EP2301731B1 - Method for manufacturing moulded objects - Google Patents

Method for manufacturing moulded objects Download PDF

Info

Publication number
EP2301731B1
EP2301731B1 EP20100009307 EP10009307A EP2301731B1 EP 2301731 B1 EP2301731 B1 EP 2301731B1 EP 20100009307 EP20100009307 EP 20100009307 EP 10009307 A EP10009307 A EP 10009307A EP 2301731 B1 EP2301731 B1 EP 2301731B1
Authority
EP
European Patent Office
Prior art keywords
lignin
fibres
mixture
derivatives
previous
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.)
Not-in-force
Application number
EP20100009307
Other languages
German (de)
French (fr)
Other versions
EP2301731A2 (en
EP2301731A3 (en
Inventor
Hans-Peter Braun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Braun Peter Marco
Original Assignee
Braun Peter Marco
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Braun Peter Marco filed Critical Braun Peter Marco
Priority to EP13001490.5A priority Critical patent/EP2612739B1/en
Priority to SI201030300T priority patent/SI2301731T1/en
Publication of EP2301731A2 publication Critical patent/EP2301731A2/en
Publication of EP2301731A3 publication Critical patent/EP2301731A3/en
Application granted granted Critical
Publication of EP2301731B1 publication Critical patent/EP2301731B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B27N5/00—Manufacture of non-flat articles

Definitions

  • the invention relates to a method according to claim 1 for the production of moldings containing lignin and / or lignin derivatives and fibers.
  • plastics are based on fossil, non-renewable sources of raw materials, such as oil and natural gas. Since the 80s of the last century, there has been a steep increase in the consumption of these plastics by the industrialized countries, since the plastics can be molded and processed very well and the molded parts produced from these plastics have a high durability. In addition to the limitations of fossil resources, there is the problem of disposing of the large amounts of waste resulting from the high consumption of plastics. The desirable durability of the plastics makes most plastics difficult, if not inaccessible, for degradation reactions in the water or in the ground. As a result, costly and possibly expensive measures for recycling or incineration are required. In addition, there is a threat of depletion of landfill space.
  • Lignin is a three-dimensional cross-linked phenolic macromolecule composed of different monomers. It serves as an additional strengthening and support element in the predominantly cellulosic cell walls of lignified plants such as grasses, perennials, shrubs and trees.
  • the lignin obtained from the wood of plants is suitable as a basis for the production of a natural material.
  • the invention is therefore based on the object to provide a process for the production of moldings, in which the fossil and natural resources are spared.
  • the invention has as its further object to provide a cost-effective method by which durable, weather-resistant and yet biodegradable molded parts can be produced in a wide variety.
  • the object is achieved by a method according to claim 1 for the production of moldings containing lignin and / or lignin derivatives and fibers.
  • the lignin and / or the Lignin derivatives are derived from lignin-containing wastes from the production and extraction of industrial products from vegetable raw materials.
  • waste material In the industrial production of paper, bioethanol, chemicals and pharmaceuticals from plant biomass, a huge amount of waste material is produced, including an immense amount of lignin and / or lignin derivatives-containing waste.
  • This waste can serve as a source of lignin and / or lignin derivatives, which are separated from the remaining waste in step a).
  • the separation of the other waste materials can be done more or less complete.
  • the separated lignin and / or the lignin derivatives may have a proportion of residual moisture.
  • the lignin and / or the lignin derivatives from step a) are mixed with fibers.
  • lignin and / or lignin derivatives are obtained from different lignin-containing wastes and mixed with the fibers.
  • the blended fibers serve to increase the strength of the molding.
  • the mixture is melted in a plasticizing zone and continuously extruded through an extrusion screw through a die and formed into a plate.
  • the plate shape can be produced by rolling.
  • the plate from step c) is then deep-drawn on plastic thermoforming machines to form a molding.
  • the molded parts thus produced are also suitable for subsequent further processing by conventional milling.
  • lignin and / or lignin derivatives from lignin-containing wastes in the manufacture and extraction of industrial products such as pulp or bioethanol, from chemicals and pharmaceuticals from lignocellulosic biomass, protects both fossil and natural resources.
  • lignin and / or lignin derivatives from the lignin-containing wastes due to savings in the field of raw material procurement cost-effective, weather-resistant, yet biodegradable molded parts can be produced.
  • the mixture from step b) is brought into granular form before further processing in step c).
  • This can be done in such a way that the mixture is first melted in an extruder.
  • the melt is formed into strands via nozzles and cooled in the water.
  • a rotating knife cuts the strands into a few millimeters long sections. Granulation is also possible by cold pressing.
  • the lignin-containing waste from the sulfite, the sulfate or the Organosolv process for pulp production Paper is made from pulp consisting essentially of cellulose. To obtain pulp from tree wood, this is first debarked and then crushed. For high-quality papers, the cellulose contained in the so-called wood pulp is digested by chemical processes and accompanying substances such as lignin, hemicellulose and resins are separated. The sulphate and sulphite processes are used industrially. In the sulphate process, the groundwood is heated in pressure vessels with essentially sodium hydroxide solution, sodium sulphide and sodium sulphate. Following cooking, the cooking liquor, the black liquor, is separated from the pulp.
  • Lignin and / or lignin derivatives as well as chemicals remain behind with the black liquor.
  • the chips are also cooked under pressure with calcium hydrogen sulfite, magnesium hydrogen sulfite or ammonium bisulfite.
  • the sulfite liquor, the lignin and / or Lignin derivatives in addition to other waste such as the chemicals used and sugar contains.
  • the lignin-containing residues obtained in the digestion liquid by the Organosolv process can likewise be used for the process according to the invention, such as wastes from the soda process or the nitric acid digestion.
  • the lignin derivatives are ligninsulfonic acids or alkali lignin from the boiling liquids of the sulfite or sulfate process.
  • lignin and / or lignin derivatives obtained in further processes, such as those derived from the Organosolv process are likewise suitable.
  • the separation of the lignin and / or the lignin derivatives from the lignin ambiencen wastes by chemical and / or by physical separation means.
  • lignin and / or lignin derivatives can be obtained from the waste by ultrafiltration or nanofiltration membrane modules.
  • a precipitation of the lignin derivatives by pH shift or the addition of complexing precipitants is possible.
  • the simple precipitation reactions compared to the filtration methods, in which the membrane must be changed relatively frequently are preferable.
  • These separation methods may also follow a previous chemical digestion of lignocellulosic waste, for example waste from the production of bioethanol.
  • the still remaining vinification after the fermentation process contains the lignin still in association with cellulose.
  • further separation and treatment steps of the lignin and / or the lignin derivatives can be integrated into the separation process at any time.
  • the fibers are natural fibers from the group of seed fibers, bast fibers, fruit fibers, wood fibers or leaf fibers of plants.
  • the fibers from the cotton, from the alpaca plant, the bamboo, the nettle, the hemp, the coconut plant or the bulrush can be used. But also poplar fluff, jute, linen, ramie or sisal are suitable.
  • natural fibers can be used that are produced as agricultural waste when growing plants.
  • the fibers are also synthetic fibers made from natural polymers. In this case, chemical fibers made of polymers based on starch are used. These chemical fibers are used either instead of or in conjunction with the natural fibers.
  • further excipients are added to the mixture from step b).
  • adjuvants having thermoplastic properties can then be blended into the blend if a thermoplasticity in excess of the natural thermoplastic properties of the lignin and / or lignin derivatives is desired in the steps listed under c) and d).
  • adjuvants having thermoplastic properties may optionally be added to the mixture.
  • the excipients are natural polymers, based on natural substances polymers, water, pigments, dyes, fillers and / or mixtures of these.
  • Natural polymers and natural-based polymers with thermoplastic properties can be used to increase the thermoplastic properties for further processing of the blend.
  • pigments and dyes an individual coloring of the molded parts is possible.
  • the addition of water can be the Processability of the mixture influence positively. Fillers may be included for additional cost reduction in the mixture used in the process.
  • the plate from step c) has a thickness of 2 mm to 15 mm, preferably from 2 mm to 10 mm. This allows the production of moldings with different wall thickness. This results in a further variety of different design options with regard to the molded parts, which can be produced by the method according to the invention.
  • a mixture containing lignin and / or lignin derivatives and fibers for the production of moldings is used by deep drawing.
  • a mixture containing lignin and / or lignin derivatives and fibers for the production of signs by deep drawing is used. These can be used, for example, for signposting field and forest trails.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Description

