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EP1390132A2 - Barres melangeuses a effet nettoyant dans le sens radial ou axial - Google Patents

Barres melangeuses a effet nettoyant dans le sens radial ou axial

Info

Publication number
EP1390132A2
EP1390132A2 EP02730151A EP02730151A EP1390132A2 EP 1390132 A2 EP1390132 A2 EP 1390132A2 EP 02730151 A EP02730151 A EP 02730151A EP 02730151 A EP02730151 A EP 02730151A EP 1390132 A2 EP1390132 A2 EP 1390132A2
Authority
EP
European Patent Office
Prior art keywords
mixing
shaft
kneader according
elements
mixing kneader
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.)
Withdrawn
Application number
EP02730151A
Other languages
German (de)
English (en)
Inventor
Alfred Kunz
Walther Schwenk
Joachim Wagner
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.)
List AG
Original Assignee
List AG
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
Priority claimed from DE10120391A external-priority patent/DE10120391A1/de
Priority claimed from DE10160535A external-priority patent/DE10160535A1/de
Priority claimed from DE10202435A external-priority patent/DE10202435A1/de
Application filed by List AG filed Critical List AG
Publication of EP1390132A2 publication Critical patent/EP1390132A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/09Stirrers characterised by the mounting of the stirrers with respect to the receptacle
    • B01F27/091Stirrers characterised by the mounting of the stirrers with respect to the receptacle with elements co-operating with receptacle wall or bottom, e.g. for scraping the receptacle wall
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/02Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/18Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/183Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
    • B29B7/186Rotors therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/19Stirrers with two or more mixing elements mounted in sequence on the same axis
    • B01F27/192Stirrers with two or more mixing elements mounted in sequence on the same axis with dissimilar elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/701Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
    • B01F27/702Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with intermeshing paddles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/701Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
    • B01F27/703Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with stirrers rotating at different speeds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/481Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with paddles, gears or discs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90Heating or cooling systems
    • B01F2035/99Heating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2805Mixing plastics, polymer material ingredients, monomers or oligomers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/112Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B01F27/1122Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades anchor-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/50Mixing receptacles
    • B01F35/54Closely surrounding the rotating element

