EP3615288A1 - Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) - Google Patents
Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs)Info
- Publication number
- EP3615288A1 EP3615288A1 EP18713575.1A EP18713575A EP3615288A1 EP 3615288 A1 EP3615288 A1 EP 3615288A1 EP 18713575 A EP18713575 A EP 18713575A EP 3615288 A1 EP3615288 A1 EP 3615288A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- strands
- wood
- steam
- wood strands
- treated
- 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
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
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- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
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- 238000010626 work up procedure Methods 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- LVBXEMGDVWVTGY-SREVYHEPSA-N 2-octenal Chemical compound CCCCC\C=C/C=O LVBXEMGDVWVTGY-SREVYHEPSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005973 Carvone Substances 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
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- 229920002522 Wood fibre Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
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- 159000000032 aromatic acids Chemical class 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
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- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K1/00—Damping wood
- B27K1/02—Apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/001—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/007—Treating of wood not provided for in groups B27K1/00, B27K3/00 using pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/0085—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27L—REMOVING BARK OR VESTIGES OF BRANCHES; SPLITTING WOOD; MANUFACTURE OF VENEER, WOODEN STICKS, WOOD SHAVINGS, WOOD FIBRES OR WOOD POWDER
- B27L1/00—Debarking or removing vestiges of branches from trees or logs; Machines therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27L—REMOVING BARK OR VESTIGES OF BRANCHES; SPLITTING WOOD; MANUFACTURE OF VENEER, WOODEN STICKS, WOOD SHAVINGS, WOOD FIBRES OR WOOD POWDER
- B27L11/00—Manufacture of wood shavings, chips, powder, or the like; Tools therefor
- B27L11/007—Combined with manufacturing a workpiece
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
- B27N3/14—Distributing or orienting the particles or fibres
- B27N3/143—Orienting the particles or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2200/00—Wooden materials to be treated
- B27K2200/10—Articles made of particles or fibres consisting of wood or other lignocellulosic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2200/00—Wooden materials to be treated
- B27K2200/15—Pretreated particles or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/10—Extraction of components naturally occurring in wood, cork, straw, cane or reed
Definitions
- VOCs volatile organic compounds
- the present invention relates to a process for treating wood strands with water vapor according to claim 1, a device for carrying out the steam treatment according to claim 7, a process for the production of OSB wood-based panels according to claim 10, a production line for the production of OSB wood-based panels according to claim 14, and the use of steam-treated wooden strands according to claim 15.
- OSB Oriented Strand Boards
- strands long chips
- OSB boards are increasingly being used in timber and prefabricated house construction, as OSB boards are lightweight and still meet the structural requirements imposed on building boards.
- OSB boards are used as building boards and as wall or roof planking or in the floor area.
- the production of OSB boards is carried out in a multi-stage process, wherein initially the chips or strands of debarked roundwood, preferably coniferous wood, are peeled off in the longitudinal direction by rotating blades. In the subsequent drying process, the natural moisture of the beach is reduced at high temperatures.
- the degree of moisture of the strands may vary depending on the adhesive used, and the humidity should be well below 10% in order to avoid breakers during later compression. Depending on the adhesive, wetting may be more favorable on rather wet beaches or on dry beaches.
- as little moisture as possible should be present in the strands during the pressing process, in order to reduce the vapor pressure generated during the pressing process as far as possible, as this could otherwise cause the raw plate to burst.
- gluing device in which the glue or adhesive is applied finely distributed to the chips.
- PMDI polymeric diphenylmethane diisocyanate
- MUPF glues melamine-urea-phenol-formaldehyde
- the glues can also be mixed in the OSB boards. These glues are used as the OSB boards as mentioned above, are often used for constructive applications. Moisture or moisture-resistant glues must be used there.
- the glued strands are scattered in scattering apparatuses alternately along and across the production direction, so that the strands are arranged crosswise in at least three layers (lower cover layer - middle layer - upper cover layer).
- the scattering direction of the lower and upper cover layer is the same, but deviate from the scattering direction of the middle layer.
- the strands used in the top and middle layers differ from each other.
- the strands used in the outer layers are flat and the strands used in the middle layer are less flat up to span-shaped.
- the strands in the middle layer may be qualitatively inferior because the flexural strength is essentially due to the cover layers Therefore, fines produced during machining can also be used in the middle layer of OSB boards.
