EP1697266A1 - Verfahren und vorrichtung zum konditionieren eines abk hlpro zessbereiches zur verringerung von korrosion - Google Patents
Verfahren und vorrichtung zum konditionieren eines abk hlpro zessbereiches zur verringerung von korrosionInfo
- Publication number
- EP1697266A1 EP1697266A1 EP04714280A EP04714280A EP1697266A1 EP 1697266 A1 EP1697266 A1 EP 1697266A1 EP 04714280 A EP04714280 A EP 04714280A EP 04714280 A EP04714280 A EP 04714280A EP 1697266 A1 EP1697266 A1 EP 1697266A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- conditioning
- conditioning gas
- cooling
- gas
- glass
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 171
- 230000003750 conditioning effect Effects 0.000 title claims abstract description 156
- 238000001816 cooling Methods 0.000 title claims abstract description 131
- 230000008569 process Effects 0.000 title claims abstract description 120
- 238000005260 corrosion Methods 0.000 title claims description 27
- 230000007797 corrosion Effects 0.000 title claims description 27
- 239000011521 glass Substances 0.000 claims abstract description 135
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000000465 moulding Methods 0.000 claims abstract description 26
- 239000000155 melt Substances 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 158
- 239000003570 air Substances 0.000 claims description 67
- 239000012080 ambient air Substances 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 28
- 239000003507 refrigerant Substances 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 230000001143 conditioned effect Effects 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000156 glass melt Substances 0.000 claims description 12
- 238000010309 melting process Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000005057 refrigeration Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 9
- 238000007906 compression Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 6
- 230000002745 absorbent Effects 0.000 claims 6
- 239000003463 adsorbent Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007730 finishing process Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000161 steel melt Substances 0.000 claims 1
- 239000002918 waste heat Substances 0.000 description 18
- 238000007670 refining Methods 0.000 description 10
- 239000005357 flat glass Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004378 air conditioning Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006124 Pilkington process Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000005329 float glass Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 239000005336 safety glass Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/265—Drying gases or vapours by refrigeration (condensation)
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
- C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B3/00—Charging the melting furnaces
- C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
- C03B3/023—Preheating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
Definitions
- the invention relates to a method and a device for conditioning - at least a partial area of a cooling process area. 5
- a manufacturing process known as the “float glass” process is known from practice.
- glass melt is continuously produced by melting a mixture of mineral glass raw materials, which typically also contain A1 2 0 3 , CaO, MgO, in addition to SiO 2 .
- ⁇ a z O, K 2 0 and 10 also sometimes include Fe 2 0 3 and TiO z or S0 3 , produced in a heated glass trough or a melting furnace.
- the glass melt is poured out onto a tin bath from liquid tin and spreads under the influence of gravity and the surface forces in the form of a glass ribbon or a glass film on the tin bath uniformly and floats on the liquid metal. This zone is therefore also called the "float zone".
- the temperature on the tin bath is initially typically about 1000 ° C.
- the glass ribbon is cooled on the tin bath to about 600 ° C to 700 ° C and thereby by means of rollers arranged at the edge of the room 20
- the pulled-off glass ribbon is then transported on a conveyor belt through a cooling system which comprises a cooling furnace and a cooling section and is called "annealing instruction" in English.
- annealing a targeted, comparatively slow cooling of the glass to Nermei fertilizing thermally induced internal stresses in the glass is carried out, also referred to as "annealing".
- annealing Normally the glass band on the flat sides would cool faster than on the inside and the high ones caused by them Stresses in the glass caused by temperature gradients would lead to cracks or breaks in the glass ribbon, especially when later cutting into individual slices 30.
- a temperature curve regulated by temperature sensors and controllers is now adhered to, which above all keeps the temperature gradients in the glass ribbon low and relaxation processes can run in the glass, so the glass is typically placed on a
- REPLACEMENT SHEET so-called annealing temperature cooled down and then kept at this temperature for a certain period of time, the period of time depending on the type of glass, the thickness of the glass, the coefficient of thermal expansion and the desired residual stress.
- annealing temperature relaxation processes take place in the glass to reduce the internal stresses.
- the glass is then cooled further with a predetermined temperature gradient. After passing through the cooling section, individual flat glass units are separated from the continuous glass band and then stored in a warehouse before further processing or transport.
- the entire float-glass process described is carried out continuously, ie the glass ribbon is continuously removed from the tin bath and the glass batch and the glass melt produced from it are adjusted accordingly.
- the glasses are formed at the high melting temperatures in the glass trough by the batch reaction from the starting substances.
