EP1874513B1 - Method for producing reduced-emission, low-thickness swell medium density fiber boards and molded fiber parts - Google Patents

Method for producing reduced-emission, low-thickness swell medium density fiber boards and molded fiber parts Download PDF

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Publication number
EP1874513B1
EP1874513B1 EP06742271A EP06742271A EP1874513B1 EP 1874513 B1 EP1874513 B1 EP 1874513B1 EP 06742271 A EP06742271 A EP 06742271A EP 06742271 A EP06742271 A EP 06742271A EP 1874513 B1 EP1874513 B1 EP 1874513B1
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EP
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Prior art keywords
tannin
fibers
added
lignocelluloses
boards
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German (de)
French (fr)
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EP1874513A1 (en
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Edmone Roffael
Thomas Schneider
Brigitte Dix
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • 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
    • 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
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder

Definitions

  • the invention relates to a method for the production of medium-density fiberboard (MDF) according to the preamble of claim 1, with reduced emission of volatile organic compounds (VOC) and at the same time low thickness swelling.
  • Volatile organic compounds subsume organic substances whose boiling point is between 50 ° C and 260 ° C. Most of the volatile organic compounds come from the wood, but sometimes also from the binder. The interaction between binder and wood also influences the composition of the volatile constituents; other influencing factors are the production conditions of the medium-density fiberboard. Wood-based materials also emit formaldehyde. However, formaldehyde is not included in the definition of volatile organic compounds.
  • Lignocelluloses can be woods and annual plants.
  • thermomechanical process also the production of fibers by the chemo-thermo-mechanical process (CTMP process) is from the EP 0 639 434 known.
  • CMP process chemo-thermo-mechanical process
  • wood chipping products such as Wood chips washed first to remove any existing sand particles. After washing, the wood chips are usually pre-steamed at temperatures between 60 ° C and 80 ° C and then get via screw conveyance in the so-called cooker, where they are usually digested thermohydrolytically at temperatures of 170 ° C to 180 ° C.
  • the digested chips are transferred to a pressure refiner, where they are fiberized under pressure at temperatures of 170 ° C to 180 ° C.
  • the defibering in the pressure refiner can be followed by a non-pressurized refining stage.
  • the digestion conditions can be varied depending on the raw material; for annual plants, lower temperatures of 140 ° C to 160 ° C can be used for digestion.
  • the fibers are conveyed by the pressure prevailing in the refiner into a blow pipe, where they are provided with a binder.
  • chemicals such as sodium sulfite and sodium hydroxide, or combinations of sodium sulfite and sodium hydroxide, are added to the wood chippings before or during digestion. The addition of other chemicals is possible.
  • binders for the production of medium-density fiberboard mainly amino resins such as urea-formaldehyde resins (UF resins) are used, other synthetic binders such as alkaline curing phenol-formaldehyde resins (PF resins) and adhesives based on polymeric diisocyanates (PMDI), however, have only a relatively small importance , It is also possible to use thermoplastic binders such as methacrylate reaction resins for bonding fibers.
  • the binder used for the production of MDF is often injected into the blast line, but it can also be applied after drying the fibers in a blender.
  • Combinations of the two methods are also possible, so only a part of the binder can be injected into the blowing line and the rest are applied only after drying in the blender. It can also enter the blowpipe Binder of certain composition introduced and used after drying another binder with different composition.
  • binders based on natural substances such as tannin-formaldehyde resins (TF resins) can be used for the production of MDF.
  • the TF resins are obtained by reaction between tannins and formaldehyde.
  • the tannins in particular the condensed tannins, are obtained by extraction from certain barks and woods. Particularly suitable for this Quebrachoholz (Quebracho colorado) and bark such as acacia bark (Acacia mearnsii), spruce bark (Picea abies), etc.
  • the extraction of tannins from wood and bark is usually carried out at temperatures between 70 ° C and 130 ° C in water in the cascade process according to the countercurrent principle.
  • binders During extraction, chemicals such as sodium sulfite and / or sodium hydroxide may also be added to predominantly increase the solubility of tannin in the water. The sulfitation of tannin can also take place after the extraction.
  • the extracted tannins are reacted with formaldehyde.
  • starch As another natural binder, starch can be used in various forms (native starch, oxidized starch, modified starch). Also combinations of tannin and starch are known as binders.
  • the volatile degradation components of the wood, coming from the refiner, may be partially emitted during the drying of the fiber to the environment since they are steam volatile. Furthermore, the volatile acids can act as a hardener and partially precondens the injected binder in the blowpipe and optionally during drying. This leads to reduced adhesion of the binder during pressing.
  • the non-volatile degraded carbohydrates formed during digestion remain in the fiberboards produced and may reduce their biological resistance.
  • the DE 101 24 638 A1 describes a process for producing tanning-bonded lignocellulosic plates from used chipboard and fibreboard in which shredded products from the used plates are digested with tannin solutions in a concentration between 1% and 30% in the temperature range between 70 ° C and 200 ° C, dried, spread into mats and be pressed hot.
  • the aim of the process is to produce medium-density fiberboard with the binder tannin-formaldehyde resin without previously controlling tannin with formaldehyde to produce tannin-formaldehyde resins.
  • the decomposition of used wood chips and used wood fiber boards releases formaldehyde and reacts with the aqueous diluted tannin solution to form tannin formaldehyde resin.
  • the object of the invention is firstly to reduce the amount of volatile constituents from medium-density fiberboard and their formation ' largely to prevent and on the other hand, the physico-technological properties of the plates produced to improve. In particular, the thickness swelling of the plates should be reduced.
  • This method with a combined application of CTMP and the presence of tannins is suitable for all lignocelluloses.
  • the addition of chemicals in the sense of the CTMP process can be carried out prior to digestion or during the digestion in a known manner.
  • sodium sulfite, sodium bisulfite and sodium hydroxide or optimized mixtures thereof may be used. Since sodium sulfite and sodium bisulfite can sulfite the tannin and increase its solubility in the water, this procedure makes it possible to combine the digestion and defibration of wood chips with the sulfitation of the condensed tannin in the refiner in a meaningful manner.
  • pine wood chips were digested at a temperature of 170 ° C, in the fiberization stage under pressure in the refiner condensed tannins were added to the wood chips before digestion in amounts of 2% (solid based on atro wood material) (Experiment 2).
  • the dried fibers were usually mixed with the UF resin Glueing amounts of 12% (solid resin based on dry fibers), shaped into fiber mats and hot pressed into medium-density fibreboard (see Experiment 1).
  • the plates thus prepared were then at 20 ° C and 65% rel. Humidity stored before they were tested for their physical-technological properties and emission.
  • medium density fiberboards were made from fibers prepared by adding 1% Na 2 SO 3 and 0.5% NaOH (solid based on dry wood material) according to the CTMP method.
  • the digestion temperature was 170 ° C.
  • the production of the MDF was carried out under the same conditions as in the case of the TMP fibers (see Experiment 1).
  • binders for the production of medium-density fibreboards can be those which lead to a moisture-resistant fiber-to-fiber bond as well as those which lead to fiber-to-fiber bonding with low moisture resistance.
  • Typical binders for the production of moisture-resistant adhesives are alkaline curing phenol-formaldehyde resins (PF resins), tannin-formaldehyde resins (TF resins), melamine-urea phenol-formaldehyde resins (MUPF resins) and adhesives based on PMDI (polymeric diphenylmethane diisocyanates). Binders that result in low moisture resistance fiber-to-fiber bonding include urea formaldehyde resins (UF resins).