- the percentage distribution between the middle and top layers is at least 70% to 30%, followed by continuous spreading of the strands the same under high pressure and high temperature of eg 200 to 250 ° C.
- OSB boards are enjoying increasing popularity and diverse applications, for example as a construction element in house construction or as formwork in concrete construction.
- the inherent hygroscopic properties of wood-based materials have a detrimental effect in some applications.
- Volatile organic compounds also VOC's called, include volatile organic compounds which evaporate easily and at lower temperatures such as at room temperature are present as a gas.
- the volatile organic compounds (VOC) are either already present in the wood material and are released during workup from this or they are formed according to the current state of knowledge by the degradation of unsaturated fatty acids, which in turn are decomposition products of wood.
- Typical conversion products which occur during processing are, for example, pentanal and hexanal, but also octanal, 2-octenal or 1-heptenal.
- softwoods from which predominantly OSB boards are produced contain large amounts of resin and fats leading to the formation of volatile organic terpene compounds and aldehydes.
- VOCs such as the aldehydes mentioned, can also be formed or released when certain adhesives are used for the production of wood-based materials.
- OSB boards are particularly critical because this material is predominantly used uncoated. This allows the ingredients to exude unhindered.
- OSB boards are often used for cladding / paneling of large areas, which usually results in a high space loading (m 2 OSB / m 3 room air). This leads in addition to a concentration of certain substances in the room air.
- VOC scavengers almost always takes place after the drying process of the strands, since this or also the temperature exposure in the press was considered to be the triggering reasons of the majority of the emission.
- the VOC scavengers were added in liquid form via the gluing system, solids were added at various points of the process (eg scattering). This required an additional installation of dosing stations to ensure a homogeneous distribution.
- the invention is now the technical object of the invention to improve the known per se method for the production of OSB boards to the effect to produce easily and safely OSB boards with a significantly reduced emission of volatile organic compounds (VOCs). At least the emission of terpenes should be reduced. If possible, the manufacturing process should be changed as little as possible and the cost should not rise disproportionately. Furthermore, the solution should include the greatest possible flexibility. Ultimately, ecological aspects should also be taken into account, d. H. the solution should not cause additional energy consumption or generate additional waste.
- VOCs volatile organic compounds
- the wood strands being made after being recovered suitable woods are treated without drying with steam, wherein the steam is passed with a temperature between 80 ° C and 120 ° C and a pressure between 0.5 bar and 2 bar on the wooden strands.
- the treatment of the wood strands with steam takes place in such a way that the water vapor at a temperature between 90 ° C and 1 10 ° C, particularly preferably of 100 ° C at a pressure between 0.7 bar and 1, 5 bar , Particularly preferably at 1 bar (atmospheric pressure) is passed over the wooden strands.
- the steam treatment is carried out at the temperature-dependent pressure with which the steam is introduced into the treatment device.
- a steam treatment at atmospheric pressure temperature of the introduced steam of 100 ° C
- it can be dispensed with the application of an additional (external) pressure (ie in addition to the pressure with the water vapor in the system).
- an additional (external) pressure ie in addition to the pressure with the water vapor in the system.
- the steam treatment of the wood strands takes place in an oxygen-poor atmosphere or with the greatest possible exclusion of oxygen.
- the present water vapor treatment of the wood strands is carried out in a separate steam treatment apparatus.
- the steam treatment is carried out outside of a chipper (e.g., knife ring chipper or disc chipper) and thus is not part of the cutting or crushing process of wood for making wooden strands. It is also essential that the steam treatment can be carried out before the drying of the wood strands.
- the steam treatment of the wood strands takes place over a period of 5 to 30 minutes, preferably from 10 to 20 minutes, particularly preferably 15 minutes.
- the amount of steam is a maximum of 1 kg of steam / kg of beach (atro).
- the duration of the steam treatment is determined primarily by the speed of the transport device on which the wood strands are continuously guided by the steam treatment device.
- the water vapor is trapped as condensate after passing the wood strands. It is advantageous that the loading of the condensate with organic compounds is relatively low.
- the COD Chemical Oxygen Demand
- the wood strands used herein may have a length of between 50 to 200 mm, preferably 70 to 180 mm, particularly preferably 90 to 150 mm; a width between 5 to 50 mm, preferably 10 to 30 mm, particularly preferably 15 to 20 mm; and a thickness between 0, 1 and 2 mm, preferably between 0.3 and 1, 5 mm, particularly preferably between 0.4 and 1 mm.