- This process is also called noise melting.
- a very inhomogeneous melt is present, in which the Si0 2 concentrations that occur as the main constituent of the glass range from saturation concentration to at least the desired concentration and the melt is also heavily permeated with bubbles, the reaction gases and enclosed void gases, in particular air or Water vapor. Therefore, in the so-called bright melt, the bubbles formed are expelled in a refining process, in particular using suitable refining agents to achieve the gas supersaturation required during the refining, and then the melt is left to stand under homogenization. At the end of the stand-off process, the melt is poured onto the tin bath and forms the glass ribbon.
- a “float glass” process in which in a melting zone of a glass melting furnace by burning fuel and oxygen-enriched oxidizing gas (or: gaseous oxidizing agent) with at least 80 vol.% Oxygen in burners Heat is generated to produce molten glass from glass raw materials. Substances are given methane, propane, oil and hydrogen. The molten glass is applied to the surface of a molten metal, typically molten tin, in a tub, spreads out there and forms a disk or plate made of glass (flat glass). The flat glass is then brought into a non-fired refining zone or "refining zone” and is cooled there without the burning of fuel and oxidizing agent.
- oxidizing gas or: gaseous oxidizing agent
- oxygen-enriched fuel gas Compared to burning with air with typically 20 to 21% by volume oxygen, the use of The advantage of oxygen-enriched fuel gas is that greater efficiency, improved refining reactions, higher temperatures, a lower gas volume and less formation of particles and nitrogen oxides are achieved.
- concentration of water vapor in the atmosphere of a glass melting furnace fired with oxygen-enriched oxidizing gas increases to 50 to 65% by volume compared to 15 to 20% by volume in an oven which is fired with an air / fuel mixture. It is now described in EP 1 285 887 ⁇ 2 that this causes higher water vapor pressure in the atmosphere, that small gas bubbles filled with water vapor formed during the refining process do not exist do not dissolve and remain in the end product, so that a higher scrap can be observed.
- EP 1 285 887 ⁇ 2 contemplates reducing the partial pressure of the water on the glass surface in the areas in which the small gas bubbles have to be desorbed by blowing air into the furnace near its outlet in order to concentration of combustion products, which is in particular also to reduce water on the glass surface.
- some disadvantages of this potential solution are given, in particular the reduction in energy efficiency, the increase in nitrogen oxide emissions and also the increase in gas volume that leaves the furnace.
- EP 1 285 887 ,2 it is therefore proposed in EP 1 285 887 ,2 to pass part of the oxidizing gas through the refining zone or in the area near the exit of the furnace before the nerburn, and with a sufficient amount low speed below 16.6 m / s to avoid mixing the oxidizing gas with gases above it.
- the passed gas stream of the oxidizing gas lowers the proportion of water vapor in the atmosphere on the surface of the molten glass in the refining zone to less than 25% by volume.
- any other dry gas that does not chemically react with the glass could be used to remove water vapor, especially air, fuel gas or carbon dioxide.
- a cooling furnace or tunnel furnace for thermal annealing or for low-stress cooling of flat glass in which a glass ribbon is passed in succession through three cooling zones, a pre-cooling zone (A), a cooling zone (B) and a post-cooling zone ( C), is performed.
- a group of cooling air heat exchangers is arranged in each of these cooling zones and cools the continuous glass ribbon by means of radiant heat exchange.
- the temperature in the individual cooling zones is regulated, so that a flat spatial negative temperature gradient in the transport direction results from an initial temperature of approximately 600 ° C. to a temperature of approximately 360 ° C.
- a cooling section with further cooling zones (D and F) is provided, in which the glass is further cooled down to an ambient temperature by direct cooling by air convection. So while in the cooling furnace or tunnel furnace ambient air is only an indirect cooling medium via the heat exchangers and the cooling by exchanging heat radiation, there is ambient air in the downstream cooling section, which corresponds to the last two zones (D, F) in EP 1 206 422 B1 provided as a direct cooling medium that is passed directly onto the glass ribbon.
- a problem which is known in practice is the different quality of the surfaces of the flat glass produced using the “float glass” process, with poorer quality and higher rejects in summer than in winter.
- Quality problems in particular cause the formation of a for further processing, in particular refinement or coating of the glass, disruptive gel layer with a silica-like composition and leaching and corrosion of the glass surface.
- These surface problems occur mainly on the atmosphere side of the glass pane, that is to say the side which did not face the tin in the tin bath - Phenomena are summarized in the present application under the uniform concept of corrosion, which should include all physical or chemical processes that change the glass surface in its structure or composition by reaction with the adjacent atmosphere.
