnet sind.Mixer according to claim 1, characterized in that there are a plurality of mixing elements (1, 1 ') and that, with respect to successive mixing elements, on the one hand adjacent separating webs (2, 2') cross and on the other hand the open partial surfaces (4, 4 ') are offset from one another are arranged. Mischer nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Rohrquerschnitt durch die Trennstege (2, 2') in zumindest angenähert gleich grosse Teilflächen unterteilt ist.Mixer according to claim 1 or 2, characterized in that the pipe cross section is divided by the separating webs (2, 2 ') into at least approximately equal partial areas. Mischer nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Trennstege (2) benachbarter Abschnitte (1a, 1b) sich unter einem Winkel von 90° kreuzen.Mixer according to one of claims 1 to 3, characterized in that the separating webs (2) of adjacent sections (1a, 1b) intersect at an angle of 90 °. Mischer nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass beide Abschnitte (1a, 1b) eines Mischelements (1) zumindest angenähert gleich gross sind.Mixer according to one of claims 1 to 4, characterized in that both sections (1a, 1b) of a mixing element (1) are at least approximately the same size. Mischer nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Länge eines Mischelements (1) kleiner als der grösste Rohrdurchmesser, vorzugsweise kleiner als die Hälfte des grössten Rohrdurchmessers ist.Mixer according to one of claims 1 to 5, characterized in that the length of a mixing element (1) is less than the largest pipe diameter, preferably less than half the largest pipe diameter. Mischer nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Umlenkscheiben (3) in einer gemeinsamen Ebene liegen und dass bei Vorliegen von mindestens zwei Trennstegen (2) pro Abschnitt (1a, 1b) mehrere Umlenkscheiben eine gemeinsame Scheibe oder alle Umlenkscheiben eine einzige Scheibe (30) bilden.Mixer according to one of claims 1 to 6, characterized in that the deflection disks (3) lie in a common plane and that if there are at least two separating webs (2) per section (1a, 1b), several deflection disks one common disk or all deflection disks one form a single disc (30). Mischer nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Umlenkscheiben (3) zur Querschnittsebene (3a) geneigt sind und dass der Winkel (α) zwischen Umlenkscheibe und Querschnittsebene kleiner als 30° ist.Mixer according to one of claims 1 to 7, characterized in that the deflection disks (3) are inclined to the cross-sectional plane (3a) and that the angle (α) between the deflection disk and the cross-sectional plane is less than 30 °. Mischer nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass mehrere aufeinander folgende Mischelemente (1, 1') in Form einer monolithischen, insbesondere durch Spritzguss hergestellten Struktur vorliegen.Mixer according to one of claims 1 to 8, characterized in that several successive mixing elements (1, 1 ') are in the form of a monolithic structure, in particular produced by injection molding. Mischer nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass zwischen mindestens zwei benachbarten Mischelementen (1, 1') ein Abstand vorgesehen ist.Mixer according to one of claims 1 to 9, characterized in that a distance is provided between at least two adjacent mixing elements (1, 1 '). Mischer nach Anspruch 10, dadurch gekennzeichnet, dass zwischen beabstandeten Mischelementen (1, 1') Verbindungselemente (35) angeordnet sind.Mixer according to claim 10, characterized in that connecting elements (35) are arranged between spaced-apart mixing elements (1, 1 '). Mischer nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass das Rohr (10) einen quadratischen oder einen kreisförmigen Querschnitt aufweist.Mixer according to one of claims 1 to 11, characterized in that the tube (10) has a square or a circular cross section. Mischer nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass zumindest einzelne Trennstege (2, 2') und/oder Umlenkscheiben (3, 3') zusätzliche Elemente (25) zur Verstärkung oder Strömungslenkung aufweisen.Mixer according to one of claims 1 to 12, characterized in that at least individual separating webs (2, 2 ') and / or deflection disks (3, 3') have additional elements (25) for reinforcement or flow control. Mischer nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass Trennstege (2, 2') benachbarter Mischelemente (1, 1') ineinander gesteckt (29) sind.Mixer according to one of claims 1 to 13, characterized in that separating webs (2, 2 ') of adjacent mixing elements (1, 1') are inserted into one another (29). Mischer nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass zumindest einzelne Trennstege (2, 2') und/oder Umlenkscheiben (3, 3') nicht eben sind.Mixer according to one of claims 1 to 14, characterized in that at least individual separating webs (2, 2 ') and / or deflection disks (3, 3') are not flat. Mischer nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass zumindest einzelne Trennstege (2, 2') und/oder Umlenkscheiben (3, 3') zusätzliche Aussparungen (26) aufweisen.Mixer according to one of claims 1 to 15, characterized in that at least individual separating webs (2, 2 ') and / or deflection disks (3, 3') have additional cutouts (26). Mischer nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass das Rohr (10) konisch, in Fliessrichtung sich verjüngend ausgebildet ist und die Mischkörper (1, 1') dem ändernden Querschnitt entsprechend verschieden gross ausgebildet sind.Mixer according to one of claims 1 to 16, characterized in that the tube (10) conical, in Flow direction is tapered and the mixing body (1, 1 ') are of different sizes according to the changing cross section. Mischer nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass zumindest zwei Mischelemente (1, 1') verschieden viele Trennstege (2, 2') pro Abschnitt (1a, 1b) aufweisen.Mixer according to one of claims 1 to 16, characterized in that at least two mixing elements (1, 1 ') have different numbers of separating webs (2, 2') per section (1a, 1b). Verwendung eines Mischers gemäss einem der Ansprüche 1 bis 18 zum Mischen von zähen Stoffen, insbesondere von Kunststoffen, Harzen oder Klebstoffen, wobei die Reynolds-zahl für jeden der durch den Mischer fliessenden Stoffe kleiner als 1 ist.Use of a mixer according to one of claims 1 to 18 for mixing viscous substances, in particular plastics, resins or adhesives, the Reynolds number for each of the substances flowing through the mixer being less than 1. Verwendung eines Mischers gemäss einem der Ansprüche 1 bis 18 als Einwegartikel, wobei der Mischer aus einem kostengünstigen, verbrennbaren Kunststoff durch Spritzgiessen hergestellt ist.Use of a mixer according to one of claims 1 to 18 as a disposable article, the mixer being produced from an inexpensive, combustible plastic by injection molding.
EP95810418A 1995-06-21 1995-06-21 Mixer with tubular housing Expired - Lifetime EP0749776B1 (en)

