CA2452775C - Filling containers with granular or pulverulent material - Google Patents

Filling containers with granular or pulverulent material Download PDF

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Publication number
CA2452775C
CA2452775C CA002452775A CA2452775A CA2452775C CA 2452775 C CA2452775 C CA 2452775C CA 002452775 A CA002452775 A CA 002452775A CA 2452775 A CA2452775 A CA 2452775A CA 2452775 C CA2452775 C CA 2452775C
Authority
CA
Canada
Prior art keywords
container
filling
cage
woven fabric
air
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.)
Expired - Lifetime
Application number
CA002452775A
Other languages
French (fr)
Other versions
CA2452775A1 (en
Inventor
Roland Schaffer
Johannes Andreas Joze Middelman
Gerd Theodor Brand
Frank Dieter Hunig
Hans-Jurgen Strempel
Hans-Joachim Seydel
Michael Hirschhauser
Thomas Riedemann
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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 DE10133666A external-priority patent/DE10133666A1/en
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to CA2569061A priority Critical patent/CA2569061C/en
Publication of CA2452775A1 publication Critical patent/CA2452775A1/en
Application granted granted Critical
Publication of CA2452775C publication Critical patent/CA2452775C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B67OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67CCLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
    • B67C3/00Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
    • B67C3/02Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D5/00Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/42Details of containers or of foldable or erectable container blanks
    • B65D5/4295Ventilating arrangements, e.g. openings, space elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B1/00Packaging fluent solid material, e.g. powders, granular or loose fibrous material, loose masses of small articles, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
    • B65B1/28Controlling escape of air or dust from containers or receptacles during filling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • B65D65/403Applications of laminates for particular packaging purposes with at least one corrugated layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D88/00Large containers
    • B65D88/16Large containers flexible
    • B65D88/1612Flexible intermediate bulk containers [FIBC]
    • B65D88/1618Flexible intermediate bulk containers [FIBC] double-walled or with linings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D88/00Large containers
    • B65D88/16Large containers flexible
    • B65D88/1612Flexible intermediate bulk containers [FIBC]
    • B65D88/1668Flexible intermediate bulk containers [FIBC] closures for top or bottom openings

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Basic Packing Technique (AREA)
  • Packages (AREA)
  • Bag Frames (AREA)
  • Filtration Of Liquid (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Cartons (AREA)
  • Supplying Of Containers To The Packaging Station (AREA)
  • Filters For Electric Vacuum Cleaners (AREA)
  • Filtering Materials (AREA)

Abstract

An apparatus for filling containers, the apparatus comprising a feed nozzle which may be placed over the feed orifice of the container, the feed nozzle being constructed so that the solids may be introduced under pressure, and in which the container is surrounded by a cage; as well as a method for filling containers, in particular with finely-divided solids having a high air content, by arranging an air-permeable container in an apparatus according to the invention, air-tight connection of the container to the feed nozzle, filling of the container under pressure, and removal of the filled container; the container having air-permeable plies.

Description

Filling Containers With Granular Or Pulverulent Material The present invention relates to the filling of containers with granular or powdered materials, in particular with finely-divided solids with a high air content, as well as to features of the container itself.

The handling of pourable finely-divided solids having a high air content and low pour density such as, for example, finely-divided silica, poses various problems.
Producers as well as final consumers are faced with the fact that these materials raise dust even in the slightest air convection. The formation of dust must be avoided to protect the personnel dealing with the product from possible damage to their health by breathing in the dust.
In addition, the low pour-density increases transportation costs, because the ratio of container weight to filling weight is high and a correspondingly large amount of packaging material is required.

Owing to its three-dimensional spatial branch structure, finely-divided silica is a product having a very low compacted bulk density of about 40 to 50 g/l. Owing to its fine structure, finely-divided silica is capable of binding a very large amount of gas, for example air, so the product is put into a quasi-fluid state of about 20 to 30 g/l.

Spontaneous escape of this removable air content takes place only very slowly and incompletely. The dust problem is also increased in this fluid state because the mobility of the finely-divided silica is extremely high.
2 Pourable finely-divided solids with a high air content and very low pour-density are therefore introduced into air-permeable bags predominantly by means of an externally applied vacuum. The duration of filling increases as the air content increases.