- the reaction of the glass with water from the atmosphere is particularly relevant.
- the water vapor reacting with the glass on the glass surface leads to an increase in the alkali metal ion concentration on the surface of the glass and to the formation of corresponding alkali hydroxides or alkali which attack (leach out) the glass.
- so-called silanol groups are formed which change the optical and mechanical properties of the glass, in particular cause discoloration and make the glass softer on the surface than inside the glass pane, which is why it is also called a gel layer.
- the exact chemical and physical processes of glass corrosion are not yet fully understood.
- Glass corrosion has a number of serious disadvantages.
- suction cup impressions can occur on the gel layer of the glass pane surfaces.
- a layer of corrosion and gel is formed The extent that even adjacent discs in disc stacks can practically stick together.
- care is therefore taken to space the glass panes in the stacks with the aid of spacers, to continuously circulate the air between the glass plates and to keep the temperature in the storage rooms as constant as possible, and to protect the warehouse buildings against the ingress of moist atmospheres.
- Another problem with glass corrosion is that there can be defects or poor quality in coatings or refinements on the gel layer or corroded layer.
- the invention is based on the object of specifying a method and a device with which the corrosion of a glass, whether it is due to or in the presence of water vapor in the atmosphere adjacent to the surface, can be reduced or delayed.
- the method according to claim 1 is for conditioning at least a partial area of a cooling process area, in which during a cooling process Processes at least one molded body, preferably formed from a melt, is cooled in accordance with a predetermined or predeterminable (spatial and / or temporal) temperature profile, thermal-induced mechanical stresses in the molded body being kept low, suitable and determined and comprising the following process steps: a) passing at least one conditioning gas over at least one surface of the molded body which is corrodible in the presence of water, at least during part of the cooling process, b) adjusting (or: regulating, controlling) the absolute water content in the conditioning gas (as conditioning variable) in a range up to at most a predetermined or predefinable limit value, at least when the conditioning gas enters the cooling process area and / or when the conditioning gas hits the surface of the molded body.
- a predetermined or predeterminable (spatial and / or temporal) temperature profile thermal-induced mechanical stresses in the molded body being kept low
- the device according to claim 35 is for conditioning at least a partial area of a cooling process area for cooling at least one shaped body shaped in a molding process, preferably from a melt, in accordance with a predetermined or predeterminable temperature profile, thermally induced mechanical stresses in the shaped body being kept low, and preferably also Carrying out a method according to the invention suitably determines and comprises and comprises at least one drying device for drying at least one conditioning gas to an absolute humidity of at most a predetermined or predeterminable limit value and at least one conditioning gas device for guiding dried conditioning gas from the at least one drying device to the cooling process area.
- the invention is based on the surprising and new finding that glass corrosion does not only take place in the warehouse or during transport, but already in the cooling furnace and in the cooling section and even assumes a considerable extent, since the supply of ambient air often cools the glass considerably Amounts of moisture are entered into the cooling process lead to corrosion problems.
- the invention is further based on the idea of supplying conditioned gas, in particular conditioned air, with an absolute water content below a predetermined or predeterminable limit value when the glass produced from the melt is cooled (annealing) and thereby the water vapor content of the corrosion-prone Keep the glass surface low. This can significantly reduce the corrosion of the glass.
- the limit value of the absolute water content of the conditioning gas is preferably adapted to a desired maximum degree of corrosion or a maximum permissible increase in the degree of corrosion (or: increase in corrosion) during the cooling process.
- the invention is further based on the consideration that the process conditioning of the surface with dry conditioning gas is suitable not only in the manufacture of glass, but also in the manufacture of all materials or process products which are to be annealed and which have their structure or composition on their surface by reaction change with water in the adjacent atmosphere, for example also steels.
- the degree of corrosion of the process product to be determined at the end of the cooling process or the manufacturing process is to be kept below a predetermined value by conditioning the atmosphere of the process, at least during part of the process.
- the cooling process area comprises a cooling furnace and / or a cooling section and the conditioning gas is then fed to the shaped body at least in a partial area of the cooling oven and / or the cooling section.
- the area within the Abkühlvons, the conditioning gas is passed through the can of a near-surface region of the molding on the one hand up to the entire Abkuhl perspectives Kunststoff other hand be chosen.
- air or a gas with a composition that at least approximately corresponds to the composition of air is used as the conditioning gas, preferably ambient air from an environment outside the cooling process area and / or from an outside environment outside a building surrounding the cooling process area, the Ambient air is preferably sucked in and then filtered.