Stand der TechnikState of the art

Die Erfindung betrifft ein Verfahren gemäß Anspruch 1 zur Herstellung von Formteilen, die Lignin und/ oder Ligninderivate sowie Fasern enthalten.The invention relates to a method according to claim 1 for the production of moldings containing lignin and / or lignin derivatives and fibers.

Zur Herstellung von Formteilen insbesondere für den Außenbereich, den Bausektor, die Fahrzeugindustrie, die Möbel- und Einrichtungsfertigung sowie in der Elektro- und elektrotechnischen Industrie kommen überwiegend Kunststoffe zum Einsatz, die auf fossilen, nicht erneuerbaren Rohstoffquellen, wie Erdöl und Erdgas basieren. Schon seit den 80er Jahren des letzten Jahrhunderts ist ein steiler Anstieg im Verbrauch dieser Kunststoffe durch die Industriestaaten zu verzeichnen, da sich die Kunststoffe sehr gut formen und verarbeiten lassen und die aus diesen Kunststoffen hergestellten Formteile eine hohe Haltbarkeit aufweisen. Neben der Begrenztheit der fossilen Ressourcen stellt sich das Problem der Entsorgung der großen Abfallmengen, die bei dem hohen Kunststoffverbrauch anfallen. Die erwünschte Haltbarkeit der Kunststoffe macht die meisten Kunststoffe schwer bis überhaupt nicht zugänglich für Abbaureaktionen im Wasser oder im Boden. Hierdurch werden aufwendige und unter Umständen kostspielige Maßnahmen für das Recycling oder die Verbrennung erforderlich. Darüber hinaus droht eine Erschöpfung von Deponieraum.For the production of molded parts, in particular for the exterior, the construction sector, the vehicle industry, furniture and furnishing production as well as in the electrical and electrical engineering industry are mainly plastics, which are based on fossil, non-renewable sources of raw materials, such as oil and natural gas. Since the 80s of the last century, there has been a steep increase in the consumption of these plastics by the industrialized countries, since the plastics can be molded and processed very well and the molded parts produced from these plastics have a high durability. In addition to the limitations of fossil resources, there is the problem of disposing of the large amounts of waste resulting from the high consumption of plastics. The desirable durability of the plastics makes most plastics difficult, if not inaccessible, for degradation reactions in the water or in the ground. As a result, costly and possibly expensive measures for recycling or incineration are required. In addition, there is a threat of depletion of landfill space.