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

For the production of fiberboards, and especially medium density fiberboards, the ligno cellulose materials are digested in a chemo-thermo hydrolytic action and then reduced to fibers in a refiner together with condensed tannin. The fibers are mixed with a bonding agent and then scattered to form a mat for compression into boards. The bonding agent can be amino resin, phenol formaledehyde resin, tannin formaldehyde resin and/or an adhesive based on diisocyanates.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von mitteldichten Faserplatten (MDF) gemäß dem Oberbegriff des Anspruchs 1, mit verminderter Emission an flüchtigen organischen Verbindungen (VOC) und zugleich niedriger Dickenquellung. Als flüchtige organische Verbindungen werden organische Stoffe subsumiert, deren Siedepunkt zwischen 50°C und 260°C liegt. Die flüchtigen organischen Verbindungen stammen größtenteils aus dem Holz, teils aber auch aus dem Bindemittel. Auch die Wechselwirkung zwischen Bindemittel und Holz beeinflusst die Zusammensetzung der flüchtigen Bestandteile, weitere Einfluss nehmende Faktoren sind die Herstellungsbedingungen der mitteldichten Faserplatten. Holzwerkstoffe emittieren auch Formaldehyd. Formaldehyd wird aber gemäß Definition den flüchtigen organischen Verbindungen nicht zugerechnet.The invention relates to a method for the production of medium-density fiberboard (MDF) according to the preamble of claim 1, with reduced emission of volatile organic compounds (VOC) and at the same time low thickness swelling. Volatile organic compounds subsume organic substances whose boiling point is between 50 ° C and 260 ° C. Most of the volatile organic compounds come from the wood, but sometimes also from the binder. The interaction between binder and wood also influences the composition of the volatile constituents; other influencing factors are the production conditions of the medium-density fiberboard. Wood-based materials also emit formaldehyde. However, formaldehyde is not included in the definition of volatile organic compounds.

Für die Herstellung von mitteldichten Faserplatten werden Fasern aus Lignocellulosen mit einem Bindemittel beleimt, zu Fasermatten gestreut und anschließend, gegebenenfalls nach einem Vorpressvorgang, heiß gepresst. Lignocellulosen können Hölzer und Einjahrespflanzen sein.For the production of medium density fiberboard fibers from lignocelluloses are glued with a binder, scattered into fiber mats and then, optionally after a pre-pressing, hot pressed. Lignocelluloses can be woods and annual plants.