- a conditioning gas with a different composition can also be used, in particular a higher proportion of inert gas, in particular carbon dioxide, nitrogen or a noble gas, for example argon, can be set, and / or the composition of the conditioning gas can be set or changed as a further conditioning variable become.
- the purity of the conditioning gas, in particular by filtering, and / or the temperature of the conditioning gas, in particular in a temperature range between 5 ° C. and a process temperature in the process area, is preferably controlled, regulated or set as a further conditioning variable.
- the average flow rate of the or each conditioning gas flow is preferably set between approximately 5 m / s and approximately 20 m / s becomes.
- the conditioning gas flow is essentially stationary (independent of time).
- the conditioning gas is used only once in the process and is discharged to an environment after use in the process.
- the conditioning gas is circulated and dried in each run after use in the process.
- the method according to the invention is used or used in a particularly advantageous embodiment in a method for producing shaped bodies, with at least one raw material being transferred into the melt in a melting process, at least one shaped body being formed from the melt in a molding process and this (r) molded body is cooled in at least one cooling process area, the method according to the invention for conditioning the cooling process area being carried out in at least one partial area.
- the shaped bodies are preferably made of glass.
- glass melt is then preferably applied to a liquid carrier medium, in particular liquid metal, preferably tin, and a flat shaped body in the form of a layer or a band of glass is formed on the surface of the liquid carrier medium.
- the flat shaped article is then typically removed from the carrier medium and supplied to the cooling process or the cooling line.
- a continuous molded body is preferably produced or the molded body is produced continuously from the melt and the molded body is separated or divided into individual molded bodies following the cooling process.
- the moldings are conditioned even after cooling even further with dry conditioning gas, in particular dry process air, and thereby largely protected against the action of water.
- dry conditioning gas in particular dry process air
- Such subsequent conditioning can be carried out by directing the dry conditioning gas onto or over the surface (s) of the shaped bodies in a storage facility and / or during transport, for example in a truck, container or the like, and / or before or during a further processing or treatment of the moldings, in particular coating, finishing and / or processing into composite bodies.
- Conditioning with dry conditioning gas is, however, also advantageous before the shaped body is cooled, in particular during the molding process, during the melting process and / or even before the melting raw materials.
- dry conditioning gas can be used for a combustion process for burning, in particular oxidizing, fuel for heating the raw materials in the melting process, in particular burners can be fed in for burning the fuel.
- dry conditioning gas can be passed over a surface of the melt and / or during at least part of the molding process over at least one surface of the molding (s).
- the conditioning gas can be used in the process disclosed in the aforementioned EP 1 285 887 72 for overflowing the glass band in the refining zone of the melting furnace.
- dry conditioning gas can be above or through the or the raw material (s) or the batch are passed before the melting process.
- At least one conditioning device preferably comprises supply means for supplying conditioning gas and at least one outlet opening arranged or opening in the cooling process area as an outlet for the conditioning gas, the supply means being in flow connection with the at least one outlet opening or being able to be brought about.
- the water content of the conditioning gas essentially comprises water vapor (or: moisture, proportion of water in the gaseous state) in the unsaturated state and additionally also water droplets entrained or floating in the conditioning gas (or: water in liquid form).
- water vapor or: moisture, proportion of water in the gaseous state
- water droplets entrained or floating in the conditioning gas or: water in liquid form.
- the absolute water vapor content or the moisture load X corresponds to the quotient of the mass of water vapor (vapor mass) contained in the conditioning gas, measured for example in grams (g), and the mass of the dry remaining conditioning gas (dry gas mass), usually stated in kg, both of which Masses in the same gas volume, for example a cubic meter (1 m 3 ), at the same temperature and at the same pressure are determined.
- the absolute vapor content or the moisture load X is therefore a dimensionless quantity.
- the relative water vapor content or the relative humidity ⁇ is related to the state of saturation and is defined as the quotient of the partial density or Concentration of the water vapor at the specified temperature, for example measured in g / m 3 , and the saturation partial density of the water vapor, which would set or would occur at the same temperature when the saturation partial pressure of the water was reached, i.e. when the conditioning gas was saturated with water, and would also be measured in g / m 3 .
- the relative humidity also corresponds to the quotient of the current vapor partial pressure and the saturation vapor partial pressure.
- the relative humidity is dimensionless and is usually given in percent (%), the relative humidity being below 100% in the undersaturated state and 100% in the saturated state.