The bags consist of three to four plies of paper, and one ply of the paper may additionally be laminated with polyethylene as a barrier against penetrating moisture. To achieve the desired air permeability during the filling process, all plies are microperforated. This has the effect that the product is compressed as it is introduced into the bag and its filling density increases relative to the natural pour density.

It also is possible to carry out preliminary deaeration using special press rollers, but this can always give rise to structural damage which may adversely affect the properties of the solids in use.

The higher proportion of the product in the container weight reduces transportation costs, but this saving is offset by additional expenditure for procuring the special container and the necessary filling devices.

A method and a receptacle for repeated filling with and emptying of pourable product having a low pouring density is known from EP 773,159. The woven fabric receptacle described therein, the so-called big bag or also super bag, consists of flexible air-permeable woven fabric, preferably a single or multiple ply of plastic woven fabric with at least one inlet. This woven fabric receptacle also is filled using vacuum filling systems. A vacuum is applied
3 to the woven fabric receptacle, and the product is aspirated through the open inlet into the woven fabric receptacle until a predetermined filling weight is achieved. The issuing gas is distributed over the entire surface of the woven fabric receptacle. During the filling process, the product is reversibly compacted, as when being poured into bags, without its structure being destroyed in the process.

DE-A-198 39 106 describes flexible large containers for finely-divided solids having a high air content for repeated filling using vacuum filling systems, which consist of at least two superimposed plies, an inner ply consisting of uncoated air-permeable woven fabric and an outer ply being dustproof and being coated with a moisture barrier and these plies being mutually connected by a special seam in such a way that the container may only be aerated through it.

With this design of containers, in particular the increase in moisture in the filling product during storage in the large container could be reduced.

As the air no longer is able to escape over the entire surface of the woven fabric receptacle, however, a drawback is that the period of time required to reach a predetermined pouring density is considerably extended, and the filling capacity therefore reduced. To compensate for this, DE-A-198 39 106 describes a particular process for filling this large container, with which the filling material is subjected to preliminary deaeration prior to filling, and a further deaeration via the seams of the fabric is carried out during filling. The preliminary
4 deaeration and therefore partial compaction of the filling product are also effected by the application of vacuum.

A drawback of the process described in DE-A-198 39 106 is the extremely high expenditure on apparatus, as vacuum systems are required for both preliminary compaction and filling of the large container. Despite this expenditure, the filling capacity is still too low, so the process described in DE-A-198 39 106 is uneconomical overall.

.It is accordingly an object of the present invention to provide an apparatus and method for filling containers, in particular with finely-divided solids having a high air content, with which a high filling capacity with adequate compression of the solids to be poured may be achieved with low expenditure on apparatus and therefore low capital outlay.

The invention provides apparatus for filling a container with granular, powdered or finely-divided solids having a high air content; the apparatus comprising a feed nozzle for introduction of the solids into a feed orifice of the container under positive pressure, the feed nozzle comprising a flexible sealing skin which provides dust-free pressure filling of the container, and the container being surrounded by a two-part or multi-part cage which is gas-permeable.

The present invention also relates to a method for filling containers, in particular with finely-divided solids having a high air content, by arranging an air-permeable container in an apparatus according to the invention, air-tight connection of the container to the feed nozzle, filling of the container under pressure, and removal of the filled container.

Finely-divided solids having a high air content may be poured with adequate compression of the solids in high capacities using the apparatus and method according to the invention, without high expenditure on apparatus. In particular, finely-divided granular powdered solids having a high air content may be pyrogenic oxides, precipitated oxides, carbon blacks and modifications thereof.

In particular, with pneumatic conveyance of the filling product, the resultant pressure is sufficient to achieve appropriate filling of the container. According to a preferred embodiment of the invention, the apparatus has a special feed nozzle which is equipped with a flexible sealing skin and therefore allows dust-free pressure filling. The feed nozzle may be deformable and may therefore allow the filling of containers of various sizes.

The cage, which is an important component of the apparatus according to the invention has to withstand, in particular, the pressure required. At the same time, the cage gives the container adequate support during the filling process, to ensure that the container withstands the pressure applied and keeps its shape during the filling process.