Die Gewinnung der Fasern aus den Lignocellulosen erfolgt in der Regel nach einem thermomechanischen Verfahren (TMP-Verfahren), auch die Herstellung von Fasern nach dem chemo-thermomechanischen Verfahren (CTMP-Verfahren) ist aus dem EP 0 639 434 bekannt. Für die Herstellung von Fasern aus Holz nach dem TMP-Verfahren werden Holzzerkleinerungsprodukte wie Hackschnitzel zuerst gewaschen, um eventuell vorhandene Sandpartikel zu entfernen. Nach dem Waschen werden die Hackschnitzel in der Regel bei Temperaturen zwischen 60°C und 80°C vorgedämpft und gelangen anschließend über Schneckenförderung in den sogenannten Kocher, wo sie üblicherweise bei Temperaturen von 170°C bis 180°C thermohydrolytisch aufgeschlossen werden. Nach dem Aufschluss werden die aufgeschlossenen Hackschnitzel in einen Druckrefiner überführt, wo sie unter Druck bei Temperaturen von ebenfalls 170°C bis 180°C zerfasert werden. Dem Zerfasern im Druckrefiner kann eine drucklose Refinerstufe folgen. Die Aufschlussbedingungen können je nach Rohstoff variiert werden, so können bei Einjahrespflanzen niedrigere Temperaturen von 140°C bis 160°C für den Aufschluss eingesetzt werden. Nach der Refinerstufe werden die Fasern durch den im Refiner herrschenden Druck in eine Blasleitung befördert, wo sie mit einem Bindemittel versehen werden. Bei der Herstellung von Fasern nach dem CTMP-Prozess werden den Holzzerkleinerungsprodukten vor oder während des Aufschlusses Chemikalien wie Natriumsulfit und Natriumhydroxid oder Kombinationen von Natriumsulfit und Natriumhydroxid zugesetzt. Auch die Zugabe anderer Chemikalien ist möglich.The extraction of the fibers from the lignocelluloses is usually carried out by a thermomechanical process (TMP process), also the production of fibers by the chemo-thermo-mechanical process (CTMP process) is from the EP 0 639 434 known. For the production of wood fibers using the TMP process, wood chipping products such as Wood chips washed first to remove any existing sand particles. After washing, the wood chips are usually pre-steamed at temperatures between 60 ° C and 80 ° C and then get via screw conveyance in the so-called cooker, where they are usually digested thermohydrolytically at temperatures of 170 ° C to 180 ° C. After digestion, the digested chips are transferred to a pressure refiner, where they are fiberized under pressure at temperatures of 170 ° C to 180 ° C. The defibering in the pressure refiner can be followed by a non-pressurized refining stage. The digestion conditions can be varied depending on the raw material; for annual plants, lower temperatures of 140 ° C to 160 ° C can be used for digestion. After the refining stage, the fibers are conveyed by the pressure prevailing in the refiner into a blow pipe, where they are provided with a binder. In the manufacture of fibers by the CTMP process, chemicals such as sodium sulfite and sodium hydroxide, or combinations of sodium sulfite and sodium hydroxide, are added to the wood chippings before or during digestion. The addition of other chemicals is possible.

Als Bindemittel werden für die Herstellung von mitteldichten Faserplatten hauptsächlich Aminoplastharze wie Harnstoffformaldehydharze (UF-Harze) eingesetzt, weitere synthetische Bindemittel wie alkalisch härtende Phenolformaldehydharze (PF-Harze) und Klebstoffe auf Basis von polymeren Diisocyanaten (PMDI) haben hierfür allerdings nur eine vergleichsweise geringe Bedeutung. Für die Bindung von Fasern können auch Thermoplast-Bindemittel wie Methacrylat-Reaktionsharze eingesetzt werden. Das für die Herstellung von MDF eingesetzte Bindemittel wird häufig in die Blasleitung eingedüst, es kann aber auch nach dem Trocknen der Fasern in einem Blender appliziert werden. Kombinationen aus den beiden Verfahren sind auch möglich, so kann in die Blasleitung nur ein Teil des Bindemittels eingedüst und der Rest erst nach dem Trocknen im Blender aufgebracht werden. Es kann auch in die Blasleitung ein Bindemittel bestimmter Zusammensetzung eingebracht und nach dem Trocknen ein anderes Bindemittel mit unterschiedlicher Zusammensetzung verwendet werden.As binders for the production of medium-density fiberboard mainly amino resins such as urea-formaldehyde resins (UF resins) are used, other synthetic binders such as alkaline curing phenol-formaldehyde resins (PF resins) and adhesives based on polymeric diisocyanates (PMDI), however, have only a relatively small importance , It is also possible to use thermoplastic binders such as methacrylate reaction resins for bonding fibers. The binder used for the production of MDF is often injected into the blast line, but it can also be applied after drying the fibers in a blender. Combinations of the two methods are also possible, so only a part of the binder can be injected into the blowing line and the rest are applied only after drying in the blender. It can also enter the blowpipe Binder of certain composition introduced and used after drying another binder with different composition.

Neben den synthetischen Bindemitteln können Bindmittel auf Basis von natürlichen Stoffen wie Tanninformaldehydharze (TF-Harze) für die Herstellung von MDF eingesetzt werden. Die TF-Harze werden durch Reaktion zwischen Tanninen und Formaldehyd gewonnen. Die Tannine, insbesondere die kondensierten Tannine, werden durch Extraktion von bestimmten Rinden und Hölzern gewonnen. Als besonders geeignet sind hierfür Quebrachoholz (Quebracho colorado) sowie Rinden wie Akazienrinde (Acacia mearnsii), Fichtenrinde (Picea abies) usw. Die Extraktion von Tanninen aus Hölzern und Rinden erfolgt in der Regel bei Temperaturen zwischen 70°C und 130°C in Wasser im Kaskadenverfahren nach dem Gegenstromprinzip. Während der Extraktion können auch Chemikalien wie Natriumsulfit und/oder Natriumhydroxid zugegeben werden, um vorwiegend die Löslichkeit des Tannins im Wasser zu erhöhen. Die Sulfitierung des Tannins kann auch nach der Extraktion erfolgen. Für die Herstellung von TF-Harzen werden die extrahierten Tannine mit Formaldehyd umgesetzt. Als ein weiteres natürliches Bindemittel kann Stärke in verschiedenen Formen (native Stärke, oxidierte Stärke, modifizierte Stärke) eingesetzt werden. Auch Kombinationen von Tannin und Stärke sind als Bindemittel bekannt.In addition to the synthetic binders, binders based on natural substances such as tannin-formaldehyde resins (TF resins) can be used for the production of MDF. The TF resins are obtained by reaction between tannins and formaldehyde. The tannins, in particular the condensed tannins, are obtained by extraction from certain barks and woods. Particularly suitable for this Quebrachoholz (Quebracho colorado) and bark such as acacia bark (Acacia mearnsii), spruce bark (Picea abies), etc. The extraction of tannins from wood and bark is usually carried out at temperatures between 70 ° C and 130 ° C in water in the cascade process according to the countercurrent principle. During extraction, chemicals such as sodium sulfite and / or sodium hydroxide may also be added to predominantly increase the solubility of tannin in the water. The sulfitation of tannin can also take place after the extraction. For the production of TF resins, the extracted tannins are reacted with formaldehyde. As another natural binder, starch can be used in various forms (native starch, oxidized starch, modified starch). Also combinations of tannin and starch are known as binders.

