EP1417059A2 - Verfahren und metallgusskasten zur schadstoffemissionsreduktion in giessereibetrieben - Google Patents
Verfahren und metallgusskasten zur schadstoffemissionsreduktion in giessereibetriebenInfo
- Publication number
- EP1417059A2 EP1417059A2 EP02767378A EP02767378A EP1417059A2 EP 1417059 A2 EP1417059 A2 EP 1417059A2 EP 02767378 A EP02767378 A EP 02767378A EP 02767378 A EP02767378 A EP 02767378A EP 1417059 A2 EP1417059 A2 EP 1417059A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- substance
- molding sand
- metal casting
- mold
- additional
- 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.)
- Granted
Links
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 47
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 47
- 238000005058 metal casting Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 4
- 150000002576 ketones Chemical class 0.000 claims abstract description 4
- 239000003110 molding sand Substances 0.000 claims description 32
- 238000005266 casting Methods 0.000 claims description 19
- 238000002485 combustion reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011162 core material Substances 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 239000004449 solid propellant Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 238000007792 addition Methods 0.000 description 8
- 239000003570 air Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012778 molding material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
Definitions
- the invention relates to a method for reducing pollutant emissions, in particular in the form of pyrolysis products, from metal casting boxes used in foundries.
- the invention further relates to metal casting boxes for carrying out the method.
- the pollutant emissions that occur during metal casting are mostly released at the casting line itself as well as at the cooling line and unpacking point, i.e. directly after the hot liquid metal is filled in.
- the pollutants escape, for example, through the neck of the two mold halves.
- a further release of a larger amount of emissions takes place when the hot molding material is removed from the metal casting mold (unpacking point).
- Occasional combustion of the escaping emissions takes place or is triggered by an ignition flame. However, such burns only take place if the local concentration, temperature and calorific value of the emissions are sufficient for this.
- the invention is therefore based on the object of further developing the method mentioned at the outset so that an effective reduction in pollutant emissions is achieved with little effort.
- the process should be applicable to all metal molds, regardless of the composition and the amount of emissions.
- this object is achieved in that at least one additional combustible substance is added to the metal casting boxes, which - if it is not gaseous - turns into a gaseous state when heated and burns together with the pollutants when it emerges from the metal casting boxes.
- the invention is therefore based on the idea of ensuring, by adding an additional combustible substance, that the pollutants then also burn. The joint combustion of pollutants and the flammable substance therefore takes place almost independently of the amount and the calorific value of the pollutants.
- Metal molds generally consist of at least two parts, preferably two mold halves. At least one of these mold halves, preferably two mold halves, enclose the molding sand, which can be, for example, a porous sand material pressed using additives and pressure. The shape of the molding sand determines the outer contour of the later cast. Optionally, one or more mold cores can be added to the casting space, which then determine the inner contour and cavities of the cast material.
- pollutant emissions to be odorous and harmful gases, smoke, dusts and / or aerosols released into the ambient air.
- An additional combustible substance used according to the invention is an organic substance which preferably contains a wax or an oil, particularly preferably a ketone, an aldehyde, ether, alkane or alcohol.
- This substance is therefore a chemical compound that burns through self-ignition or with the help of an ignition flame when it comes out of the mold box in gaseous form and comes into contact with the outside air.
- This substance is added to the metal casting box in addition to the additives commonly used in metal casting.
- Such a combustible substance preferably has a high calorific value.
- flammable substances which only burn in the presence of ambient air or are highly flammable or ignite themselves are preferred for carrying out the method according to the invention. Flammable substances are particularly preferred which, under the conditions of a metal casting, only burn under self-ignition or with the aid of an ignition flame when they exit the metal casting mold.
- a flammable gas (natural gas) can also be used as the flammable substance. This can be pushed into the molding sand with the help of injection pipes and can be controlled as required.
- the use of gas is particularly favorable in the case of stationary, that is to say molds which are not produced on the line - without transporting the container.
- the combustible substance added to the metal casting mold mixes in gaseous form with the pollutants in the metal casting mold and escapes together with them. When this mixture is burned, the pollutants are also burned by the heat of combustion of the additional combustible substance added according to the invention.
- the additional substance is preferably the metal casting boxes in the outer molding sand
- the additional combustible substance is introduced into at least one of the mold sand halves after pressing and casting by injection and / or before pressing by mixing with the molding sand or parts of the molding sand.
- liquid combustible substance basically enables the substance to be stored in the cavities between the molding sand grains and to be distributed by capillary forces.
- the additional flammable substance can namely be added to the metal mold evenly or locally concentrated.