- the wooden strands have e.g. a length between 150 and 200 mm, a width between 15 and 20 mm, a thickness between 0.5 and 1 mm and a humidity of max. 50% up.
- the steam treatment of the wooden strands is carried out in a device comprising the following elements or features: at least one housing, in particular a tubular housing;
- Transport device located wooden strands is arranged.
- the at least one housing may be in the form of a metal tube or tubular body.
- the at least one transport device consists of at least one conveyor belt.
- the conveyor belt should have perforations or other openings so that the water vapor can be passed from the top of the conveyor belt past the wooden strands to the underside of the conveyor belt.
- the wooden strands are distributed on the conveyor belt so that a homogeneous flow through the wood strands with steam is possible.
- more than one spraying means is provided on the steam supply line.
- the number of spray is particularly dependent on the total length of the housing.
- the spray can be controlled individually, so that the required amount of water vapor is specifically adjustable.
- a spray nozzle or other suitable injectors can be used, which allow a uniform spraying and a uniform distribution of water vapor on and between the wooden strands.
- the water vapor is collected after passing through the wood strands as condensate.
- at least one means for collecting the condensate is provided in the vaporization system below the conveyor belt (based on the flow direction of the water vapor).
- the tubular body may be angled upwards in the feed direction.
- the condensate thus collected contains wood components washed out of the wood strands, in particular aldehydes, organic acids and / or terpenes, in particular those which have a certain water solubility.
- the steam-treated strands After leaving the steam treatment apparatus, the steam-treated strands have a temperature of 80 to 90 ° C. At this temperature, the wood strands from the steam treatment station enter a dryer (as part of the OSB board production line), resulting in an increase in dryer performance. This will continue to use the energy needed to remove wood constituents for the drying process. In a normal process, the inlet temperature of the strands into the dryer is about 25 ° C.
- the water-treated wood strands are used according to the invention for the production of OSB wood-based panels with reduced emission of volatile organic compounds (VOCs).
- the production of OSB wood-based panels with reduced emission of volatile organic compounds (VOCs) is carried out in a process comprising the following steps: a) producing wood strands from suitable timbers; b) treating at least a portion of the wood strands with water vapor according to the method described above; c) drying the steamed wood strands; d) lining the steam-treated and dried wood strands and optionally lining non-steamed wood strands with at least one binder; e) sprinkling the glued wooden strands on a conveyor belt; and f) pressing the glued wooden strands into an OSB wood-based panel.
- the present method enables the production of OSB wood-based panels using steam-treated wooden strands which are introduced into a known manufacturing process in addition to or as an alternative to untreated wood strands.
- An OSB wood-based panel produced by the process according to the invention comprising steam-treated wood strands has a reduced emission of volatile organic compounds, in particular of terpenes and aldehydes.
- the strands are fed to the standard drying process. This is done z. B. immediately before gluing, whereby a complete substitution or even a partial substitution of the standard strands can take place.
- steam-treated wood strands or a mixture of steam-treated wood strands and non-steam-treated wood strands are used as the middle layer and / or top layer of the OSB wood-based panel. Accordingly, in one variant, a complete substitution of the wood strands is possible, wherein the steam-treated wood strands are used in the middle layer, and in one or both cover layers or in all layers.
- the middle and outer layers in each case a mixture with any ratio of steam-treated wood strands and non-steam-treated wood strands.
- the mixture may comprise between 10 and 50% by weight, preferably between 20 and 30% by weight of untreated or non-steamed wood strands and between 50 and 90% by weight, preferably between 70 and 80% by weight of steam-treated wood strands.
- the step of steam treatment of the wood strands can be carried out separately from the production process of the OSB wood-based panels. Accordingly, the steam treatment in this embodiment of the present method takes place outside the overall process or the process line.
- the wood strands are removed from the manufacturing process and introduced into the steam treatment device (eg, steaming system). Subsequently, the steam-treated wood strands may, if appropriate, be introduced into the conventional production process again after intermediate storage, for example immediately before gluing. This allows a high flexibility in the manufacturing process.
- the steam treatment of the wood strands can be integrated in a still further embodiment variant in the manufacturing process of the OSB wood-based panels, i.