- the relative humidity of a gas decreases with increasing temperature at the same pressure.
- the gas contains absolutely more moisture at the higher temperature than at the lower temperature.
- the warmer gas can therefore absorb more moisture than the colder gas.
- the absolute moisture loading of the conditioning gas in particular the conditioning air, is kept below or at most 0.006, ie 6 g of water per 1 kg or 100 g of dry gas (X ⁇ 0.006). This applies to the conditioning of the cooling process area, but preferably also to the aforementioned conditioning of additional process areas.
- This maximum absolute moisture load X 0.006 as the absolute limit corresponds to a limit of the relative water content or the relative humidity of 30% at 25 ° C or 20% at 32 ° C or 10% at 45 ° C.
- the condition of the conditioning gas generally has to be entered into the process area, since the conditioning gas generally absorbs moisture again in the process area.
- the water content of the atmosphere on the surface of the moldings is reduced to such an extent that corrosion of a glass surface in the conditioned process area is practically completely avoided.
- conditioning gas that is to say extracting moisture from the conditioning gas
- cold is generated by means of a refrigeration cycle or a refrigeration machine and moisture is condensed out of the conditioning gas with the generated cold for drying the conditioning gas (cold drying, condensation drying) ).
- Chillers that are particularly useful for drying the conditioning gas are compression chillers and / or absorption chillers.
- Chillers remove heat from an area to be cooled to a delivery area from.
- a refrigerant is evaporated in an evaporator that is in heat exchange with the area to be cooled, and the heat or evaporation enthalpy required for the evaporation of the refrigerant is thereby removed from the area to be cooled.
- the refrigerant is then released in a condenser or condenser which is in heat exchange with the delivery area, the heat corresponding to the evaporation enthalpy and released to the delivery area.
- the liquefied refrigerant is then returned to the evaporator and the cycle starts again. in general, since the temperature in the discharge area is higher than in the area to be cooled, to overcome this negative temperature gradient operation S energie required for the refrigerating machine.
- a compressor or compressor In a compression refrigeration machine, usually a compressor or compressor is operated, which draws the vapor of the refrigerant out of the evaporator and compresses it and then feeds it to the condenser.
- the pressure in the refrigerant vapor which is increased in this way enables it to be liquefied, with both the thermal energy according to the evaporation enthalpy and the compression energy in the condenser being released to the delivery area.
- the condensed refrigerant is returned to the evaporator via a throttle section for pressure build-up in the condenser during compression.
- an absorber circuit in which a liquid or gas as a refrigerant in a (different) liquid is absorbed as a solvent in an absorber and then separated or desorbed from it again in a cooker or expeller by supplying heat as thermal operating energy is, for example, a system of lithium bromide as a solvent and water as a refrigerant or a system of water as a solvent and ammonia as a refrigerant.
- the refrigerant has a lower evaporation or boiling temperature than the solvent.
- the refrigerant vapor generated in the evaporator is fed to the absorber and absorbed in the solvent.
- the solution of solvent and refrigerant is pumped to the stove via a solution pump.
- the conditioning gas to be dried is then generally brought into the area of the refrigeration machine to be cooled or cooled and is brought into heat exchange with the evaporator, for example in a heat exchanger which is connected to a supply line for the conditioning gas.
- the condensed and walls precipitating water is collected in a particular flash tank and pumped regularly or continuously.
- the condensed water which is still carried in the form of droplets in the conditioning gas is preferably separated off in a droplet separator known per se and the condensate water formed in the process is also removed.
- the dried conditioning gas is then preferably reheated to a desired conditioning temperature, for example in a further heat exchanger or a heating device which is connected to the supply line for the conditioning gas.
- the conditioning gas can also be dried by adsorbing or absorbing or absorbing water vapor on an adsorbing, absorbing or hygroscopic material, for example silica, and then regenerating or expelling it, in particular by means of a regeneration device, which preferably uses the process waste heat as heating energy ,
- drying for example, drying with an absorption chiller (s) as the basic load and an additional drying with compression chiller ⁇ ) and / or hygroscopic material or for further drying.
- absorption chiller s
- compression chiller ⁇ additional drying with compression chiller ⁇
- enthalpy h of the moist gas which is composed of the enthalpy h g of the dry gas and the enthalpy h d of the steam.
- the enthalpy h of the dry gas corresponds approximately to the product of the temperature T and the specific heat c of the dry gas.
- the enthalpy h d of the steam corresponds approximately to the sum of the product of the temperature T and the specific heat c d of the steam on the one hand and additionally the evaporation enthalpy on the other.