Definitions

  • the invention relates to a mixer kneader for carrying out mechanical, chemical and / or thermal processes with mixing elements on a shaft which have scraping edges running approximately in the longitudinal direction of the shaft or at a slightly inclined angle.
  • Mixing kneaders of this type serve a very wide range of purposes.
  • the first thing to mention is evaporation with solvent recovery, which is carried out batchwise or continuously and often under vacuum.
  • solvent recovery which is carried out batchwise or continuously and often under vacuum.
  • distillation residues and especially toluene diisocyanates are treated, but also production residues with toxic or high-boiling solvents from chemistry and pharmaceutical production, washing solutions and lacquer sludges, polymer solutions, elastomer solutions from solvent polymerization, adhesives and sealants.
  • a continuous or batchwise is further 'knung, water and / or solvent-moist products, often also under vacuum carried out.
  • the application is primarily intended for pigments, dyes, fine chemicals, additives such as salts, oxides, hydroxides, antioxidants, temperature-sensitive pharmaceutical and vitamin products, active ingredients, polymers, synthetic rubbers, polymer suspensions, latex, hydrogels, waxes, pesticides and residues from the chemical or pharmaceutical production, such as salts, catalysts, slags, leaching.
  • additives such as salts, oxides, hydroxides, antioxidants, temperature-sensitive pharmaceutical and vitamin products, active ingredients, polymers, synthetic rubbers, polymer suspensions, latex, hydrogels, waxes, pesticides and residues from the chemical or pharmaceutical production, such as salts, catalysts, slags, leaching.
  • Degassing and / or devolatilization can take place in mixing kneaders. This is applied to polymer melts, to spinning solutions for synthetic fibers and to polymer or elastomer granules or powder in the solid state.
  • a polycondensation reaction usually continuous and mostly in the melt, can take place in a mixing kneader and is mainly used in the treatment of polyamides, polyesters, polyacetates, polyimides, thermoplastics, elastomers, silicones, urea resins, phenolic resins, detergents and fertilizers.
  • a polymerization reaction can also take place, usually also continuously. This is applied to polyacrylates, hydrogels, polyols, thermoplastic Polymers, elastomers, syndiotactic polystyrene and polyacrylamides.
  • solid / liquid and multiphase reactions can take place in the mixer. This applies above all to baking reactions in the treatment of hydrofluoric acid, stearates, cyanates, polyphosphates, cyanuric acids, cellulose derivatives, esters, ethers, polyacetal resins, sulfanilic acids, Cu phthalocyanines, starch derivatives, ammonium polyphosphates, sulfonates, pesticides and fertilizers.
  • reactions can take place in solid / gaseous form (e.g. carboxylation) or liquid / gaseous form. This is used in the treatment of acetates, acids, Kolbe-Schmitt reactions, e.g. BON, Na salicylates, parahydroxibenzoates and pharmaceutical products.
  • Liquid / liquid reactions take place during neutralization reactions and transesterification reactions.
  • Dissolving and / or degassing in such mixing kneaders takes place in spinning solutions for synthetic fibers, polyamides, polyesters and celluloses.
  • Solid-state post-condensation takes place in the production or treatment of polyester and polyamides, continuous mashing, for example in the treatment of fibers, for example cellulose fibers with solvents, crystallization from the melt or from solutions in the treatment of salts, fine chemicals, Polyols, alcoholates, compounding, Mixing (continuously and / or in batches) in the case of polymer mixtures, silicone compositions, sealing compositions, fly ash, coagulation (in particular continuously) in the treatment of polymer suspensions.
  • Multifunctional processes can also be combined in a mixer kneader, for example heating, drying, melting, crystallizing, mixing, degassing, reacting - all of this continuously or in batches. This produces or treats polymers, elastomers, inorganic products, residues, pharmaceutical products, food products, printing inks.
  • a vacuum sublimation / desublimation can also take place in * - kneaders, whereby chemical precursors, e.g. Anthraquinone, metal chlorides, organometallic compounds, etc. can be cleaned. Pharmaceutical intermediates can also be produced.
  • chemical precursors e.g. Anthraquinone, metal chlorides, organometallic compounds, etc.
  • Pharmaceutical intermediates can also be produced.
  • Continuous carrier gas desublimation takes place e.g. organic intermediates, e.g. Anthraquinone and fine chemicals instead.
  • Mixing kneaders can be single or double-shaft, turn in the same direction or in opposite directions at the same or different speed.
  • a mixer kneader of the type mentioned above is known for example from EP 0 517 068 B1. With it, two axially parallel shafts rotate either in opposite directions or in the same direction in a mixer housing. Mixed bars placed on disc elements work together. In addition to the function of mixing, the mixing bars have the task of cleaning the surfaces of the mixer housing, the shafts and the disc elements that come into contact with the product as well as possible and thus avoid unmixed zones. Particularly in the case of highly compacting, hardening and crusting products, the fact that the mixed bars are marginal leads to high local mechanical loads on the mixed bars and the shafts. These force peaks occur in particular when the mixed bars engage in those zones where the product is difficult to avoid. Such zones exist, for example, where the disk elements are placed on the shaft.
  • the present invention has for its object to provide a mixer kneader of the type mentioned above, in which the cleaning effect is maintained, but the load on the mixer bars or the shafts is reduced.
  • clearance angles are formed in each case away from the scraping edges against the direction of movement of the mixing element.
  • Clear angle is understood to mean that a surface with an angle that opens towards the surface to be cleaned adjoins the respective scraping edge.
  • the mixing element tapers against the direction of movement.
  • the clearance angles run away from them in relation to the surfaces to be cleaned.
  • the clearance angle can be 3 ° to 45 °, preferably 10 ° to 20 °. This counteracts crust compression and a brake drum effect.
  • the mixing elements can be placed directly on the shaft, but they are preferably arranged on the circumference of disk elements, which in turn are on the shafts are put on.
  • mixing elements come especially mixing or Kneading bar shapes into consideration, all possible kneading bars such as chopper, crust breaker, clamp, etc. being within the scope of the invention.
  • An additional process advantage results from the fact that no compression zones arise in the engagement area of the mixed bars of two shafts. This results in comminution or granulation of a pasty product mass (e.g. during drying or polymerization) without grinding effects, i.e. that is, there is no fine fraction. This is a particular advantage of the present invention.
  • Such mixing elements according to the invention should be applicable to all known single-shaft or twin-shaft mixer kneaders which rotate in the same direction or in the opposite direction, at the same or different speed, etc.