- the point of addition should be chosen so that thorough mixing with the pollutants in the gas phase is achieved, which can flow, for example, along gaps or channels provided in the molding sand or the outer casting mold itself. Avoid direct contact of the added flammable substance with the hot liquid castings, as this would generate a strong spontaneous pressure wave.
- the method according to the invention is also not intended to influence existing, optimized molding techniques and / or materials.
- the addition of the additional fuel has therefore proven to be particularly advantageous only after the liquid metal has been poured into the casting mold. Even a small spread of the additional fuel - gaseous or liquid
- the aim is to position the additional combustible substance in the molding sand in such a way that it mixes with the pollutants of the casting mold in the sense of optimal combustion of the pollutant / substance mixture.
- an advantageous optimal dosage of the additional substance take place.
- combustion of the pollutants can be optimized for the entire emission period. In a particularly advantageous manner, just so much additional flammable gas is emitted that the escaping pollutants burn in a permanent flame.
- At least one additional combustible substance is positioned in front of the attachment edge of the mold and / or in front of at least one outlet opening of the mold, particularly preferably in the molding sand in front of the attachment edge of the mold and / or in front of at least one outlet opening of the mold.
- the amount of the combustible substance to be added depends on the dimensions, the structure and the composition of the respective metal casting mold. In addition to positioning in the metal casting box, the amount of substance and the composition of the substance also determine the extent of the combustion of the released pollutants.
- At least such an amount of additional combustible substance is added to the mold that combustion of the pollutants is ensured at least during part of the cooling phase of the casting process, preferably until the mold is opened, particularly preferably until the cast goods are detached.
- An additional addition of fuel is particularly preferred which, by penetrating the entire molding material - when the casting box is broken open to remove the cast goods - ensures complete combustion of all contaminants which are still stored in the molding sand.
- the entire molding sand burns openly with a large surface.
- a second or repeated addition / injection of fuel into the mold can also be carried out.
- any compound or a mixture of compounds which is combustible and flammable under the conditions of a metal casting process can be used as the flammable substance.
- a large number of such compounds or mixtures are known to the person skilled in the art which, at the higher temperatures and ambient conditions in the metal Casting box and / or at the edge of the neck have the required properties during escape and contact with atmospheric oxygen.
- the additional combustible substances used in the process preferably contain at least one organic substance, preferably a wax or an oil, particularly preferably a ketone, an aldehyde, ether, alkanes or alcohol.
- Substances are particularly advantageous which do not decompose due to the low heat exposure caused by the positioning according to the invention, but pass chemically unchanged into the gas phase.
- Flammable substances which have a boiling point between 20 ° C. and 200 ° C. are preferably used, particularly preferably substances with a boiling point between 50 ° C. and 100 ° C.
- substances which burn to form low-odor and harmless compounds are preferred for carrying out the process.
- gases which burn to form carbon dioxide and water are very preferably gas mixtures which burn to form carbon dioxide and water.
- the added substances can be present, for example, as a solid, but preferably as a liquid when added to the metal casting mold. It is particularly favorable if the substances are present as a liquid when added to the metal casting mold and evaporate / boil when the hot metal or the hot exhaust gas emissions convey heat.
- the transfer of the combustible substances into the gas phase is preferably mediated by thermal bridges on the part of the hot cast goods over the molding sand.
- the heat spreading throughout the casting box which emanates from the cooling of the cast goods, reaches the combustible substance added according to the invention with a constant rise in temperature in the molding sand and converts it into the gas phase.
- the substance evaporates due to the hot pollutants that are formed during the casting process, and preferably only burns together with the pollutants when it emerges from the mold and comes into contact with air.
- the mixture of substances and pollutants can only be burned when it comes into contact with an ignition flame.
- a good mixing of the pollutants with the additional substance is advantageous, which is ensured by a sufficiently long mixing section of the two gases before they come into contact with the outside air.
- the invention further relates to a metal casting box which is modified to carry out the method according to the invention. It has proven to be particularly favorable if the metal casting box consists of at least two casting mold parts, in which at least one of the halves in the attachment edge has a groove as an outlet opening for gases. Grooves and holes in the molding sand that facilitate the removal of the gases can also be provided in an advantageous manner.
- gas guides are provided within the molding sand, which lead into an outlet opening.
- At least one of the two mold halves has a cutout in the molding sand for receiving combustible substances.
- FIG. 3 shows a schematic vertical sectional view of a molded box part to illustrate the flow course of the pollutants when an additional fuel is used away from the casting mold, towards the attachment edge of the molded box and
- Fig. 4 three different ways A, B and C of adding flammable substances in a metal mold.
- the dashed line shows the course of the total mass of hydrocarbons in the exhaust air, after a short mixing with the outside air and its partial (Fig. 1) or fully constant combustion (Fig. 2).