- the so-called Mollier diagram is very often used, in which the enthalpy h of the moist gas, usually moist air, is plotted against its moisture load X, the moisture load X and on the abscissa on two orthogonal axes of the diagram the ordinate the temperature T can also be read. Starting from the corresponding temperature values, isotherms are plotted on the ordinate as straight lines with a gradient that increases with temperature.
- the Mollier diagram shows the various application cases, in particular the following numerical example:
- the (absolute) moisture load X of the moist air is about 0.017 or 17 g water per 1 kg dry air.
- the volume flow of the conditioning gas stream in particular the ambient air, can typically be selected between 10,000 and 500,000 m 3 / h.
- the cooling capacity required to dehumidify a given amount of air is calculated according to the relationship that the cooling capacity is the product of the density of the air, the enthalpy (diff er enz) and the volume flow.
- a cooling capacity of 0.24 MW would be, for example, at a volume flow of 10,000 m 3 / h, and a cooling capacity of 2 at a volume flow of 100,000 m 3 / h , 43 MW, with a volume flow of 250,000 m 3 / h a cooling capacity of 6.08 MW and with a volume flow of 500,000 m 3 / h a cooling capacity of 12.16 MW is required.
- heat recovery of process waste heat from the melting process and / or the molding process and / or the cooling process is carried out.
- the process waste heat is preferably used as operating energy for the refrigeration cycle or the refrigeration machine (s) for condensation drying of the conditioning gas, for example directly as thermal energy in the absorption refrigeration machines or the regeneration heating devices or by generator conversion into electrical energy for the compression refrigeration machines.
- the conditioning of one or the process area and / or the conduction or flow of conditioning gas over the molded article or articles can be carried out continuously in all embodiments, ie essentially without interruptions, or also discontinuously, ie with interruptions or in individual conditioning intervals or conditioning phases.
- This is particularly advantageous for the transport of the molded articles over long distances.
- the atmosphere in the container or the casing can also be replaced or reconditioned every now and then in order to remove any moisture that may have entered.
- a batch feed device 2 feeds a batch of mineral glass raw materials to a melting area 30 of a glass melting device (or: glass melting pan) 3.
- a glass melting device or: glass melting pan
- the batch is melted into a noise melt.
- a subsequent Blank melting region 31 of the glass-melting device 3 the glass melt (melt Blank) is purified.
- the hot exhaust gases A from the glass melting device 3, in particular the bright melting area 31, are discharged to the outside into an environment via an exhaust gas discharge device 32, which in particular comprises pipelines and / or a chimney.
- the refined glass melt is now supplied from the bright melting area 31 of the melting device 3 to a float bath, in particular a tin bath 4.
- the glass melt is poured onto the liquid metal, in particular tin, and prepares itself in the form of a band or a layer on the bath. While the temperature during the melting process in the glass Melting device 3 is still 1100 ° C to 1400 ° C, for example, the temperatures in the float bath 4 are still 1000 ° C at the entrance and approx. 600 ° C to 700 ° C at the exit.
- the viscous glass ribbon formed is drawn off from the float bath 4 and passed through a cooling device 7.
- the glass sheet first passes through a cooling oven 5, and then a cooling section 6 of the cooling device 7.
- a cooling furnace 5 In the cooling furnace 5, an indirect cooling by emission of heat radiation at the heat exchanger is performed with a secondary cooling circuit.
- the cooling section 6 In the cooling section 6 is cooled by cooling air directed directly onto the glass ribbon.
- a separating device (not shown) is provided, with which individual glass raw panes, typically with the dimensions 5 m by 5 m, are cut out from the glass band.
- the raw glass panes are then stored in a glass warehouse 8. From the glass warehouse 8, the raw glass panes or cut panes already adapted to the final dimensions are fed to a coating system 9, in particular a magnetron coating system, a glass finishing or other glass processing 10 or also a laminated safety glass (VSG) and / or insulating glass system 11.
- a coating system 9 in particular a magnetron coating system, a glass finishing or other glass processing 10 or also a laminated safety glass (VSG) and / or insulating glass system 11.
- the exhaust gases A which emerge from the glass melting device 3 into the exhaust gas removal device 32, still contain a considerable amount of heat Q or waste heat.
- This waste heat Q is used in the context of waste heat recovery for process air conditioning at different process locations.
- a first amount of waste heat Q1 is branched off from the waste heat Q and used for preheating the combustion air for the burners of the glass melting device 3, which are in particular assigned to the noise melting area 30.