Containers of a wide variety of shapes and of various materials may be filled in the apparatus according to the invention. The materials may be: air-permeable plastic woven fabric, preferably polypropylene woven fabric, plastic woven fabric, textile woven fabric, cardboard, paper, paper plastic woven material, plastic non-woven fabric, textile non-woven fabric or composites of the aforementioned materials. The filling pressure is generally 0 to 8 bar, preferably 0 to 2 bar, and particularly preferably 0.2 to 1.2 bar.

The containers employed in the apparatus and method according to the invention may be of any conventional shapes and materials. For example, the containers may have a base area selected from a group consisting of polygon, circle, semicircle, ellipse, trapezium, triangle, rhombus, square and rectangle or a star-shaped base area. The containers may also have the shape of a hood, of assembled pockets or the shape of a tied-up bag. To ensure safe handling even during pressure filling, however, it is advantageous if, during the filling process, the cage contacts the container to be filled, as uniformly and snugly as possible. It is therefore expedient if the cage substantially corresponds to the shape of the container.
Additional fittings in the cage allow adaptation to the respective container to be filled.

Owing to the excess pressure.prevailing in the interior of the container, the air is carried off over the surface of the container. As the excess pressure is able to escape, compression of the filling product is also achieved. To enable the excess pressure to escape as rapidly as possible from the container, in particular in the case of a snugly fitting cage, it is expedient if the cage itself is also gas-permeable. The cage may have walls with openings or with adequate porosity. This may be achieved, for example, by openings in the cage walls. It is particularly advantageous if the cage walls are produced from a material selected from perforated plate,-mesh or netting, woven fabric or sintered material or a mesh material, because this allows high gas permeability with adequate stability to ensure that the container does not explode even under high filling pressures. The cage may be in several parts, preferably two parts. The cage may have a bottom and may be designed without a bottom. Preferably, the cage has no bottom.

According to a particularly preferred embodiment of the apparatus according to the invention, the cage may be in two or more parts and the apparatus comprises additional devices with which the two parts of the cage may be separated from one another and may be driven apart manually or automatically, preferably electro-pneumatically, to release the filled container. In particular in the case of cage shapes with a polygonal base area, it is expedient if the cage can be separated along a diagonal as this prevents damage to the container.

According to a particularly preferred embodiment of the present invention, the cage has no bottom, in other words the cage is open at the bottom. This embodiment allows particularly simple management of the filling process. After the two-part cage has been closed and the two parts have been connected to one another, the actual filling process can begin. For example, the container can then be positioned directly on a plate or a pallet, the feed nozzle can then be introduced into the feed orifice of the container and can be connected in an airtight manner to the container. On completion of the filling process, the two cage wedges can then be separated from one another and driven apart to release the filled container. As the filled container is then standing on a plate or pallet, it can easily be removed by a transportation device.

Another subject matter of the invention is a flexible container for finely-divided solids for repeated filling and draining, characterized in that it consists of at least two plies, one above the other, wherein one ply consists of an air-permeable supporting material that is preferably non-coated and the other ply consists of a filter material.

According to one embodiment, the air-permeable, supporting material can be arranged on the outside and filter material on the inside. However, other combinations of the plies, from the inside toward the outside, are possible, wherein the combination of supporting and filtering element of the container is present. The material used for each ply can be commercially available material.

The container can be designed for optional amounts of finely-divided filler materials. The container preferably can be used for amounts up to 1,200 kg. In contrast, containers according to prior art could only accommodate filling amounts of 90 to 100 kg.

The container permits a dust-free filling through compacting on the inside of the container, in particular using the apparatus according to the invention, wherein clearly higher bulk weights can be achieved.

The finely-divided material can be drained from the container through a preceding fluidization and simultaneous conveying. For this, known drainage devices can be used.

Another embodiment is a corrugated cardboard container (carton) for finely-divided materials, which can be ventilated.
This container is characterized by its design, in which one side of the corrugated cardboard consists of a highly air-permeable paper, and the inside undulation(s) as well as the other sides and intermediate plies consist of non air-permeable standard corrugated cardboard with microperforation.

Optional combinations of the outer plies, the inner plies and the intermediate plies are possible, wherein the container (corrugated cardboard container) has a supporting as well as filtering design.