  • the invention is not limited in this sense.
  • At least one mixing element of a ring should have only radially oriented scraping edges and the other mixing elements of a ring essentially axially oriented scraping edges, or vice versa.
  • the shafts preferably rotate at different speeds, which means that the mixing bars constantly change lanes during rotation and so treatment of different areas takes place, in particular on the disk elements and the shaft surfaces.
  • the different speed is preferably not an integer.
  • adjoining wreaths on the same shaft and / or also on opposing shafts or meshing with one another on the inner wall of the housing have a different number of mixing elements or counter-elements.
  • the cleaning and kneading action can also be varied in this way.
  • the mixing elements or counter-elements can be placed directly on the respective shaft or on the inner wall of the housing, but they are preferably arranged on the shaft on the circumference of disk elements.
  • Mixing or kneading bar shapes are particularly suitable as mixing elements, all possible kneading bars such as within the scope of the invention for example Schnetzler, crust breaker, Klemmer, etc.
  • the individual scraping edges of the respective counter or mixing bar or the edges not required for cleaning can be provided with the clearance angles mentioned above, i.e. they run away from them in relation to the surfaces to be cleaned.
  • the clearance angle can be 3 ° to 45 °, preferably 10 ° to 20 °. This counteracts crust compression and a brake drum effect.
  • An additional process advantage results from the fact that no compression zones arise in the engagement area of the mixed bars of the two shafts. This results in comminution or granulation of a pasty product mass (e.g. during drying or polymerization) without grinding effects, ie there is no fine fraction. This is a particular advantage of the present invention.
  • FIG. 1 shows a cross section through a mixing kneader according to the invention
  • FIG. 2 shows part of an enlarged longitudinal section through the mixer kneader according to FIG. 1;
  • Figure 3 is a plan view of an inventive mixing element arranged on a shaft
  • Figure 4 shows three views of the mixing element of Figure 3 with corresponding reference lines
  • FIG. 5 shows a plan view of a further exemplary embodiment of a mixing element arranged on a shaft
  • FIG. 6 shows three views of the mixing element according to FIG. 5 with corresponding reference lines
  • FIG. 7 shows three longitudinal sections through a mixing kneader according to the invention, which show the combination of different mixing elements.
  • FIG. 1 there are two shafts 2 and 3 in a mixer housing 1, which run axially parallel to one another and are preferably heated. They turn in the same direction according to arrows 4 and 5.
  • the mixing elements 10 also slide close to the inner surface 8 of the housing part assigned to the shaft 3. Furthermore, parts of the disk elements and mixing elements of both shafts 2 and 3 interlock, i.e. they mesh with one another. The mixing elements are arranged such that they also graze along near the outer surface of the opposite shaft 2 or 3.
  • each ring 11 or 12 can seen alone, be equipped with different mixing elements A and R.
  • the mixing element R used in the "substantially the cleaning of radially extending surfaces, while the mixing element A preferably for cleaning of axially extending surfaces is used.
  • Radially extending surfaces in particular the surfaces of the disc elements 6 and 9.
  • Axially extending surfaces in particular, the housing inner wall 8 and the outer surfaces of waves 2 and 3, respectively.
  • a mixing element for A preferred cleansing is shown of axially extending surfaces ⁇ . It sits on the disc element 6/9 as a mixed bar 13, which is connected to the shaft 2/3. Overall, the mixing bar 13 is approximately triangular. It has a scraping edge 14 which extends axially to the shaft 2/3. At both ends there are rounded corner areas 15.1 and 15.2 which merge into side flanks 16.1 and 16.2 which converge towards one another.
  • the mixing bar 13 is triangular, the mixing bar tapering towards the rear against the direction of movement. Furthermore, the scraping edge 14 is set at an angle, so that a clearance angle that opens against the direction of movement arises in relation to an inner surface 8 or surface of the shaft 2 or 3 to be brushed. As a result, there is no pinching of products to be treated.
  • the mixing bar 13 is shown in FIG. 4 for a better representation of the clearance angles viewed from three sides, the contours of the mixing bar 13 being illustrated by corresponding reference lines.
  • wi can preferably be 15 °, w 2 preferably 20 °.
  • the clearance angle wi is formed between a tangent, applied to the housing inner wall, which extends through the scraping edge 14, while the clearance angle w 2 is formed with respect to a radial which extends between the scraping edge 14 and a shaft axis.
  • a third clearance angle w 3 with a base 27 This can be 25 °, for example.
  • the base 27 extends approximately at right angles to the radial which runs through the center of the base 27.
  • the side flanks 16.1 and 16.2 also form a clearance angle w 4 .
  • the mixing element R for preferred cleaning of radially extending surfaces according to FIG. 5 also sits on a disk element 6/9 and this in turn rests on a shaft 2/3.
  • This mixing element R is of a somewhat Roman shape and has two mutually opposite, approximately radially running edges 17 and 18.
  • the edge 18 is designed as a scraping edge, which is followed by a surface 19 counter to the direction of movement of the mixing element R or towards the rear, which, for example, faces one sweeping disc area includes a not specified clearance angle. This configuration again results in a triangular configuration for the mixing element R in section.
  • An outer edge 20 assigned to the inner surface 8 is also shaped such that only a small central part 21 passes close to the inner surface 8.
  • the side parts 22.1 and 22.2 of the outer edge 20 leading away from the middle part 21 run at an incline or form a clearance angle w6 with respect to the inner surface 8.
  • the operation of the present invention is as follows: When the mixer kneader is operating, a product to be treated is introduced into the mixer housing 1 and treated by rotating the shafts 2 and 3. It can be transported in one housing direction from an inlet to an outlet. At least the shafts 2 and 3 or else the disk elements 6 and 9 are preferably tempered.
  • the product is mixed and kneaded by the mixing elements 7 and 10. Here in 'near cooperating surfaces are also held shears.
  • different mixing bars A and R are provided in a ring 11 and 12 of mixing elements 7 and 10, respectively.
  • four mixing bars A and only one mixing bar R can be provided in the ring 11.
  • the middle arrangement shows a mixing bar R 3 for cleaning radial surfaces, which passes through a mixing space, which is also formed by mixing bars Ri and R 2 for cleaning radial surfaces.
  • a mixing chamber is formed by two mixing bars Ri and R 2 for cleaning radially extending surfaces, which is coated by a mixing bar A for cleaning axially extending surfaces.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Accessories For Mixers (AREA)