Aus diesem Grund werden zwar zwischenzeitlich mehr und mehr alternative Materialien aus nachwachsenden Rohstoffen entwickelt. Zu diesen Materialien gehören auch solche auf der Basis von Lignin und/ oder Ligninderivaten. Bei Lignin handelt es sich um ein dreidimensional vernetztes phenolisches Makromolekül, das sich aus verschiedenen Monomeren zusammensetzt. Es dient in den vornehmlich aus Zellulose bestehenden Zellwänden von verholzten Pflanzen wie Gräsern, Stauden, Sträuchern und Bäumen als zusätzliches Festigungs- und Stützelement. Das aus dem Holz von Pflanzen gewonnene Lignin eignet sich als Basis zur Herstellung eines natürlichen Werkstoffes. Jedoch führt eine Nutzung der Lignins und/ oder der Ligninderivate in einem für die Industrie erheblichem Maßstab zu einem starken Anstieg von Anbauflächen für diesen nachwachsenden Rohstoff mit den damit verbundenen Nachteilen wie großflächiger Anbau in Monokulturen, der großflächige Einsatz von Pestiziden und Rückgang der vielseitigen Landwirtschaft.For this reason, although in the meantime, more and more alternative materials are being developed from renewable raw materials. These materials also include those based on lignin and / or lignin derivatives. Lignin is a three-dimensional cross-linked phenolic macromolecule composed of different monomers. It serves as an additional strengthening and support element in the predominantly cellulosic cell walls of lignified plants such as grasses, perennials, shrubs and trees. The lignin obtained from the wood of plants is suitable as a basis for the production of a natural material. However, use of lignin and / or lignin derivatives at a significant scale for the industry results in a large increase in acreage for this renewable resource, with its attendant disadvantages such as large-scale monoculture cultivation, large-scale pesticide use, and decline in versatile agriculture.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Herstellung von Formteilen bereit zu stellen, bei dem die fossilen und natürlichen Ressourcen geschont werden. Zudem liegt der Erfindung als weitere Aufgabe zugrunde, ein kostengünstiges Verfahren bereitzustellen, mit dem haltbare, witterungsbeständige und dennoch biologisch abbaubare Formteile in einer großen Vielfalt hergestellt werden können.The invention is therefore based on the object to provide a process for the production of moldings, in which the fossil and natural resources are spared. In addition, the invention has as its further object to provide a cost-effective method by which durable, weather-resistant and yet biodegradable molded parts can be produced in a wide variety.

Die Erfindung und ihre VorteileThe invention and its advantages

Die Aufgabe wird gelöst durch ein Verfahren gemäß Anspruch 1 zur Herstellung von Formteilen, die Lignin und/ oder Ligninderivate und Fasern enthalten. Das Lignin und/ oder die Ligninderivate stammen aus ligninhaltigen Abfällen der Herstellung und Gewinnung von industriellen Produkten aus pflanzlichen Rohstoffen.The object is achieved by a method according to claim 1 for the production of moldings containing lignin and / or lignin derivatives and fibers. The lignin and / or the Lignin derivatives are derived from lignin-containing wastes from the production and extraction of industrial products from vegetable raw materials.