Im Zuge der thermohydrolytischen Behandlung im Kocher und im Refiner kommt es zum einen zum chemischen Teilabbau des Holzes. Es entstehen leicht flüchtige Verbindungen wie Formaldehyd, Furfural, Hydroxymethylfurfural, Ameisensäure und Essigsäure. Die Hemicellulosen des Holzes werden auch teilweise zu löslichen Kohlenhydraten abgebaut. Die aus dem Holz frei werdenden Ameisen- und Essigsäure haben eine gewisse Aufschlusswirkung auf das Holz. Neben dem Abbau an den Kohlenhydraten kann aber auch Lignin in geringem Umfang angegriffen werden, wodurch Ligninabbauprodukte wie Methanol und Formaldehyd entstehen können. Die chemische Zusammensetzung der flüchtigen organischen Verbindungen aus dem Holzmaterial bzw. aus den daraus hergestellten Fasern ist von den Holzarten abhängig. Im Falle von Kiefernholz können Aldehyde wie Pentanal, Hexanal und Heptanal in großen Mengen entstehen. Auf die Zusammensetzung der flüchtigen Bestandteile nehmen auch Aufschlussart und Aufschlussbedingungen Einfluss.In the course of thermohydrolytic treatment in the digester and in the refiner, on the one hand, the chemical degradation of the wood occurs. Volatile compounds such as formaldehyde, furfural, hydroxymethylfurfural, formic acid and acetic acid are formed. The hemicelluloses of the wood are also partially degraded to soluble carbohydrates. The ants and acetic acid released from the wood have a certain disruptive effect on the wood. In addition to the degradation of the carbohydrates and lignin can be attacked to a small extent, whereby Ligninabbauprodukte how Methanol and formaldehyde can arise. The chemical composition of the volatile organic compounds from the wood material or from the fibers produced therefrom depends on the wood species. In the case of pine wood, aldehydes such as pentanal, hexanal and heptanal can be produced in large quantities. On the composition of the volatile constituents also Aufschlussart and digestion conditions influence.

Die flüchtigen Abbaubestandteile des Holzes können, aus dem Refiner kommend, während der Trocknung der Faser an die Umgebung teilweise emittiert werden, da sie wasserdampfflüchtig sind. Weiterhin können die leicht flüchtigen Säuren als Härter fungieren und das eingedüste Bindemittel in der Blasleitung und gegebenenfalls während des Trocknens teilweise vorkondensieren. Dies führt zu verringerter Klebewirkung des Bindemittels während des Pressens. Die während des Aufschlusses entstehenden nicht flüchtigen abgebauten Kohlenhydrate verbleiben in den hergestellten Faserplatten und verringern womöglich ihre biologische Resistenz.The volatile degradation components of the wood, coming from the refiner, may be partially emitted during the drying of the fiber to the environment since they are steam volatile. Furthermore, the volatile acids can act as a hardener and partially precondens the injected binder in the blowpipe and optionally during drying. This leads to reduced adhesion of the binder during pressing. The non-volatile degraded carbohydrates formed during digestion remain in the fiberboards produced and may reduce their biological resistance.

Die DE 101 24 638 A1 beschreibt ein Verfahren zur Herstellung tanningebundener Lignocelluloseplatten aus Gebrauchtspan- und -faserplatten, bei dem Zerkleinerungsprodukte aus den gebrauchten Platten mit Tanninlösungen in einer Konzentration zwischen 1 % und 30% im Temperaturbereich zwischen 70°C und 200°C aufgeschlossen, getrocknet, zu Matten gestreut und heiß gepresst werden. Ziel des Verfahrens ist es, mitteldichte Faserplatten mit dem Bindemittel Tanninformaldehydharz herzustellen, ohne das Tannin vorher mit Formaldehyd regieren zu lassen, um Tanninformaldehydharze herzustellen. Durch den Aufschluss von Gebrauchtholzspan- und Gebrauchtholzfaserplatten wird Formaldehyd frei und reagiert mit der wässrig verdünnten Tanninlösung zu Tanninformaldehydharz.The DE 101 24 638 A1 describes a process for producing tanning-bonded lignocellulosic plates from used chipboard and fibreboard in which shredded products from the used plates are digested with tannin solutions in a concentration between 1% and 30% in the temperature range between 70 ° C and 200 ° C, dried, spread into mats and be pressed hot. The aim of the process is to produce medium-density fiberboard with the binder tannin-formaldehyde resin without previously controlling tannin with formaldehyde to produce tannin-formaldehyde resins. The decomposition of used wood chips and used wood fiber boards releases formaldehyde and reacts with the aqueous diluted tannin solution to form tannin formaldehyde resin.