- the steam treatment step is integrated into the overall process or process line and takes place online.
- steam treatment may be carried out i) immediately after cutting and providing the strands of wood or ii) only after sifting and separating the strands of wood according to the use of the strands for the middle or top layer.
- a separate water vapor treatment of the wood strands can be made according to the requirements of the wood strands used in the middle and top layers.
- the steam treatment of the wood strands is carried out in at least one vaporization plant, preferably in two vapor deposition plants.
- the vaporization system used in the present case can be present or function as a batch plant or as a continuously operated plant, wherein a continuously operated plant is preferred.
- the steam treatment of wood strands used for the middle layer and the top layers of the OSB wood-based panel may each be carried out separately in at least two vapor deposition units.
- the two vapor deposition systems used are preferably connected in parallel or arranged in this case.
- the contacting of the wood strands with the at least one binder in step d) is preferably carried out by spraying or atomizing the binder onto the wood strands.
- Many OSB systems work with rotating coils (drums with atomizer gluing). A mixer gluing would also be possible.
- the strands are intimately mixed with the glue in a mixer by rotating blades.
- a polymer adhesive is preferably used as a binder, which is selected from the group consisting of formaldehyde adhesives, such as urea-formaldehyde resin adhesive (UF), melamine-urea-phenol-formaldehyde adhesive (MUPF) and / or melamine-formaldehyde resin adhesive (MF), polyurethane adhesives, epoxy adhesives, polyester adhesives.
- formaldehyde adhesives such as urea-formaldehyde resin adhesive (UF), melamine-urea-phenol-formaldehyde adhesive (MUPF) and / or melamine-formaldehyde resin adhesive (MF), polyurethane adhesives, epoxy adhesives, polyester adhesives.
- polyurethane adhesive is preferred, wherein the polyurethane adhesive is based on aromatic polyisocyanates, in particular polydiphenylmethane diisocyanate (PMDI), tolylene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI), with PMDI being particularly preferred.
- aromatic polyisocyanates in particular polydiphenylmethane diisocyanate (PMDI), tolylene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI), with PMDI being particularly preferred.
- PMDI polydiphenylmethane diisocyanate
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- the steam-treated and non-steam-treated wood strands are used with a binder amount of from 1.0 to 10% by weight, in particular from 1.0 to 5.0% by weight, preferably from 2 to 4% by weight, particularly preferably 3% by weight on the total amount of wooden strands). It is conceivable that the same binder or different binders are used for the top and middle layers.
- the cover layers can each be provided with 2.6% by weight PMDI on atro wood and the middle layer with 2.9% by weight PMDI on atro wood.
- cover layers can each be provided with 10% by weight MUPF on atro wood and the middle layer with 2.9% by weight PMDI on atro wood.
- cover layers can each be provided with 10% by weight MUF on atro wood and the middle layer with 2.9% by weight PMDI on atro wood.
- the alternatives mentioned relate in each case to the gluing of the cover layers and the middle layer of a 3-layer OSB with a thickness of 19 to 22 mm. It is also possible to supply at least one flame retardant to the wood strands together or separately with the binder.
- the flame retardant may typically be added in an amount between 1 and 20% by weight, preferably between 5 and 15% by weight, particularly preferably> 10% by weight, based on the total amount of wood strands.
- Typical flame retardants are selected from the group comprising phosphates, sulfates borates, in particular ammonium polyphosphate, tris (tri-bromneopentyl) phosphate, zinc borate or boric acid complexes of polyhydric alcohols.
- the glued (steam-treated and / or non-steam-treated) wood strands are scattered on a conveyor belt to form a first cover layer along the transport direction, then forming a middle layer transversely to the transport direction and finally forming a second cover layer along the transport direction.
- the glued wooden strands are pressed at temperatures between 200 and 250 ° C., preferably 220 and 230 ° C., to form an OSB wood-based panel.
- the present process for producing an OSB wood-based panel with reduced VOC emission comprises the following steps:
- the present process for producing an OSB wood-based panel with reduced VOC emission comprises the following steps:
- the present method enables the production of an OSB wood-based panel with reduced emission of volatile organic compounds (VOCs) comprising water-treated wood strands.
- VOCs volatile organic compounds
- the present OSB wood-based panel may consist entirely of steam-treated wood strands or of a mixture of steam-treated and non-steam-treated wood strands.