- An exemplary measuring point is indicated at point 8 in FIG. 3.
- the Y axis shows the mass of the pollutant quantity.
- liquid metal is added to the metal mold and ignition of the pollutants is triggered at time t1.
- the combustion has ended because the relatively low emission of pollutants no longer enables further combustion.
- the integral of the area below the dashed line is a measure of the still large amount of pollutants emitted.
- adding a combustible substance increases the level of hydrocarbon emission on the Y axis.
- a part of a molding box 1 is shown.
- the cast goods 3 lie in the molding sand 2.
- the increasing blackening in the area of the cast goods is intended to indicate the temperature profile.
- the additional combustible substance 4 is located in the vicinity of a gas outlet opening (for example in the area of the attachment edge of the two halves of the molding box 1.
- the flow lines 5 shown show that the gasified fuel is mixed with the harmful gases of the cast goods 3. This gas mixture escapes in the The area of the attachment edges of the two halves of the molding box 1 in the direction of the arrow 6 outwards and reaches the point at which the total emission shown in Figures 1 and 2.
- Fig. 4 shows an example of various addition options for the combustible substance 4 in the casting box 1.
- the additional substance 4 is stored in partial areas of the molding sand 2, namely by injection or storage before the assembly of the halves of the molding box 1 on both sides of the dividing line 9 or by injection after casting.
- the combustible substance 4 can be stored in only one half by pouring or storing in partial areas of the molding sand 2 before the assembly of the box halves.
- FIG. 4C illustrates another possibility, according to which the combustible substance 4 is embedded in partial areas of the molding sand 2, namely after the casting by means of injection into the molding sand.
- the additional combustible substance 4 is always stored separately from the cast goods 3, in such a way that it does not reach its surface. Regardless of which of the three storage options is chosen, it is always a storage which ensures that the substance, without decomposition, is only forced out of the mold by heating with the resultant evaporation / boiling, without pyrolysis taking place.
- the substance can be stored in the mold box in such a way that it is distributed in gaseous or vaporous form when heated in high concentration, with the aim of escaping and burning together with the pollutants when the mold is opened (unpacking point).
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Processing Of Solid Wastes (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI200230084T SI1417059T1 (de) | 2001-08-14 | 2002-08-13 | |
| DK02767378T DK1417059T3 (da) | 2001-08-14 | 2002-08-13 | Fremgangsmåde og metalstöbekasse til reduktion af emissioner af skadelige stoffer i stöberivirksomheder |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10139801 | 2001-08-14 | ||
| DE10139801 | 2001-08-14 | ||
| PCT/EP2002/009078 WO2003015956A2 (de) | 2001-08-14 | 2002-08-13 | Verfahren und metallgusskasten zur schadstoffemissionsreduktion in giessereibetrieben |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1417059A2 true EP1417059A2 (de) | 2004-05-12 |
| EP1417059B1 EP1417059B1 (de) | 2004-12-15 |
Family
ID=7695348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02767378A Expired - Lifetime EP1417059B1 (de) | 2001-08-14 | 2002-08-13 | Verfahren und metallgusskasten zur schadstoffemissionsreduktion in giessereibetrieben |
Country Status (17)
| Country | Link |
|---|---|
| US (2) | US20040238155A1 (de) |
| EP (1) | EP1417059B1 (de) |
| JP (1) | JP2004538151A (de) |
| AT (1) | ATE284766T1 (de) |
| AU (1) | AU2002331242A1 (de) |
| BR (1) | BR0212184A (de) |
| CA (1) | CA2456936A1 (de) |
| DE (2) | DE10237147A1 (de) |
| EA (1) | EA005446B1 (de) |
| ES (1) | ES2235088T3 (de) |
| HR (1) | HRP20040182A2 (de) |
| HU (1) | HUP0401327A2 (de) |
| MX (1) | MXPA04001392A (de) |