Bei der industriellen Herstellung von Papier, Bioethanol, Chemikalien und Pharmazeutika aus pflanzlicher Biomasse fällt eine gewaltige Menge an Abfallstoffen an, darunter auch eine immense Menge an lignin- und/ oder ligninderivate-haltiger Abfälle. Diese Abfälle können als Quelle für Lignin- und/ oder Ligninderivate dienen, die in Schritt a) von den übrigen Abfällen abgetrennt werden. Die Abtrennung von den übrigen Abfallstoffen kann hierbei mehr oder weniger vollständig erfolgen. Auch kann das abgetrennte Lignin und/ oder die Ligninderivate einen Anteil an Restfeuchte aufweisen. Im nächsten Schritt wird das Lignin und/ oder die Ligninderivate aus Schritt a) mit Fasern vermischt. Hierbei ist auch denkbar, dass Lignin und/ oder Ligninderivate aus unterschiedlichen ligninhaltigen Abfällen gewonnen und mit den Fasern gemischt werden. Die zugemischten Fasern dienen der Erhöhung der Festigkeit des Formteils. Bei der Extrusion in Schritt c) wird das Gemisch in einer Plastifizierzone geschmolzen und mittels Extruderschnecke kontinuierlich durch eine Formdüse gepresst und zu einer Platte geformt. Die Plattenform kann hierbei durch Walzen erzeugt werden. Die Platte aus Schritt c) wird anschließend auf Kunststofftiefziehmaschinen zu einem Formteil tiefgezogen. Hierbei sind alle durch das Tiefziehen zugänglichen Formgebungen möglich. Die so erzeugten Formteile eignen sich auch zu einer anschließenden Weiterbearbeitung durch herkömmliche Fräsen. Die Verwendung von Lignin und/ oder Ligninderivaten aus ligninhaltigen Abfällen, die bei der Herstellung und Gewinnung von industriellen Produkten wie Zellstoff oder Bioethanol, von Chemikalien und Pharmazeutika aus ligninhaltiger Biomasse anfallen, schont sowohl die fossilen als auch die natürlichen Ressourcen. Zudem lassen sich auf Basis von Lignin und/ oder Ligninderivaten aus den ligninhaltigen Abfällen aufgrund von Einsparungen im Bereich der Rohstoffbeschaffung kostengünstig haltbare, witterungsbeständige und dennoch biologisch abbaubare Formteile herstellen.In the industrial production of paper, bioethanol, chemicals and pharmaceuticals from plant biomass, a huge amount of waste material is produced, including an immense amount of lignin and / or lignin derivatives-containing waste. This waste can serve as a source of lignin and / or lignin derivatives, which are separated from the remaining waste in step a). The separation of the other waste materials can be done more or less complete. Also, the separated lignin and / or the lignin derivatives may have a proportion of residual moisture. In the next step, the lignin and / or the lignin derivatives from step a) are mixed with fibers. It is also conceivable that lignin and / or lignin derivatives are obtained from different lignin-containing wastes and mixed with the fibers. The blended fibers serve to increase the strength of the molding. In the extrusion in step c), the mixture is melted in a plasticizing zone and continuously extruded through an extrusion screw through a die and formed into a plate. The plate shape can be produced by rolling. The plate from step c) is then deep-drawn on plastic thermoforming machines to form a molding. Here are all accessible by thermoforming shapes possible. The molded parts thus produced are also suitable for subsequent further processing by conventional milling. The use of lignin and / or lignin derivatives from lignin-containing wastes in the manufacture and extraction of industrial products such as pulp or bioethanol, from chemicals and pharmaceuticals from lignocellulosic biomass, protects both fossil and natural resources. In addition, on the basis of lignin and / or lignin derivatives from the lignin-containing wastes due to savings in the field of raw material procurement cost-effective, weather-resistant, yet biodegradable molded parts can be produced.