- both cover layers and the middle layer of OSB consist of steam-treated wood strands
- the two cover layers consist of non-steam-treated wood strands and the middle layer of steam-treated wood strands
- the two cover layers consist of steam-treated wood strands and the middle layer from non-steamed wooden strands.
- the present OSB wood-based panel may have a bulk density between 300 and 1000 kg / m 3 , preferably between 500 and 800 kg / m 3 , particularly preferably between 500 and 600 kg / m 3 .
- the thickness of the present OSB wood-based panel may be between 5 and 50 mm, preferably between 10 and 40 mm, wherein in particular a thickness between 15 and 25 mm is preferred.
- the OSB wood-based panel produced by the present method has, in particular, a reduced emission of aldehydes released during wood pulping, in particular pentanal or hexanal, and / or terpenes, in particular carene and pinene.
- the release of aldehydes takes place during the cutting process and an associated aqueous workup and cleaning of the wood strands.
- specific aldehydes can be formed from the basic building blocks of cellulose or hemicellulose.
- the aldehyde furfural is formed from mono- and disaccharides of cellulose or hemicellulose, while aromatic aldehydes can be liberated from lignin.
- the aliphatic aldehydes saturated and unsaturated are formed by the fragmentation of fatty acids with the participation of oxygen.
- Due to the use of steam-treated wood strands is a reduction in the emission of C2-C10 aldehydes, particularly preferably acetaldehyde, pentanal, hexanal or furfural, and a reduction of liberated terpenes, especially Cio-monoterpenes and cis-sesquiterpenes, particularly preferably acyclic or cyclic Monoterpenes in the OSB wood-based panels.
- Typical acyclic terpenes are terpene hydrocarbons such as myrcene, terpene alcohols such as gerianol, linaool, ipsinol and terpene aldehydes such as citral.
- Typical representatives of the monocyclic terpenes are p-menthane, terpeninol, limonene or carvone, and typical representatives of the bicyclic terpenes are caran, pinane, bornan, in particular 3-carene and ⁇ -pinene being of importance.
- Terpenes are components of the tree resins and therefore especially in very resinous tree species such as pine or spruce.
- organic acids in particular the emission of acetic acid from OSB wood-based panels can be reduced.
- Organic acids are obtained in particular as cleavage products of the wood components cellulose, hemicellulose and lignin, wherein preferably alkanoic acids, such as acetic acid and propionic acid or aromatic acids are formed.
- alkanoic acids such as acetic acid and propionic acid or aromatic acids are formed.
- the strong reduction of aldehydes was foreseeable in any way for the skilled person.
- such additions are usually due to the low electrophilicity of water only in the presence of mineral acids (sulfuric acid, phosphoric acid, etc.) at higher temperatures.
- the present process is carried out in a production line for producing an OSB board and comprises the following elements:
- At least one dryer for drying the steam-treated
- the steamer can be designed continuously.
- the wooden strands are applied to a Tramsportband which leads the wood strands with a given speed through the steamer.
- the wood strands are sprayed evenly with steam, which is introduced from above the conveyor belt provided nozzles.
- the steamer may be provided upstream (upstream) of the device for sifting and separating the strands of wood.
- upstream upstream
- two steaming plants to be provided behind (downstream) the device for sifting and separating the wooden strips.
- this case serves a steaming the steam treatment of the wood strands which are provided for the middle class, and the other steaming system of the steam treatment of the wood strands which are provided for the outer layers. This allows optional steam treatment of the strands for the middle layer or the strands of wood for the cover layers.
- Figure 1 is a schematic representation of an embodiment of a device for
- Figure 2 is a schematic representation of a first embodiment of the method according to the invention for the production of OSB boards
- Figure 3 is a schematic representation of a second embodiment of the method according to the invention.
- FIG. 1 shows a variant of a device 10 for steam treatment of wooden strands.
- the device comprises a (thermally insulated) tubular body 1 1 with the tubular body 1 1 continuous perforated conveyor belt 12 above the conveyor belt 12 is a supply line 13 for the steam provided, wherein the feed line 13 a plurality of nozzles 14 for spraying the water vapor on Having the conveyor belt 12 located wooden strands.
- a collecting means 15 is provided below the conveyor belt 12, for the forming water vapor condensate.