| PL (1) | PL365635A1 (de) |
| PT (1) | PT1417059E (de) |
| WO (1) | WO2003015956A2 (de) |
| ZA (1) | ZA200401994B (de) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008025311A1 (de) | 2008-05-27 | 2009-12-03 | Ashland-Südchemie-Kernfest GmbH | Geruchs- und schadstoffadsorbierende Beschichtungsmasse für den kastengebundenen Metallguss |
| DE102022129733A1 (de) * | 2022-11-10 | 2024-05-16 | Man Truck & Bus Se | Verfahren und Vorrichtung zum Zünden von Gießgasen |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1239437B (de) * | 1965-02-13 | 1967-04-27 | Gruenzweig & Hartmann | Verfahren zur Herstellung von Giessformen und verlorenes Modell zu seiner Durchfuehrung |
| DE2916911A1 (de) * | 1979-04-26 | 1980-10-30 | Maschf Augsburg Nuernberg Ag | Verfahren zur unschaedlichmachung von giessgasen |
| US4266595A (en) * | 1979-08-06 | 1981-05-12 | Ford Motor Company | Use of mold venting practices in green sand molding for odor reduction |
| DE3246324C2 (de) * | 1982-12-15 | 1994-07-14 | CBF Carboform Ewald Schmidt, 4600 Dortmund | Verwendung von Kohlenstoffprodukten als Zusatz zu tongebundenen Gießereiformsandmassen |
| GB2188267B (en) * | 1986-03-14 | 1989-11-15 | Morikawa Sangyo | Casting method and apparatus |
| DE4226327A1 (de) * | 1991-11-07 | 1993-05-13 | Ruetgerswerke Ag | Ligninmodifizierte bindemittel |
| DE4327292C2 (de) * | 1993-08-13 | 1996-04-25 | Ashland Suedchemie Kernfest | Bindemittel zur Herstellung von Gießereikernen und -formen und ihre Verwendung |
| DE4327396C2 (de) * | 1993-08-14 | 1996-10-17 | Kessler & Luch Gmbh | Verfahren und Vorrichtung zum Erfassen, Absaugen und Abscheiden von beim Abgießen von Formkästen frei werdenden Pyrolyse-Produkten |
-
2002
- 2002-08-13 JP JP2003520501A patent/JP2004538151A/ja active Pending
- 2002-08-13 DE DE10237147A patent/DE10237147A1/de not_active Withdrawn
- 2002-08-13 HR HR20040182A patent/HRP20040182A2/hr not_active Application Discontinuation
- 2002-08-13 DE DE50201808T patent/DE50201808D1/de not_active Expired - Lifetime
- 2002-08-13 AU AU2002331242A patent/AU2002331242A1/en not_active Abandoned
- 2002-08-13 CA CA002456936A patent/CA2456936A1/en not_active Abandoned
- 2002-08-13 AT AT02767378T patent/ATE284766T1/de not_active IP Right Cessation
- 2002-08-13 ES ES02767378T patent/ES2235088T3/es not_active Expired - Lifetime
- 2002-08-13 EP EP02767378A patent/EP1417059B1/de not_active Expired - Lifetime
- 2002-08-13 PT PT02767378T patent/PT1417059E/pt unknown
- 2002-08-13 WO PCT/EP2002/009078 patent/WO2003015956A2/de not_active Ceased
- 2002-08-13 HU HU0401327A patent/HUP0401327A2/hu unknown
- 2002-08-13 US US10/486,772 patent/US20040238155A1/en not_active Abandoned
- 2002-08-13 PL PL02365635A patent/PL365635A1/xx unknown
- 2002-08-13 BR BR0212184-0A patent/BR0212184A/pt not_active Application Discontinuation
- 2002-08-13 MX MXPA04001392A patent/MXPA04001392A/es not_active Application Discontinuation
- 2002-08-13 EA EA200400250A patent/EA005446B1/ru not_active IP Right Cessation
-
2004
- 2004-03-11 ZA ZA200401994A patent/ZA200401994B/xx unknown
-
2006
- 2006-10-31 US US11/591,035 patent/US7299858B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03015956A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003015956A3 (de) | 2003-10-09 |
| US20040238155A1 (en) | 2004-12-02 |
| US7299858B2 (en) | 2007-11-27 |
| ES2235088T3 (es) | 2005-07-01 |
| HUP0401327A2 (en) | 2004-10-28 |
| EA005446B1 (ru) | 2005-02-24 |
| ZA200401994B (en) | 2005-04-20 |
| CA2456936A1 (en) | 2003-02-27 |
| US20070102137A1 (en) | 2007-05-10 |
| MXPA04001392A (es) | 2005-06-06 |
| AU2002331242A1 (en) | 2003-03-03 |
| ATE284766T1 (de) | 2005-01-15 |
| PT1417059E (pt) | 2005-05-31 |
| DE10237147A1 (de) | 2003-02-27 |
| JP2004538151A (ja) | 2004-12-24 |
| BR0212184A (pt) | 2004-10-05 |
| PL365635A1 (en) | 2005-01-10 |
| EA200400250A1 (ru) | 2004-08-26 |
| EP1417059B1 (de) | 2004-12-15 |
| HRP20040182A2 (en) | 2004-08-31 |
| WO2003015956A2 (de) | 2003-02-27 |
| DE50201808D1 (de) | 2005-01-20 |
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