Aufgabe der Erfindung ist es, zum einen die Menge an leicht flüchtigen Bestandteilen aus mitteldichten Faserplatten zu verringern und ihre Bildung' weitgehend zu unterbinden und zum anderen die physikalisch-technologischen Eigenschaften der hergestellten Platten zu verbessem. Insbesondere sollte die Dickenquellung der Platten vermindert werden.The object of the invention is firstly to reduce the amount of volatile constituents from medium-density fiberboard and their formation ' largely to prevent and on the other hand, the physico-technological properties of the plates produced to improve. In particular, the thickness swelling of the plates should be reduced.

Der Lösung für die der vorliegenden Erfindung zu Grunde liegende Aufgabe wird gemäß dem kennzeichnenden Teil des Anspruchs 1 definiert.The solution to the problem underlying the present invention is defined according to the characterizing part of claim 1.

Dieses Verfahren unterscheidet sich von der Lehre der EP 1 266 730 A1 , die die Zugabe von kondensierten Tanninen zu den nassen Spänen oder Fasern vor dem Beleimen der Späne oder der Fasern zum Gegenstand hat. Nach der Lehre der EP 1 266 730 A1 sind die Tannine während des Aufschlusses nicht zugegen, auch die Fasern müssen nicht nach dem CTMP-Verfahren gewonnen werden. In der vorliegenden Erfindung ist der Aufschluss nach dem CTMP-Verfahren ebenso obligatorisch wie die Zugabe von optimierten Mengen an kondensierten Tanninen. Selbstverständlich können die polyphenolischen kondensierten Tannine gemeinsam mit anderen Additiven wie Hydrophobierungsmitteln und/oder mit anderen polyphenolischen Stoffen wie Cashew-Nuss-Öle in den Refiner eingegeben werden.This procedure is different from the doctrine of EP 1 266 730 A1 which relates to the addition of condensed tannins to the wet chips or fibers prior to gluing the chips or fibers. After the apprenticeship of EP 1 266 730 A1 If the tannins are not present during the digestion, the fibers do not have to be obtained by the CTMP process. In the present invention digestion by the CTMP process is as compulsory as the addition of optimized amounts of condensed tannins. Of course, the polyphenolic condensed tannins may be added to the refiner along with other additives such as water repellents and / or other polyphenolic materials such as cashew nut oils.

Ferner wurde überraschend festgestellt, dass die vermindernde Wirkung des Tannins auf die Emission der hergestellten Platten an Formaldehyd auch nach ihrer Herstellung anhält. Die Formaldehydabgabe der Platten, die unter Einsatz von Tannin im Refiner hergestellt werden, nimmt weitaus schneller ab als die derjenigen, die ohne Einsatz von Tannin hergestellt sind.Further, it has surprisingly been found that the diminishing effect of tannin on the emission of the produced plates to formaldehyde also persists after their production. The formaldehyde release of the plates made using tannin in the refiner decreases much faster than that produced without the use of tannin.

Dieses Verfahren mit einer kombinierten Anwendung von CTMP und der Präsenz an Tanninen eignet sich für alle Lignocellulosen. Die Zugabe von Chemikalien im Sinne des CTMP-Prozesses kann vor dem Aufschluss oder während des Aufschlusses in bekannter Weise erfolgen. Als Chemikalien können Natriumsulfit, Natriumbisulfit und Natriumhydroxid oder optimierte Gemische hiervon eingesetzt werden. Da Natriumsulfit und Natriumbisulfit das Tannin sulfitieren können und dessen Löslichkeit im Wasser erhöhen, lässt sich mit dieser Vorgehensweise der Aufschluss und die Zerfaserung von Hackschnitzeln mit der Sulfitierung des kondensierten Tannins im Refiner in sinnvoller Weise kombinieren.This method with a combined application of CTMP and the presence of tannins is suitable for all lignocelluloses. The addition of chemicals in the sense of the CTMP process can be carried out prior to digestion or during the digestion in a known manner. As chemicals, sodium sulfite, sodium bisulfite and sodium hydroxide or optimized mixtures thereof may be used. Since sodium sulfite and sodium bisulfite can sulfite the tannin and increase its solubility in the water, this procedure makes it possible to combine the digestion and defibration of wood chips with the sulfitation of the condensed tannin in the refiner in a meaningful manner.

Das folgende Beispiel beschreibt die Erfindung ohne sie darauf festzulegen.The following example describes the invention without specifying it.