This results in the following advantages as compared to the known technology:

The highly air-permeable inner ply acts as a filter for the product and permits the air to escape;

The outer ply and the intermediate ply (plies) and the undulation(s) absorb the forces, but permit the air to escape.
As a result of this configuration, air is moved quickly through the walls and the product can be highly compacted inside the container with considerably higher filling weights than is possible with known systems (up to 1,200 kg as compared to the known 90-100 kg, depending on the product type).

The invention will now be described in further detail with reference to the accompanying drawings, in which:

Figure 1 is a side view of a preferred embodiment of the present invention;

Figure 2 is a plan view of the embodiment according to Figure 1 with opened cage;

Figure 3 shows schematically a representation of a container according to the invention;

Figure 4 shows the drain of Figure 3 in schematic detail;
Figure 5 shows a schematic representation of a corrugated cardboard container according to the invention.

As shown in the Figures, a preferred embodiment of the invention comprises a framework 1 with two rails 2 at the top, along which the two halves 3a and 3b of the cage 3 which may be moved by conventional drive devices.

In the embodiment shown in Figures 1 and 2, the cage has a square base area and is divided along the diagonal into the two halves 3a and 3b. This ensures that two halves easily can be separated from the filled container, even when the container has been pressed against the cage owing to a high filling pressure.

The cage also has two half shells 4a and 4b which surround the feed nozzle (not shown) when closed.

As shown in Figure 2, the cage 3 is open at the bottom and the container is positioned on a pallet or plate during the filling process. It also is advantageous, as shown in the drawings, if the filling nozzle is arranged symmetrically with respect to the frame 1, so a cage half 3a may be removed further from the pallet or plate 5 to allow easy access, for example, for a transportation device for removing the filled container.

A container according to the invention is shown schematically in Figure. 3.

On the one hand, a container 6 according to Figure 3 consists of two plies, namely a supporting, air-permeable outer material 7 (PP woven ribbon material with a weight of 75 to 300 g/m3) The material is not coated so that air can pass through.
This outer layer is supporting as well as carrying for product amounts up to 1,200 kg.

On the other hand, a second ply, the inner ply 8 (inliner), consists of a filter material (e.g. HDPE nonwoven Tyvek' by DuPont, which holds back the finely-divided product, but permits the air escaping from the product to pass through (filter effect).

The drain 9 is shown schematically in Figure 4A. The drain has a conical design and is thus particularly suitable for a special draining apparatus according to EP 761,566. Sticky tapes 10 and 11 are provided, and Figures 4B and 4C are a side view and a view from above, respectively, of the tape 11 which is equipped with a D-ring.

Another container according to the invention is shown schematically in Figure 5, with highly permeable paper 12 on the product side, microperforate undulation 13, and non-porous paper 14.

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. Apparatus for filling a container with granular, powdered or finely-divided solids having a high air content, the apparatus comprising a feed nozzle for introduction of the solids into a feed orifice of the container under positive pressure, the feed nozzle comprising a flexible sealing skin which provides dust-free pressure filling of the container, and the container being surrounded by a two-part or multi-part cage which is gas-permeable.
2. Apparatus as defined in claim 1, wherein the cage has two or more parts, which can be separated from one another to release a filled container.
3. Apparatus as defined in claim 2, wherein the apparatus comprises a device for separating the two or more parts of the cage, and wherein separation is manual or involves drive mechanisms.
4. Apparatus as defined in claim 1, 2 or 3, wherein the cage has walls provided with orifices or pores.
5. Apparatus as defined in claim 4, wherein the walls are perforated plate, mesh, netting, woven fabric, or sintered material.
6. Apparatus as defined in any one of claims 1 to 5, wherein the cage is provided with a bottom.
7. ~Apparatus as defined in any one of claims 1 to 5, wherein the cage does not have a bottom.
8. ~Apparatus as defined in any one of claims 1 to 5, wherein the base area of the cage has a shape which is a polygon, a circle, a semicircle, an ellipse, a trapezium, a triangle, a rhombus, a square or rectangle, or the base area is star-shaped.
9. ~A method for filling a container with finely-divided granular, powdered solids having a high air content, the method comprising:

placing an air-permeable container in an apparatus as defined in any one of claims 1 to 8;