- the amount of heat Q1 via the heat branch 33 in particular via Heat exchangers or recuperators, a combustion air preheater 14 supplied.
- the remaining heat quantity of the heat quantity Q1 is fed to a batch preheating device 13, which preheats the batch in the batch supply device 2 and also includes heat exchangers or recuperators for this purpose. It is of course also possible to provide a separate heat branch for the batch preheating device 13.
- a second heat quantity Q2 is coupled out from the remaining heat quantity Q - Ql transported by the exhaust gas A and fed to a cooling device 15 which generates cold from the waste heat Q2 by means of at least one absorption refrigerator.
- This refrigerant is fed via a first refrigerant line 40 to a first condensation drying device 16 and a second refrigerant line 41, a second condensation drying device 17th
- condensation drying devices 16 and 17 of the ambient air U is dried by means of air supplied from the cold producing device 15 refrigerant by condensing moisture contained in it to a predetermined absolute humidity or moisture load.
- the air UT dried by the first condensation drying device 16 is now fed via an air supply 50 to the batch feed device 2 for conditioning, in particular drying or setting, a predetermined degree of drying of the batch.
- the second condensation drying device 17 supplies dried ambient air UT to the glass melting device 3 via an air supply 51 to the melting area 3, to the bright melting area 31 via a further air supply 52 and to the float bath 4 via a third air supply 53 Air outlets arranged above and / or to the side of the glass melt or the glass ribbon, due to the conditioned ambient air UT is introduced and passed to the glass melt or the glass ribbon in the float bath 4 for conditioning the glass melt or the glass, in particular keeping the moisture below a certain value.
- a third amount of heat Q3 is branched off from the residual heat Q-Ql-Q2 in the exhaust gas A, which is fed to a conditioning device 18.
- ambient air U is dried from the waste heat Q3 by means of at least one absorption refrigerator, in which the cold generated by the absorption refrigerator by means of the waste heat Q3 as operating energy is again used to condense out water.
- the conditioned or dried ambient air UT is fed to the cooling furnace 5 via a first air supply 54 and passed through the glass ribbon running through the cooling furnace 5 during the cooling process.
- the overall dry ambient air UT is introduced via a second air feed 55 in the cooling section 6 and also headed there via the continuous glass ribbon.
- a further quantity of heat Q4 is now diverted from the residual heat Q-Ql-Q2-Q3, by means of which ambient air UT is again generated from the ambient air U by condensation drying in at least one absorption refrigerator by means of a conditioning device 19 and this is fed to the glass bearing 8 via an air supply 56.
- air outlets are arranged in the area of the glass stacks for targeted fanning of individual glass stacks with dried air UT.
- a fifth heat quantity Q5 is branched off from the remaining heat Q - Ql - Q2 - Q3 - Q4, which in a further conditioning device 20 for drying ambient air U by condensing out water by means of a further absorption refrigerator is used.
- the dried ambient air UT of the further conditioning device 20 can now via a Air supply 57 to the coating device 9 and / or a further air supply 58 to the glass finishing or glass processing 10 and / or via an air supply 59 to the laminated safety glass and / or insulating glass system 11 are supplied for conditioning these glass processing devices with dry process air.
- the heat branches generally comprise heat transfer circuits with transfer media, for example water or gas, and possibly pumps and / or heat exchangers and form a waste heat transfer device for transferring the waste heat Q1 to Q5.
- transfer media for example water or gas
- the absorption chillers for drying the air are each arranged in the vicinity of the process area to be conditioned, since the waste heat quantities Q1 to Q5 can be transported over longer distances with greater efficiency than the cold of the absorption chillers and also as the dried ambient air UT underneath maintaining the set humidity level. but it would also be possible in appropriate isolation measures, including the cold and / or dried ambient air UT over long distances to carry through the process plant.
- the absolute residual moisture in the dried ambient air UL in all conditioning devices is preferably set to a maximum of 6 grams (maximum 11 grams) of water to 1 kg of dry air, but can at least partly be set differently.
- each process area 2, 3, 4, 5, 6, 8 can also be , 9, 10, 11 each be assigned an associated cooling device and / or conditioning device for conditioning this process area with process air, or individual cooling device and / or conditioning devices supply different combinations of process areas as shown with conditioned air.
- any known embodiment in particular according to the prior art mentioned at the outset, and also in principle any future one Be used from management form.