Nach einer vorteilhaften Ausgestaltung der Erfindung wird das Gemisch aus Schritt b) vor der Weiterverarbeitung in Schritt c) in Granulatform gebracht. Dies kann derart erfolgen, dass das Gemisch in einem Extruder zunächst aufgeschmolzen wird. Die Schmelze wird über Düsen zu Strängen geformt und im Wasser abgekühlt. Anschließend schneidet ein rotierendes Messer die Stränge in wenige Millimeter lange Abschnitte. Eine Granulierung ist auch durch Kaltpressverfahren möglich.According to an advantageous embodiment of the invention, the mixture from step b) is brought into granular form before further processing in step c). This can be done in such a way that the mixture is first melted in an extruder. The melt is formed into strands via nozzles and cooled in the water. Then a rotating knife cuts the strands into a few millimeters long sections. Granulation is also possible by cold pressing.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung stammen die ligninhaltigen Abfälle aus dem Sulfit-, dem Sulfat- oder dem Organosolv-Verfahren zur Zellstoffgewinnung. Papier wird aus Zellstoff hergestellt, der im wesentlichen aus Zellulose besteht. Zur Gewinnung von Zellstoff aus Baumholz, wird dieses zunächst entrindet und anschließend zerkleinert. Für hochwertige Papiere wird die im sogenannten Holzschliff enthaltene Zellulose durch chemische Verfahren aufgeschlossen und Begleitsubstanzen wie Lignin, Hemizellulose und Harze abgetrennt. Es werden großtechnisch das Sulfat- und das Sulfitverfahren eingesetzt. Beim Sulfatverfahren wird der Holzschliff in Druckkesseln mit im wesentlichen Natronlauge, Natriumsulfid und Natriumsulfat erhitzt. Im Anschluss an die Kochung wird die Kochflüssigkeit, die Schwarzlauge, vom Zellstoff getrennt. Mit der Schwarzlauge bleiben unter anderem Lignin und/ oder Ligninderivate sowie Chemikalien zurück. Bei dem Sulfitverfahren werden die Hackschnitzel ebenfalls unter Druck mit Calciumhydrogensulfit, Magnesiumhydrogensulfit oder Ammoniumhydrogensulfit gekocht. Man erhält nach Abtrennung des Zellstoffs die Sulfitablauge, die Lignin und/ oder Ligninderivate neben weiteren Abfallstoffen wie die eingesetzten Chemikalien und Zucker enthält. Die in der Aufschlussflüssigkeit nach dem Organosolv-Verfahren anfallenden ligninhaltigen Rückstände können ebenso für das erfindungsgemäße Verfahren verwendet werden, wie Abfälle aus dem Natronverfahren oder dem Salpetersäureaufschluss.According to a further advantageous embodiment of the invention, the lignin-containing waste from the sulfite, the sulfate or the Organosolv process for pulp production. Paper is made from pulp consisting essentially of cellulose. To obtain pulp from tree wood, this is first debarked and then crushed. For high-quality papers, the cellulose contained in the so-called wood pulp is digested by chemical processes and accompanying substances such as lignin, hemicellulose and resins are separated. The sulphate and sulphite processes are used industrially. In the sulphate process, the groundwood is heated in pressure vessels with essentially sodium hydroxide solution, sodium sulphide and sodium sulphate. Following cooking, the cooking liquor, the black liquor, is separated from the pulp. Lignin and / or lignin derivatives as well as chemicals remain behind with the black liquor. In the sulfite process, the chips are also cooked under pressure with calcium hydrogen sulfite, magnesium hydrogen sulfite or ammonium bisulfite. After removal of the pulp, the sulfite liquor, the lignin and / or Lignin derivatives in addition to other waste such as the chemicals used and sugar contains. The lignin-containing residues obtained in the digestion liquid by the Organosolv process can likewise be used for the process according to the invention, such as wastes from the soda process or the nitric acid digestion.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung handelt es sich bei den Ligninderivaten um Ligninsulfonsäuren oder Alkali-Lignin aus den Kochflüssigkeiten des Sulfit- oder Sulfatverfahrens. Jedoch eignet sich ebenfalls bei weiteren Verfahren anfallendes Lignin und/ oder Ligninderivate, wie das aus dem Organosolv-Verfahren stammende.According to a further advantageous embodiment of the invention, the lignin derivatives are ligninsulfonic acids or alkali lignin from the boiling liquids of the sulfite or sulfate process. However, lignin and / or lignin derivatives obtained in further processes, such as those derived from the Organosolv process, are likewise suitable.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung erfolgt das Abtrennen des Lignins und/ oder der Ligninderivate aus den ligninhaltigen Abfällen durch chemische und/ oder durch physikalische Separationsmittel. Hierbei können Lignin und/ oder Ligninderivate durch Ultra- oder Nanofiltrations-Membranmodule aus den Abfällen gewonnen werden. Auch ein Ausfällen der Ligninderivate durch pH-Shift oder den Zusatz von komplexbildenden Fällungsmitteln ist möglich. Wobei aufgrund von geringeren Kosten die einfachen Fällungsreaktionen gegenüber den Filtrationsmethoden, bei denen die Membran relativ häufig gewechselt werden muss, vorzuziehen sind. Diese Abtrennungsmethoden können sich auch an einen vorhergehenden chemischen Aufschluss ligninhaltiger Abfälle anschließen, wenn es sich beispielsweise um Abfälle aus der Gewinnung von Bioethanol handelt. In diesen Fällen enthält die nach dem Vergärungsprozess zurückbleibende Schlempe das Lignin noch in Vergesellschaftung mit Zellulose. Darüber hinaus können jederzeit weitere Separierungs- und Behandlungsschritte des Lignins und/ oder der Ligninderivate in den Abtrennungsprozess integriert werden. Es ist jedoch aus Kostengründen erwünscht, die Anzahl an Schritten zur Abtrennung des Lignins und/ oder der Ligninderivate möglichst gering zu halten.According to a further advantageous embodiment of the invention, the separation of the lignin and / or the lignin derivatives from the ligninhaltigen wastes by chemical and / or by physical separation means. In this case, lignin and / or lignin derivatives can be obtained from the waste by ultrafiltration or nanofiltration membrane modules. A precipitation of the lignin derivatives by pH shift or the addition of complexing precipitants is possible. However, due to lower costs, the simple precipitation reactions compared to the filtration methods, in which the membrane must be changed relatively frequently, are preferable. These separation methods may also follow a previous chemical digestion of lignocellulosic waste, for example waste from the production of bioethanol. In these cases, the still remaining vinification after the fermentation process contains the lignin still in association with cellulose. In addition, further separation and treatment steps of the lignin and / or the lignin derivatives can be integrated into the separation process at any time. However, it is desirable for reasons of cost to keep the number of steps for separating the lignin and / or the lignin derivatives as low as possible.