connecting the feed nozzle to the container by air-tight connector;

filling the container under positive pressure; and removing the filled container.
10. A method as defined in claim 9, wherein the container is removed by separating the two or more parts of the cage.
11. A method as defined in claim 9 or 10, wherein the container is an air-permeable plastic woven fabric, a plastic woven fabric, a textile woven fabric, cardboard, paper, paper-plastic woven fabric, plastic non-woven fabric, textile non-woven fabric, or composites thereof.
12. ~A method as defined in claim 9, 10 or 11, wherein the filling pressure is 0 to 8 bar.
13. ~A method as defined in claim 12, wherein the filling pressure is 0 to 2 bar.
14. ~A method as defined in claim 12, wherein the filling pressure is 0.2 to 1.2 bar.
15. ~A method as defined in any one of claims 9 to 14, wherein the finely-divided granular powdered solids having a high air content are pyrogenic oxides, precipitated oxides, carbon black or modifications thereof.
16. ~A method as defined in any one of claims 9 to 15, wherein the container has a base area shape which is a polygon, circle, a semicircle, an ellipse, a trapezium, a triangle, a rhombus, a square or rectangle, or the base area has a star-shape or the shape of a hood, of assembled pockets.
17. ~A method as defined in any one of claims 9 to 15, wherein the container has the form of a tied bag.
CA002452775A 2001-07-11 2002-07-09 Filling containers with granular or pulverulent material Expired - Lifetime CA2452775C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA2569061A CA2569061C (en) 2001-07-11 2002-07-09 Containers for granular or pulverulent material

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10133666A DE10133666A1 (en) 2001-07-11 2001-07-11 Device and method for filling large containers of different sizes and shapes
DE10133666.7 2001-07-11
EP01122734 2001-09-21
EP01122734.5 2001-09-21
PCT/EP2002/007615 WO2003006314A1 (en) 2001-07-11 2002-07-09 Apparatus and process for filling containers with granular or pulverulent material

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CA2569061A Division CA2569061C (en) 2001-07-11 2002-07-09 Containers for granular or pulverulent material

Publications (2)

Publication Number Publication Date
CA2452775A1 CA2452775A1 (en) 2003-01-23
CA2452775C true CA2452775C (en) 2007-09-25

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ID=26009681

Family Applications (2)

Application Number Title Priority Date Filing Date
CA002452775A Expired - Lifetime CA2452775C (en) 2001-07-11 2002-07-09 Filling containers with granular or pulverulent material
CA2569061A Expired - Lifetime CA2569061C (en) 2001-07-11 2002-07-09 Containers for granular or pulverulent material

Family Applications After (1)

Application Number Title Priority Date Filing Date
CA2569061A Expired - Lifetime CA2569061C (en) 2001-07-11 2002-07-09 Containers for granular or pulverulent material

Country Status (12)

Country Link
EP (3) EP1661612A1 (en)
JP (1) JP4088668B2 (en)
KR (1) KR100599026B1 (en)
CN (1) CN1248912C (en)
AT (2) ATE345266T1 (en)
CA (2) CA2452775C (en)
DE (2) DE60216095T2 (en)
DK (1) DK1404576T3 (en)
ES (1) ES2276943T3 (en)
PL (1) PL207558B1 (en)
UA (1) UA76169C2 (en)
WO (1) WO2003006314A1 (en)

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Publication number Publication date
KR20040019054A (en) 2004-03-04
ES2276943T3 (en) 2007-07-01
CN1525921A (en) 2004-09-01
CA2452775A1 (en) 2003-01-23
JP4088668B2 (en) 2008-05-21
DE60231261D1 (en) 2009-04-02
KR100599026B1 (en) 2006-07-12
ATE345266T1 (en) 2006-12-15
DK1404576T3 (en) 2007-03-19
PL207558B1 (en) 2011-01-31
EP1404576B1 (en) 2006-11-15
CA2569061C (en) 2010-09-28
ATE423070T1 (en) 2009-03-15
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JP2004533978A (en) 2004-11-11
EP1404576A1 (en) 2004-04-07
UA76169C2 (en) 2006-07-17
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PL367330A1 (en) 2005-02-21
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DE60216095T2 (en) 2007-06-21

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