- the present apparatus 10 allows steaming of the strands prior to drying the strands in the tumble dryer.
- all or parts of the strands, which are intended for the later production of the OSB can be treated.
- the treatment is carried out at normal pressure and achieved by the use of the conveyor belt 12 made of metal fabric, the homogeneous treatment of the beach with steam.
- the band of the transport device is dimensioned so that the beaches can not fall through the gaps.
- the strands are passed directly to the production of the conveyor belt 12, which passes through the tubular body 1 1.
- the strands are distributed so that a homogeneous flow through the Strands with steam is possible.
- Periodically positioned separation stations provide for the dissolution of existing or forming beach piles. Since the conveyor belt 12 is cooled by condensate forming upon heating of the strands and has a relatively high mass compared to the strands, heating of the strip prior to spreading of the strands is to be provided. This speeds up the heating of the beaches and thus reduces the treatment time with steam. The heating can be done by resistance heating or by radiation.
- the steam is then applied through nozzles 14 on the beaches.
- the steam has a temperature of about 100 ° C.
- the insulation of the metal tube 1 1 ensures that the heat losses are minimized.
- the forming condensate is collected under the transport device 12, freed of suspended matter and returned to the system after a cleaning step to remove dissolved substances.
- the residence time of the beaches in the saturated steam atmosphere is 5 to 15 min. At regular intervals, the progress of the beach heating is detected by thermocouples. The temperature of the beaches should be near 90 ° C at the end of the treatment.
- the first embodiment of the method according to the invention shown in FIG. 2 describes the individual method steps beginning with the provision of the wood starting product up to the finished OSB wood-based panel. Accordingly, in step 1 suitable wood starting material for the production of the wood strands is first provided.
- wood source material all conifers, hardwoods or mixtures thereof are suitable.
- the debarking (step 2) and the cutting (step 3) of the wood starting material takes place in suitable chippers, wherein the size of the wood strands can be controlled accordingly.
- the strands of wood are introduced into an evaporator (step 4).
- the steam treatment of the wooden strands takes place in a temperature range between 80 ° and 120 ° C at a pressure between 0.5 bar and 2 bar.
- the resulting condensate can be collected and washed out of the wood strands substances (terpenes, aldehydes) can be supplied from the condensate for further use.
- step 9 After completion of the steam treatment, which takes in the present case about 10-20 minutes, the steam-treated wood strands are dried (step 9), spotted and separated (step 5). There is a separation in wooden strands for use as a middle layer (step 6a) or as a cover layer (step 6b) with respective gluing.
- the glued steam-treated wooden strands are spread on a conveyor belt in the order of first lower cover layer, middle layer and second upper cover layer (step 7) and then pressed into an OSB wood-based panel (step 8).
- the wood starting material is initially provided (step 1), debarked (step 2) and machined (step 3) in analogy to FIG.
- the strands of wood may be subjected to a predrying process, with a humidity of 5-10% being adjusted in relation to the initial moisture content of the strands of wood (step 3a).
- a separation into wood strands for use as a middle layer or as a cover layer takes place already after the optional drying (step 5).
- step 4a the steam treatment of the wood strands provided for the middle layer (step 4a) and / or steam treatment of the wood strands (step 4b) provided for the cover layer (s) in a suitable vapor deposition system.
- the steam treatment of the wood strands takes place in a temperature range between 80 ° and 120 ° C at a pressure between 0.5 bar and 2 bar.
- the resulting condensate can be collected and washed out of the wood strands substances (terpenes, aldehydes) can be supplied from the condensate for further use.
- the glued water-treated wood strands are scattered onto a conveyor belt in the order of the first lower cover layer, middle layer and second upper cover layer (step 7) and then pressed into an OSB wood-based panel (step 8). In the finishing, the obtained OSB wood-based panel is assembled in each case in a suitable manner.
- Embodiment 1 Strands are produced from pine trunks (length: max 200 mm, width: 20 mm, thickness: max 1 mm, humidity max 50%) and treated in a continuous process with about 100 ° C hot steam. During treatment, the strands are loosely piled up on a conveyor belt which has perforations and thereby allows the passage of the steam after passing the beaches. The steam treatment was preferably from top to bottom. The conveyor belt is guided through a tubular body.
- nozzles are attached above the conveyor belt with the loosely piled up strands, which distributes the steam evenly over the beach.