Nach der Erfindung handelt es sich bei den Fasern um natürliche Fasern aus der Gruppe der Samenfasern, Bastfasern, Fruchtfasern, Holzfasern oder Blattfasern von Pflanzen. Hierbei können die Fasern aus der Baumwolle, aus der Alpaka-Pflanze, des Bambus, der Brennnessel, des Hanfs, der Kokospflanze oder der Binse Verwendung finden. Aber auch Pappelflaum, Jute, Leinen, Ramie oder Sisal sind geeignet. Um die pflanzlichen Ressourcen weiter zu schonen, können natürliche Fasern eingesetzt werden, die beim Anbau von Pflanzen als Agroabfall anfallen. Es handelt sich bei den Fasern auch um Chemiefasern aus natürlichen Polymeren. Hierbei kommen Chemiefasern aus Polymeren auf der Basis von Stärke zur Anwendung . Diese Chemiefasern werden entweder anstelle der natürlichen Fasern oder gemeinsam mit diesen eingesetzt.According to the invention, the fibers are natural fibers from the group of seed fibers, bast fibers, fruit fibers, wood fibers or leaf fibers of plants. Here, the fibers from the cotton, from the alpaca plant, the bamboo, the nettle, the hemp, the coconut plant or the bulrush can be used. But also poplar fluff, jute, linen, ramie or sisal are suitable. In order to further conserve the plant's resources, natural fibers can be used that are produced as agricultural waste when growing plants. The fibers are also synthetic fibers made from natural polymers. In this case, chemical fibers made of polymers based on starch are used. These chemical fibers are used either instead of or in conjunction with the natural fibers.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung werden dem Gemisch aus Schritt b) weitere Hilfsstoffe zugemischt. Beispielsweise können Hilfsstoffe mit thermoplastischen Eigenschaften dann dem Gemisch zugemischt werden, falls eine über die natürlichen thermoplastischen Eigenschaften des Lignins und/ oder der Ligninderivate hinausgehende Thermoplastizität in den unter c) und d) aufgeführten Schritten erwünscht ist. Auch für eine Granulierung des Gemisches durch Verfahren unter Hitzeeinwirkung können dem Gemisch gegebenenfalls Hilfsstoffe mit thermoplastischen Eigenschaften zumischt werden.According to a further advantageous embodiment of the invention, further excipients are added to the mixture from step b). For example, adjuvants having thermoplastic properties can then be blended into the blend if a thermoplasticity in excess of the natural thermoplastic properties of the lignin and / or lignin derivatives is desired in the steps listed under c) and d). Also, for granulation of the mixture by heat-affected processes, adjuvants having thermoplastic properties may optionally be added to the mixture.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung handelt es sich bei den Hilfsstoffen um natürliche Polymere, auf natürlichen Stoffen basierende Polymere, Wasser, Pigmente, Farbstoffe, Füllstoffe und /oder um Mischungen dieser. Natürliche Polymere und auf natürlichen Stoffen basierende Polymere mit thermoplastischen Eigenschaften können zur Erhöhung der thermoplastischen Eigenschaften für die weitere Verarbeitung des Gemisches eingesetzt werden. Durch den Zusatz von Pigmenten und Farbstoffen ist eine individuelle Farbgebung der Formteile möglich. Der Zusatz von Wasser kann die Verarbeitbarkeit des Gemisches positiv beeinflussen. Füllstoffe können zur zusätzlichen Kostensenkung in dem bei dem Verfahren verwendeten Gemisch enthalten sein.According to a further advantageous embodiment of the invention, the excipients are natural polymers, based on natural substances polymers, water, pigments, dyes, fillers and / or mixtures of these. Natural polymers and natural-based polymers with thermoplastic properties can be used to increase the thermoplastic properties for further processing of the blend. By the addition of pigments and dyes, an individual coloring of the molded parts is possible. The addition of water can be the Processability of the mixture influence positively. Fillers may be included for additional cost reduction in the mixture used in the process.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung weist die Platte aus Schritt c) eine Stärke von 2 mm bis 15 mm auf, bevorzugt von 2 mm bis 10 mm. Dies ermöglicht die Herstellung von Formteilen mit unterschiedlicher Wanddicke. Hieraus ergibt sich eine weitere Vielzahl an unterschiedlichen Gestaltungsmöglichkeiten hinsichtlich der Formteile, welche durch das erfindungsgemäße Verfahren hergestellt werden können.According to a further advantageous embodiment of the invention, the plate from step c) has a thickness of 2 mm to 15 mm, preferably from 2 mm to 10 mm. This allows the production of moldings with different wall thickness. This results in a further variety of different design options with regard to the molded parts, which can be produced by the method according to the invention.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung wird ein Gemisch enthaltend Lignin und/ oder Ligninderivate und Fasern zur Herstellung von Formteilen durch Tiefziehen verwendet.According to a further advantageous embodiment of the invention, a mixture containing lignin and / or lignin derivatives and fibers for the production of moldings is used by deep drawing.

Nach einer weiteren vorteilhaften Ausgestaltung der Erfindung wird ein Gemisch enthaltend Lignin und/ oder Ligninderivate und Fasern zur Herstellung von Hinweisschildern durch Tiefziehen verwendet. Dieser können beispielsweise zur Beschilderung von Feld- und Waldwegen dienen.According to a further advantageous embodiment of the invention, a mixture containing lignin and / or lignin derivatives and fibers for the production of signs by deep drawing is used. These can be used, for example, for signposting field and forest trails.