Im ersten Versuch wurden Holzhackschnitzel aus Kiefernholz bei einer Temperatur von 170°C thermohydrolytisch aufgeschlossen und anschließend unter Druck bei einer Temperatur von 170°C im Refiner zerfasert (TMP-Verfahren). Nach der Zerfaserung wurden die Fasern getrocknet und mit einem UF-Harz in Mengen von 12 % (Festharz bezogen auf atro Fasern) beleimt und anschließend zu Matten verformt und bei einer Temperatur von 200°C zu mitteldichten Faserplatten mit einer Soll-Rohdichte von 750 kg/m3 und einer Dicke von 16 mm heiß gepresst. Der Presszeitfaktor betrug 15 s/mm. Die so hergestellten Platten wurden anschließend bei einem Klima von 20°C und 65 % relativer Luftfeuchte gelagert, ehe sie auf ihre physikalisch-technologischen Eigenschaften und Emission geprüft wurden.In the first experiment wood chips from pine wood were digested thermohydrolytically at a temperature of 170 ° C and then defibrated under pressure at a temperature of 170 ° C in the refiner (TMP process). After defibering, the fibers were dried and glued with a UF resin in amounts of 12% (solid resin based on atro fibers) and then formed into mats and at a temperature of 200 ° C to medium density fiberboard with a target density of 750 kg / m 3 and a thickness of 16 mm hot pressed. The pressing time factor was 15 s / mm. The plates thus produced were then stored in a climate of 20 ° C and 65% relative humidity before they were tested for their physico-technological properties and emission.

Zum Vergleich wurden Kiefernholzhackschnitzel bei einer Temperatur von 170°C aufgeschlossen, in der Zerfaserungsstufe unter Druck im Refiner wurden den Hackschnitzeln vor dem Aufschluss kondensierte Tannine in Mengen 2 % (Feststoff bezogen auf atro Holzmaterial) zugegeben (Versuch 2). Nach der Zerfaserung wurden die getrockneten Fasern üblicherweise mit dem UF-Harz in Mengen von 12 % (Festharz bezogen auf Trockenfasern) beleimt, zu Fasermatten geformt und zu mitteldichten Faserplatten heiß gepresst (vgl. Versuch 1). Die so hergestellten Platten wurden anschließend bei 20°C und 65 % rel. Luftfeuchte gelagert, ehe sie auf ihre physikalisch-technologischen Eigenschaften und Emission geprüft wurden.For comparison, pine wood chips were digested at a temperature of 170 ° C, in the fiberization stage under pressure in the refiner condensed tannins were added to the wood chips before digestion in amounts of 2% (solid based on atro wood material) (Experiment 2). After defibering, the dried fibers were usually mixed with the UF resin Glueing amounts of 12% (solid resin based on dry fibers), shaped into fiber mats and hot pressed into medium-density fibreboard (see Experiment 1). The plates thus prepared were then at 20 ° C and 65% rel. Humidity stored before they were tested for their physical-technological properties and emission.

In einem dritten Versuch wurden mitteldichte Faserplatten aus Fasern hergestellt, die unter Zugabe von 1 % Na2SO3 und 0,5 % NaOH (Feststoff bezogen auf atro Holzmaterial) nach dem CTMP-Verfahren hergestellt wurden. Die Aufschlusstemperatur betrug 170°C. Die Herstellung der MDF erfolgte unter den gleichen Bedingungen wie im Fall der TMP-Fasern (vgl. Versuch 1).In a third experiment, medium density fiberboards were made from fibers prepared by adding 1% Na 2 SO 3 and 0.5% NaOH (solid based on dry wood material) according to the CTMP method. The digestion temperature was 170 ° C. The production of the MDF was carried out under the same conditions as in the case of the TMP fibers (see Experiment 1).

In einem vierten Versuch wurden den Kiefernholzhackschnitzeln sowohl 1 % Na2SO3 und 0,5 % NaOH (Feststoff bezogen auf atro Holzmaterial) als auch Quebrachoholztannin in Mengen von 2 % (Feststoff bezogen auf atro Holzmaterial) zugegeben. Die Aufschlusstemperatur lag ebenfalls bei 170°C. Nach der Zerfaserung wurden die getrockneten Fasern zu MDF weiterverarbeitet. Die Herstellung der MDF erfolgte unter den gleichen Bedingungen wie im Falle der TMP-Fasern (Versuch 1).In a fourth experiment, the pine wood chips were added with both 1% Na 2 SO 3 and 0.5% NaOH (solid based on dry wood material) and Quebrachoholztannin in amounts of 2% (solid based on dry wood material). The digestion temperature was also 170 ° C. After defibration, the dried fibers were further processed into MDF. The production of the MDF was carried out under the same conditions as in the case of the TMP fibers (Experiment 1).

Die Ergebnisse sind in den Tabellen 1 bis 3 zusammengefasst.The results are summarized in Tables 1 to 3.