- the treatment with steam takes about 15 minutes.
- the steam treatment takes place with the greatest possible exclusion of oxygen, so that one can speak of a reductive process control.
- the tube body has a diameter of 50 cm at a length of 3 m to achieve a residence time of about 15 minutes.
- the conveyor belt was moved through the pipe body at a speed of about 2 m / 10 minutes. In the feed direction of the tube body was slightly angled upward (2 to 10 degrees), so that the forming condensate could be easily collected. This is a pilot plant with which the effect should be demonstrated. For a production plant, this can be increased and easily optimized in terms of transport speed and quantity by the expert.
- the strands are dried in a conventional drum dryer. The energy requirement of the drum dryer is reduced significantly, as the beaches when entering the Dryers already have a temperature of about 90 ° C. Then they are glued in a coil with glue, preferably with PMDI (about 3% by weight on atro wood).
- the glued stands are sprinkled in a standard OSB plant as a top and middle layer.
- the percentage distribution between middle and top layer is preferably 70% to 30%.
- the strands are pressed into slabs with a density of about 570 kg / m3.
- the test plate was tested together with a standard plate in the same thickness in a micro-chamber on the VOC delivery.
- Chamber parameters temperature: 23 ° C; Humidity: 0%; Air flow: 150 ml / min; Air exchange: 188 / h; Load: 48.8 m 2 / m 3 ; Sample surface: 0, 003 m 2 ; Chamber volume: 48 ml.
- Table 1 The values of the quantitatively most important parameters are shown in Table 1.
- Chamber parameters temperature: 23 ° C; Humidity: 0%; Air flow: 150 ml / min; Air exchange: 188 / h; Load: 48.8 m 2 / m3; Sample surface: 0, 003 m 2 ; Chamber volume: 48 ml.
- Table 2 The values of the quantitatively most important parameters are shown in Table 2.
- the top layer consists of standard strands.
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Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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EP17167974.9A EP3395520B1 (de) | 2017-04-25 | 2017-04-25 | Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) |
PCT/EP2018/056070 WO2018197094A1 (de) | 2017-04-25 | 2018-03-12 | Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) |
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EP3615288A1 true EP3615288A1 (de) | 2020-03-04 |
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EP3615288C0 EP3615288C0 (de) | 2023-07-05 |
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EP17167974.9A Active EP3395520B1 (de) | 2017-04-25 | 2017-04-25 | Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) |
EP19201042.9A Active EP3620282B1 (de) | 2017-04-25 | 2017-04-25 | Osb-holzwerkstoffplatte |
EP18713575.1A Active EP3615288B1 (de) | 2017-04-25 | 2018-03-12 | Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) |
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EP17167974.9A Active EP3395520B1 (de) | 2017-04-25 | 2017-04-25 | Verfahren zur herstellung von osb-holzwerkstoffplatten mit reduzierter emission an flüchtigen organischen verbindungen (vocs) |
EP19201042.9A Active EP3620282B1 (de) | 2017-04-25 | 2017-04-25 | Osb-holzwerkstoffplatte |
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EP (3) | EP3395520B1 (de) |
CN (2) | CN110545971B (de) |
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ES (3) | ES2904805T3 (de) |
HU (3) | HUE048530T2 (de) |
PL (3) | PL3395520T3 (de) |
PT (2) | PT3620282T (de) |
RU (1) | RU2728871C1 (de) |
UA (1) | UA127129C2 (de) |
WO (1) | WO2018197094A1 (de) |
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PT3620282T (pt) * | 2017-04-25 | 2022-01-13 | SWISS KRONO Tec AG | Painel à base de madeira osb |
SE543059C2 (en) * | 2019-03-07 | 2020-09-29 | Stora Enso Oyj | Device and method of processing logs using a thermal camera |