Weitere Vorteile und vorteilhafte Ausgestaltungen der Erfindung sind den Ansprüchen zu entnehmen.Further advantages and advantageous embodiments of the invention can be found in the claims.

Claims (9)

  1. Method for manufacturing moulded objects containing lignin and/or lignin derivatives from waste containing lignin from the manufacture and extraction of industrial products from vegetable raw materials and fibres,
    comprising the steps:
    a) Separation of the lignin and/or the lignin derivatives from the waste containing lignin
    b) Producing a mixture at least from the lignin and/or the lignin derivatives from step a) with the addition of fibres
    c) Extrusion of the mixture into a plate
    d) Deep drawing of the plate into a moulded part,
    characterised in that the natural polymer starch in the form of synthetic fibres is added to the mixture from step b) as an additive.
  2. Method according to claim 1, characterised in that the mixture from step b) is made into a granulate before being processed further in step c).
  3. Method according to claim 1 or 2, characterised in that the waste containing lignin comes from the sulphite, sulphate or organosolv method for pulping.
  4. Method according to one of the previous claims, characterised in that the lignin derivatives concerned are lignosulphonic acids, alkali lignin or organosolv lignin.
  5. Method according to one of the previous claims, characterised in that the separation of the lignin and/or the lignin derivatives from the waste containing lignin occurs by means of chemical and/or physical means of separation.
  6. Method according to one of the previous claims, characterised in that the fibres concerned are natural fibres from the group of seed fibres, bast fibres, fruit fibres, wood fibres or leaf fibres from plants.
  7. Method according to one of the previous claims, characterised in that additional additives are added to the mixture from step b).
  8. Method according to claim 7, characterised in that the additives concerned are natural polymers, water, waxes, pigments, dyes, fillers and/or mixtures of these.
  9. Method according to one of the previous claims, characterised in that the plate from step c) has a thickness of 2 mm to 15 mm, preferably 2 mm to 10 mm.
EP20100009307 2009-09-24 2010-09-07 Method for manufacturing moulded objects Not-in-force EP2301731B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13001490.5A EP2612739B1 (en) 2009-09-24 2010-09-07 Method and use of lignin for manufacturing of moulded objects
SI201030300T SI2301731T1 (en) 2009-09-24 2010-09-07 Method for manufacturing moulded objects

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE200910042595 DE102009042595A1 (en) 2009-09-24 2009-09-24 Process for the production of molded parts

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP13001490.5A Division EP2612739B1 (en) 2009-09-24 2010-09-07 Method and use of lignin for manufacturing of moulded objects
EP13001490.5 Division-Into 2013-03-22

Publications (3)

Publication Number Publication Date
EP2301731A2 EP2301731A2 (en) 2011-03-30
EP2301731A3 EP2301731A3 (en) 2011-11-09
EP2301731B1 true EP2301731B1 (en) 2013-05-15

Family

ID=43309507

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13001490.5A Not-in-force EP2612739B1 (en) 2009-09-24 2010-09-07 Method and use of lignin for manufacturing of moulded objects
EP20100009307 Not-in-force EP2301731B1 (en) 2009-09-24 2010-09-07 Method for manufacturing moulded objects

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13001490.5A Not-in-force EP2612739B1 (en) 2009-09-24 2010-09-07 Method and use of lignin for manufacturing of moulded objects

Country Status (4)

Country Link
EP (2) EP2612739B1 (en)
DE (1) DE102009042595A1 (en)
DK (1) DK2301731T3 (en)
SI (1) SI2301731T1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104191472B (en) * 2014-08-28 2016-04-27 潘建朋 A kind of wood-based plate reducing pernicious gas
CN110539382B (en) * 2018-05-29 2021-08-06 中国石油化工股份有限公司 Medium-density fiberboard and preparation method thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT62949B (en) * 1912-09-27 1914-01-10 Franz Breitschopf Automatic brake mount lock.
US3296963A (en) * 1964-07-27 1967-01-10 Continental Can Co Electrostatic screen printing of articles made of highly insulating materials
US3903229A (en) * 1968-12-23 1975-09-02 Andre Mark Method for producing a compressed band of wood fibers for the production of wood fiber boards
DE2122817B2 (en) * 1971-05-08 1978-05-24 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V., 8000 Muenchen Process for the production of chipboard
DE2221353C3 (en) * 1972-05-02 1981-03-19 Helmitin-Werke Chemische Fabrik Heinicke Kg, 6780 Pirmasens Process for the production of wood-based materials and panels coated with plastic and for the bonding of wood-based materials and plastics
JPS5464578A (en) * 1977-11-02 1979-05-24 Shigeru Kogyo Kk Method of making interior core material having three dimensionally curved configuration
DE3644397C1 (en) * 1986-12-24 1988-05-05 Pfleiderer Fa G A Low-emission binder for wood and cellulose-containing materials
FI83348C (en) * 1987-03-09 1996-01-09 Metsae Serla Oy Process for making products from lignocellulosic material
US5686170A (en) * 1995-12-21 1997-11-11 Minnesota Mining And Manufacturing Company Labor-saving process and article for making dimensional sign graphics
FI970157A (en) * 1997-01-14 1998-07-15 Neste Oy Fiberboard adhesives and method of making them
EP0961813B1 (en) * 1997-02-20 2004-04-21 Kronospan Technical Co. Ltd. Adhesive composition and its use
US5997784A (en) * 1998-01-06 1999-12-07 Karnoski; Wayne Method of manufacture of wood substitute articles
DE10021952A1 (en) * 2000-05-05 2001-11-22 Fraunhofer Ges Forschung Production of binder liquor for wood-to-wood bonding, especially in chipboard and fiberboard manufacture, using waste liquor from manufacture of wood product, e.g. chipboard and fiberboard, for dissolving binder powder
DE102006057566B4 (en) * 2006-11-30 2011-02-24 Sächsisches Institut für Angewandte Biotechnologie e.V. (SIAB) Process for producing a low-emission lignocellulosic raw material or material, component or product