Abstract

L'invention concerne un mélangeur mixte utilisé dans des processus mécaniques, chimiques et/ou thermiques, comportant des éléments mélangeurs (A, R) sur un arbre (2, 3), qui s'étendent approximativement dans le sens longitudinal de l'arbre (2, 3) ou sont légèrement inclinés et présentent au moins une arête de grattage (14, 18, 21). Ce mélangeur mixte se caractérise en ce que des angles de dépouille (w1 w6) sont formés dans chaque cas à partir de l'arête de grattage (14, 18, 21), à l'encontre du sens de mouvement de l'élément mélangeur.
EP02730151A 2001-04-25 2002-04-12 Barres melangeuses a effet nettoyant dans le sens radial ou axial Withdrawn EP1390132A2 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10120391 2001-04-25
DE10120391A DE10120391A1 (de) 2001-04-25 2001-04-25 Radial oder axial reingende Mischbarren
DE10160535 2001-12-10
DE10160535A DE10160535A1 (de) 2001-12-10 2001-12-10 Radial oder axial reinigende Mischbarren
DE10202435A DE10202435A1 (de) 2002-01-22 2002-01-22 Radial oder axial reinigende Mischbarren
DE10202435 2002-01-22
PCT/EP2002/004099 WO2002089963A2 (fr) 2001-04-25 2002-04-12 Barres melangeuses a effet nettoyant dans le sens radial ou axial

Publications (1)

Publication Number Publication Date
EP1390132A2 true EP1390132A2 (fr) 2004-02-25

Family

ID=27214407

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02730151A Withdrawn EP1390132A2 (fr) 2001-04-25 2002-04-12 Barres melangeuses a effet nettoyant dans le sens radial ou axial

Country Status (6)

Country Link
US (1) US20040145964A1 (fr)
EP (1) EP1390132A2 (fr)
CN (1) CN1241679C (fr)
AU (1) AU2002302530A1 (fr)
CA (1) CA2445074A1 (fr)
WO (1) WO2002089963A2 (fr)

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CA2445074A1 (fr) 2002-11-14
WO2002089963A3 (fr) 2003-12-11
AU2002302530A8 (en) 2002-11-18
CN1241679C (zh) 2006-02-15
AU2002302530A1 (en) 2002-11-18
WO2002089963A2 (fr) 2002-11-14
CN1531456A (zh) 2004-09-22
US20040145964A1 (en) 2004-07-29

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