HRP20220416T1 (hr) | 2020-02-28 | 2022-05-27 | Fiberboard Gmbh | Postupak i sustav obrade radi smanjenje hlapljivih organskih spojeva iz drvene sječke |
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DE3914106A1 (de) * | 1989-04-28 | 1990-10-31 | Siempelkamp Gmbh & Co | Verfahren und anlage zur kontinuierlichen herstellung von spanplatten, faserplatten u. dgl. |
US5447686A (en) * | 1994-06-17 | 1995-09-05 | Seidner; Marc A. | Method for heat-treating wood and wood products |
DE4423632A1 (de) | 1994-07-06 | 1996-01-11 | Siempelkamp Gmbh & Co | Verfahren zum Vorwärmen von Streugut auf eine vorgebbare Vorwärmtemperatur im Zuge der Herstellung von Holzwerkstoffplatten |
US5665798A (en) * | 1995-12-27 | 1997-09-09 | North Pacific Paper Corporation | Composite wood products from solvent extracted wood raw materials |
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DE20109675U1 (de) * | 2001-06-12 | 2002-10-24 | Fritz Egger Ges. M.B.H. & Co., Unterradlberg | Grossformatige OSB-Platte mit verbesserten Eigenschaften, insbesondere für den Baubereich |
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DE102012101716A1 (de) * | 2012-03-01 | 2013-09-05 | Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts | Verfahren zur Herstellung von Holz- und/oder Verbundwerkstoffen |
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PT3620282T (pt) * | 2017-04-25 | 2022-01-13 | SWISS KRONO Tec AG | Painel à base de madeira osb |
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2017
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- 2017-04-25 EP EP17167974.9A patent/EP3395520B1/de active Active
- 2017-04-25 PT PT171679749T patent/PT3395520T/pt unknown
- 2017-04-25 PL PL19201042T patent/PL3620282T3/pl unknown
- 2017-04-25 EP EP19201042.9A patent/EP3620282B1/de active Active
- 2017-04-25 ES ES19201042T patent/ES2904805T3/es active Active
- 2017-04-25 ES ES17167974T patent/ES2767090T3/es active Active
- 2017-04-25 HU HUE19201042A patent/HUE057379T2/hu unknown
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2018
- 2018-03-12 EP EP18713575.1A patent/EP3615288B1/de active Active
- 2018-03-12 PL PL18713575.1T patent/PL3615288T3/pl unknown
- 2018-03-12 ES ES18713575T patent/ES2958617T3/es active Active
- 2018-03-12 UA UAA201910564A patent/UA127129C2/uk unknown
- 2018-03-12 RU RU2019133765A patent/RU2728871C1/ru active
- 2018-03-12 HU HUE18713575A patent/HUE063434T2/hu unknown
- 2018-03-12 WO PCT/EP2018/056070 patent/WO2018197094A1/de unknown
- 2018-03-12 US US16/497,535 patent/US11007668B2/en active Active
- 2018-03-12 CN CN201880027301.XA patent/CN110545971B/zh active Active
- 2018-03-12 CA CA3060986A patent/CA3060986C/en active Active
- 2018-03-12 CN CN202011072179.3A patent/CN112476694B/zh active Active
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Also Published As
Publication number | Publication date |
---|---|
PL3615288T3 (pl) | 2023-12-18 |
ES2767090T3 (es) | 2020-06-16 |
US11904496B2 (en) | 2024-02-20 |
CN112476694B (zh) | 2022-06-28 |
UA127129C2 (uk) | 2023-05-10 |
PT3395520T (pt) | 2020-02-03 |
CA3060986A1 (en) | 2018-11-01 |
ES2904805T3 (es) | 2022-04-06 |
HUE063434T2 (hu) | 2024-01-28 |
EP3615288B1 (de) | 2023-07-05 |
EP3395520A1 (de) | 2018-10-31 |
US20200108523A1 (en) | 2020-04-09 |
HUE057379T2 (hu) | 2022-05-28 |
US11007668B2 (en) | 2021-05-18 |
ES2958617T3 (es) | 2024-02-12 |
PL3620282T3 (pl) | 2022-02-21 |
WO2018197094A1 (de) | 2018-11-01 |
US20210245391A1 (en) | 2021-08-12 |
EP3620282B1 (de) | 2021-11-03 |
EP3620282A1 (de) | 2020-03-11 |
HUE048530T2 (hu) | 2020-07-28 |
CA3060986C (en) | 2023-08-15 |
RU2728871C1 (ru) | 2020-07-31 |
EP3615288C0 (de) | 2023-07-05 |
PL3395520T3 (pl) | 2020-05-18 |
CN112476694A (zh) | 2021-03-12 |
CN110545971B (zh) | 2020-11-03 |
PT3620282T (pt) | 2022-01-13 |
EP3395520B1 (de) | 2019-10-30 |
CN110545971A (zh) | 2019-12-06 |
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