Priority Applications (12)

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DE59508992T DE59508992D1 (en) 1995-06-21 1995-06-21 Mixer arranged in a tube
AT95810418T ATE198839T1 (en) 1995-06-21 1995-06-21 MIXER PLACED IN A TUBE
EP95810418A EP0749776B1 (en) 1995-06-21 1995-06-21 Mixer with tubular housing
ES95810418T ES2155509T3 (en) 1995-06-21 1995-06-21 TUBE SHAPED BODY MIXER.
DE29522199U DE29522199U1 (en) 1995-06-21 1995-06-21 Mixer arranged in a tube
TW085105453A TW315314B (en) 1995-06-21 1996-05-08
CA002178065A CA2178065C (en) 1995-06-21 1996-06-03 A mixer arranged in a tube
US08/660,434 US5944419A (en) 1995-06-21 1996-06-07 Mixing device
KR1019960020691A KR100420822B1 (en) 1995-06-21 1996-06-11 Mixer disposed in the tube
CN96111003A CN1052171C (en) 1995-06-21 1996-06-19 Mixer fitted in a tube
BR9602858A BR9602858A (en) 1995-06-21 1996-06-20 Mixer placed in a tube and use
JP15997396A JP4283901B2 (en) 1995-06-21 1996-06-20 Mixer placed in the tube

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EP0749776B1 EP0749776B1 (en) 2001-01-24

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JP (1) JP4283901B2 (en)
KR (1) KR100420822B1 (en)
CN (1) CN1052171C (en)
AT (1) ATE198839T1 (en)
BR (1) BR9602858A (en)
CA (1) CA2178065C (en)
DE (2) DE59508992D1 (en)
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CN1148518A (en) 1997-04-30
TW315314B (en) 1997-09-11
DE59508992D1 (en) 2001-03-01
ATE198839T1 (en) 2001-02-15
BR9602858A (en) 1998-04-22
KR100420822B1 (en) 2004-05-22
CA2178065C (en) 2000-05-30
CN1052171C (en) 2000-05-10
EP0749776B1 (en) 2001-01-24
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JPH09901A (en) 1997-01-07
CA2178065A1 (en) 1996-12-22
KR970000319A (en) 1997-01-21
DE29522199U1 (en) 2000-08-17
ES2155509T3 (en) 2001-05-16

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