Aus Tabelle 1 wird deutlich, dass die Querzugfestigkeit der aus nach dem CTMP-Verfahren gewonnenen Fasern und unter Einsatz von Tannin im Refiner hergestellten Platten (Versuch 4) wesentlich höher liegt als die der anderweitig hergestellten Platten (Versuche 1 bis 3). Des Weiteren wird ersichtlich, dass durch die kombinierte Anwendung von CTMP und Tannin (Versuch 4) die Dickenquellung (24h) der hergestellten Platten deutlich erniedrigt wird. Ebenfalls die Biegefestigkeit der hergestellten Platten wird durch die kombinierte Anwendung von CTMP und Tannin (Versuch 4) wesentlich erhöht. Mit diesem Verfahren werden sowohl die Festigkeitseigenschaften (Querzugfestigkeit, Biegefestigkeit) der Platten erheblich verbessert als auch ihre Dickenquellung deutlich vermindert. Tabelle 1: Physikalisch-technologische Eigenschaften von nach dem TMP- und CTMP-Verfahren hergestellten mitteldichten Faserplatten, die ohne und unter Zugabe von kondensierten Tanninen hergestellt worden sind Versuch-Nr. 1 2 3 4 Physikalisch-technolgische Eigenschaften Platten aus TMP-Fasern und ohne Tanninzugabe hergestellt Platten aus TMP-Fasern und unter Tanninzugabe hergestellt Platten aus CTMP-Fasern und ohne Tanninzugabe hergestellt Platten aus CTMP-Fasern und unter Tanninzugabe hergestellt Dickenquellung 2 h (%) 2,9 3,0 2,6 2,4 Dickenquellung 24 h (%) 25,8 20,3 22,7 17,4 Querzugfestigkeit (N/mm2) 1,14 1,18 1,30 1,67 Biegefestigkeit (N/mm2) 30,9 34,1 36,5 39,2 From Table 1 it is clear that the transverse tensile strength of the fibers obtained by the CTMP process and plates made using tannin in the refiner (test 4) is substantially higher than those of the plates produced otherwise (tests 1 to 3). Furthermore, it can be seen that the combined use of CTMP and tannin (experiment 4) significantly reduces the thickness swelling (24 h) of the plates produced. Also, the flexural strength of the panels produced is substantially increased by the combined use of CTMP and tannin (Experiment 4). With this method, both the strength properties (Transverse tensile strength, flexural strength) of the plates significantly improved as well as their thickness swelling significantly reduced. <b> Table 1: </ b> Physical-technological properties of TMP and CTMP medium density fiberboards produced without and with the addition of condensed tannins Experiment no. 1 2 3 4 Physico-technological properties Plates made of TMP fibers and without tannin addition Plates made of TMP fibers and added with tannin Plates made of CTMP fibers and without addition of tannin Plates made of CTMP fibers and added with tannin Thickness swelling 2 h (%) 2.9 3.0 2.6 2.4 Thickness swelling 24 h (%) 25.8 20.3 22.7 17.4 Transverse tensile strength (N / mm 2 ) 1.14 1.18 1.30 1.67 Bending strength (N / mm 2 ) 30.9 34.1 36.5 39.2

Wie aus Tabelle 2 hervorgeht, werden durch die kombinierte Anwendung von CTMP und Tannin (Versuch 4) die Emissionen der Platten an flüchtigen organischen Bestandteilen (VOC) wie Hexanal und Pentanal deutlich vermindert. Tabelle 2: VOC-Emissionen (Hexanal, Pentanal) von nach dem TMP- und CTMP-Verfahren hergestellten mitteldichten Faserplatten (MDF), die ohne und unter Zugabe von kondensierten Tanninen hergestellt worden sind. Die VOC-Emissionen wurden nach 5h Lagerung der Platten in der Prüfkammer ermittelt. Versuch-Nr. 1 2 3 4 VOC-Emission Platten aus TMP-Fasern und ohne Tanninzugabe hergestellt Platten aus TMP-Fasern und unter Tanninzugabe hergestellt Platten aus CTMP-Fasern und ohne Tanninzugabe hergestellt Platten aus CTMP-Fasern und unter Tanninzugabe hergestellt Hexanal (µg/m3) 404 604 43 16 Pentanal (µg/m3) 162 113 Nicht nachweisbar Nicht nachweisbar As shown in Table 2, the combined use of CTMP and tannin (Run 4) significantly reduces emissions of volatile organic content (VOC) plates such as hexanal and pentanal. <b> Table 2: </ b> VOC emissions (hexanal, pentanal) of TMP and CTMP medium density fiberboard (MDF) manufactured without and with the addition of condensed tannins. The VOC emissions were determined after 5h storage of the plates in the test chamber. Experiment no. 1 2 3 4 VOC emissions Plates made of TMP fibers and without tannin addition Plates made of TMP fibers and added with tannin Plates made of CTMP fibers and without addition of tannin Plates made of CTMP fibers and added with tannin Hexanal (μg / m 3 ) 404 604 43 16 Pentanal (μg / m 3 ) 162 113 Not detectable Not detectable

Die Zugabe von Tannin bei der Herstellung von Fasern nach dem CTMP-Verfahren (Versuch 4) führt zu einer zusätzlichen deutlichen Verringerung der Formaldehydabgabe (24h) des Faserstoffs (vgl. Tabelle 3). Tabelle 3: Formaldehydabgabe (24h) (mg/1000 g atro Fasern) von nach dem TMP-und CTMP-Verfahren hergestellten Fasern, die ohne und unter Zugabe von kondensierten Tanninen hergestellt worden sind Versuch-Nr. 1 2 3 4 Platten aus TMP-Fasern und ohne Tanninzugabe hergestellt Platten aus TMP-Fasern und unter Tanninzugabe hergestellt Platten aus CTMP-Fasern und ohne Tanninzugabe hergestellt Platten aus CTMP-Fasern und unter Tanninzugabe hergestellt Formaldehydabgabe (24h) (Flaschemethode) mg/1000 g atro Fasern 14,1 10,5 8,6 6,3 The addition of tannin in the production of fibers by the CTMP method (Experiment 4) leads to an additional significant reduction in the formaldehyde release (24h) of the pulp (see Table 3). <b> Table 3: Formaldehyde release (24h) (mg / 1000 g of atro fibers) from TMP and CTMP fibers made without and with the addition of condensed tannins Experiment no. 1 2 3 4 Plates made of TMP fibers and without tannin addition Plates made of TMP fibers and added with tannin Plates made of CTMP fibers and without addition of tannin Plates made of CTMP fibers and added with tannin Formaldehyde release (24h) (bottle method) mg / 1000 g atro fibers 14.1 10.5 8.6 6.3