- the conditioning according to the invention can be used and is compatible with any known float glass process, but also with other glass production processes and also with steel production processes or the like.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Glass Compositions (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10361449A DE10361449A1 (de) | 2003-12-23 | 2003-12-23 | Verfahren und Vorrichtung zum Konditionieren eines Abkühlprozessbereiches zur Verringerung von Korrosion |
| PCT/EP2004/001862 WO2005066083A1 (de) | 2003-12-23 | 2004-02-25 | Verfahren und vorrichtung zum konditionieren eines abkühlprozessbereiches zur verringerung von korrosion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1697266A1 true EP1697266A1 (de) | 2006-09-06 |
Family
ID=34706620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04714280A Withdrawn EP1697266A1 (de) | 2003-12-23 | 2004-02-25 | Verfahren und vorrichtung zum konditionieren eines abk hlpro zessbereiches zur verringerung von korrosion |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1697266A1 (de) |
| JP (1) | JP2007519595A (de) |
| DE (2) | DE20321794U1 (de) |
| WO (1) | WO2005066083A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5585034B2 (ja) * | 2009-09-18 | 2014-09-10 | 旭硝子株式会社 | 光学素子の製造方法及びアニール処理装置 |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2529155A (en) * | 1946-04-10 | 1950-11-07 | Cook Electric Co | Method of and means for removing contamingation from an atmosphere controlled furnace |
| US2712981A (en) * | 1953-02-24 | 1955-07-12 | Surface Combustion Corp | Gas generator and process for producing dry gas |
| GB1211225A (en) * | 1966-05-26 | 1970-11-04 | Ford Motor Co | Manufacture of glass |
| US3531306A (en) * | 1966-12-29 | 1970-09-29 | Corning Glass Works | Method of making infrared transmitting silicate glasses |
| US3528323A (en) * | 1968-07-19 | 1970-09-15 | Simplicity Mfg Co Inc | Differential transmission for coaxial axle shafts with means to frictionally resist relative rotation therebetween |
| AU5311973A (en) * | 1972-03-27 | 1974-09-12 | Anchor Hocking Corp | Muffle furnace |
| ZA90813B (en) * | 1989-03-29 | 1991-03-27 | Boc Group Inc | Method of reducing the oxygen concentration in a psa nitrogen product stream |
| US4923423A (en) * | 1989-06-30 | 1990-05-08 | Rca Licensing Corporation | Integrated thermal processing for kinescopes |
| JPH0443823A (ja) * | 1990-06-11 | 1992-02-13 | Akasaka Tekkosho:Kk | 乾燥結露防止装置 |
| JPH07922U (ja) * | 1993-06-08 | 1995-01-06 | 川崎製鉄株式会社 | ウエハカセットストッカ |
| JPH08325631A (ja) * | 1995-05-31 | 1996-12-10 | Nippon Steel Corp | 焼鈍コイル冷却ヤード |
| US5925158A (en) * | 1997-12-19 | 1999-07-20 | Praxair Technology, Inc. | Gas recycle for float glass system |
| FR2797627B1 (fr) | 1999-08-19 | 2001-10-26 | Stein Heurtey | Perfectionnements apportes aux etenderies de recuisson de verre plat |
| JP4101487B2 (ja) * | 2000-08-17 | 2008-06-18 | Hoya株式会社 | ガラスの製造方法およびそれに用いるガラス溶融装置 |
| JP3743749B2 (ja) * | 2001-07-12 | 2006-02-08 | Hoya株式会社 | ガラス成形体の製造方法、プレス成形用プリフォームの製造方法、プレス成形品の製造方法、及び光学素子の製造方法 |
| US6532771B1 (en) | 2001-08-21 | 2003-03-18 | Praxair Technology, Inc. | Method for controlling glass furnace atmosphere |
| JP2003238174A (ja) * | 2002-02-15 | 2003-08-27 | Asahi Glass Co Ltd | フロートガラスの製造方法 |
-
2003
- 2003-12-23 DE DE20321794U patent/DE20321794U1/de not_active Expired - Lifetime
- 2003-12-23 DE DE10361449A patent/DE10361449A1/de not_active Withdrawn
-
2004
- 2004-02-25 JP JP2006545928A patent/JP2007519595A/ja active Pending
- 2004-02-25 EP EP04714280A patent/EP1697266A1/de not_active Withdrawn
- 2004-02-25 WO PCT/EP2004/001862 patent/WO2005066083A1/de not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005066083A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10361449A1 (de) | 2005-07-28 |
| WO2005066083A1 (de) | 2005-07-21 |
| JP2007519595A (ja) | 2007-07-19 |
| DE20321794U1 (de) | 2010-03-04 |
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