Also Published As

Publication number Publication date
DE102009042595A1 (en) 2011-03-31
EP2301731A2 (en) 2011-03-30
SI2301731T1 (en) 2013-09-30
EP2612739B1 (en) 2014-08-27
DK2301731T3 (en) 2013-07-29
EP2612739A1 (en) 2013-07-10
EP2301731A3 (en) 2011-11-09

Similar Documents

Publication Publication Date Title
Yu et al. Nanocellulose from various biomass wastes: Its preparation and potential usages towards the high value-added products
Pennells et al. Trends in the production of cellulose nanofibers from non-wood sources
EP3266810A1 (en) Lignin based composite material and method for its production
EP2953997A1 (en) Micro-structured composite material, method for producing same, mouldings made of same, and uses thereof
Pratama et al. The extraction of cellulose powder of water hyacinth (Eichhornia crassipes) as reinforcing agents in bioplastic
Ilyas et al. Mechanical testing of sugar palm fiber reinforced sugar palm biopolymer composites
Miléo et al. Thermal and chemical characterization of sugarcane bagasse cellulose/lignin-reinforced composites
Muangmeesri et al. Holistic valorization of hemp through reductive catalytic fractionation
EP2301731B1 (en) Method for manufacturing moulded objects
EP4139519B1 (en) Method for manufacturing a dimensionally stable object from renewable biomass
Souza et al. The use of curaua fibers as reinforcements in composites
Chadijah et al. Determination of the optimum concentration cellulose baggase in making film bioplastic
DE102009051884A1 (en) Processing a biomass comprises separating the biomass into a lignin fraction and (hemi)cellulose fraction, processing the (hemi)cellulose fraction, and converting the lignin fraction into an organo-mineral fertilizer
DE102014215627A1 (en) Composite material and molded part of this
CN104497606A (en) Preparation method of lignin thermoplastic material
CN104356663A (en) Preparation method of lignin thermoplastic material
DE102009027635A1 (en) Process for the acetylation of lignocelluloses, hemicelluloses, celluloses with ketene
EP2670895A1 (en) Process for providing and processing natural fibres
CN113386233B (en) Cellulose-based section bar and processing technology
Yacob et al. Effect of cellulose fiber from sago waste on properties of starch-based films
WO2021001197A1 (en) Composite material with a matrix on the basis of organic plastics, and use thereof
EP0346836A3 (en) Process and apparatus for the continuous production of 2-furaldehyde, cellulose and lignine from lignocellulosic materials
CN104371341A (en) Preparation method of lignin thermoplastic material
EP3980595B1 (en) Joint processing of lignocellulose raw material and cellulose-containing lignine-free product
Cheng-Shun et al. Parameter Optimization of a Biodegradable Agricultural Film Manufactured with Wheat Straw Fiber.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME RS

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME RS

RIC1 Information provided on ipc code assigned before grant

Ipc: B27N 1/00 20060101AFI20111004BHEP

Ipc: B27N 5/00 20060101ALI20111004BHEP

Ipc: B27N 3/04 20060101ALI20111004BHEP

17P Request for examination filed

Effective date: 20120418

17Q First examination report despatched

Effective date: 20120618

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 611886

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502010003317

Country of ref document: DE

Effective date: 20130711

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: OFFICE ERNEST T. FREYLINGER S.A., CH

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20130718

Year of fee payment: 4

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130816

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130916

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130815

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130826

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130915

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SI

Payment date: 20130618

Year of fee payment: 4

Ref country code: NL

Payment date: 20130916

Year of fee payment: 4

Ref country code: DK

Payment date: 20130826

Year of fee payment: 4

Ref country code: SE

Payment date: 20130722

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20130930

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20140218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502010003317

Country of ref document: DE

Effective date: 20140218

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130907

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20140930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140907

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140908

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150401

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

REG Reference to a national code

Ref country code: SI

Ref legal event code: KO00

Effective date: 20150504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140908

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100907

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140907

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140930

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160922

Year of fee payment: 7

Ref country code: CH

Payment date: 20160926

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20160921

Year of fee payment: 7

Ref country code: FR

Payment date: 20160922

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160922

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502010003317

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 611886

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170907

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170930

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170907

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515