Als Bindemittel für die Herstellung von mitteldichten Faserplatten können im Sinne der Erfindung sowohl solche, die zu einer feuchtebeständigen Faser-zu-Faser-Bindung führen, als auch solche, die zu Faser-zu-Faser-Bindung mit geringer Feuchtebeständigkeit führen, verwendet werden. Typische Bindemittel für die Herstellung von feuchtebeständigen Verleimungen sind alkalisch härtende Phenolformaldehydharze (PF-Harze), Tanninformaldehydharze (TF-Harze), Melaminharnstoffphenolformaldehydharze (MUPF-Harze) und Klebstoffe auf Basis von PMDI (polymere Diphenylmethandiisocyanate). Zu den Bindemitteln, die zu einer Faser-zu-Faser-Bindung mit geringer Feuchtgebeständigkeit führen, gehören die Harnstoffformaldeydharze (UF-Harze). For the purposes of the invention, binders for the production of medium-density fibreboards can be those which lead to a moisture-resistant fiber-to-fiber bond as well as those which lead to fiber-to-fiber bonding with low moisture resistance. Typical binders for the production of moisture-resistant adhesives are alkaline curing phenol-formaldehyde resins (PF resins), tannin-formaldehyde resins (TF resins), melamine-urea phenol-formaldehyde resins (MUPF resins) and adhesives based on PMDI (polymeric diphenylmethane diisocyanates). Binders that result in low moisture resistance fiber-to-fiber bonding include urea formaldehyde resins (UF resins).

Claims (11)

  1. Method for producing fibre boards, in particular medium-density fibre boards, from lignocelluloses, in which the lignocelluloses are subjected to chemothermohydrolytic digestion and then defibrated in a refiner, provided with a binder, spread to give fibre mats and pressed to give fibre boards, characterized in that the defibration of the lignocelluloses is effected in the presence of condensed tannins added in the refiner, and the binders are supplied to the fibres in the blow-line method and/or in a blender.
  2. Method according to Claim 1, characterized in that the binder used is an aminoplast resin, phenolformaldehyde resin, tannin-formaldehyde resin and/or an adhesive based on diisocyanates.
  3. Method according to claim 1 or 2, characterized in that starch is added as an extender to the binder.
  4. Method according to any of the preceding claims, characterized in that the binder used is a combination of tannin, formaldehyde and starch.
  5. Method according to any one of Claims 1 to 3, characterized in that methacrylate reaction resins are used as binders.
  6. Method according to any of the preceding claims, characterized in that the fibre boards produced are further processed to give moulded parts.
  7. Method according to any of the preceding claims, characterized in that sodium sulphite, sodium bisulphite and/or sodium hydroxide is (are) added to the lignocelluloses prior to digestion.
  8. Method according to Claim 7, characterized in that the amounts of sodium sulphite, sodium bisulphite and/or sodium hydroxide added are between 0.1% and 2% of solid, based on absolutely dry lignocelluloses.
  9. Method according to any of the preceding claims, characterized in that the added tannin is a sulphited or unsulphited tannin.
  10. Method according to any of the preceding claims, characterized in that the boards produced are stored or are stored at elevated temperature.
  11. Method according to any of the preceding claims, characterized in that the boards produced have a density of at least 1000 kg/m3.
EP06742271A 2005-04-26 2006-04-25 Method for producing reduced-emission, low-thickness swell medium density fiber boards and molded fiber parts Not-in-force EP1874513B1 (en)

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DE102005019627A DE102005019627B3 (en) 2005-04-26 2005-04-26 Medium density fiberboards, of digested ligno cellulose refined into fibers, contains a bonding agent giving a low emission of volatile organic compounds
PCT/DE2006/000728 WO2006114089A1 (en) 2005-04-26 2006-04-25 Method for producing reduced-emission, low-thickness swell medium density fiber boards and molded fiber parts

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DE102007054123B4 (en) * 2006-11-15 2012-03-15 Edmone Roffael Process for the production of fiberboard with reduced formaldehyde emission, high moisture resistance and hydrolysis resistance of the gluing
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DE102009042361B4 (en) * 2009-09-23 2012-12-20 Siempelkamp Maschinen- Und Anlagenbau Gmbh & Co. Kg Process for the production of cardboard-like fiberboard from wood fibers
DE102015103511B4 (en) 2015-03-10 2018-09-20 Fritz Egger Gmbh & Co. Og Process for producing a wood chipboard and aminoplast curing agents used therein
IT202000019033A1 (en) * 2020-08-03 2022-02-03 Davide Bertinazzo METHOD FOR OBTAINING A PRECURSOR OF A WOOD-INORGA HYBRID MATERIAL AND METHOD FOR OBTAINING A WOOD-INORGA HYBRID MATERIAL
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DE4327774A1 (en) * 1993-08-18 1995-02-23 Fraunhofer Ges Forschung Process for the production of medium density fibreboard (MDF)
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WO1998037147A2 (en) * 1997-02-20 1998-08-27 Kronospan Gmbh Adhesive composition and its use
DE10054163A1 (en) * 2000-11-02 2002-06-06 Wacker Polymer Systems Gmbh Process for the production of pressed wood panels
DE10124638A1 (en) * 2001-05-18 2002-11-21 Edmone Roffael Preparation of tannin-bonded lignocellulose boards from used wood chips and fiberboard, useful in the production of reconstituted wood chipboard and fiberboard
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