EP2727691B1 - Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material - Google Patents

Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material Download PDF

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Publication number
EP2727691B1
EP2727691B1 EP12191376.8A EP12191376A EP2727691B1 EP 2727691 B1 EP2727691 B1 EP 2727691B1 EP 12191376 A EP12191376 A EP 12191376A EP 2727691 B1 EP2727691 B1 EP 2727691B1
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EP
European Patent Office
Prior art keywords
wood
activated carbon
additive
process according
adhesive
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.)
Revoked
Application number
EP12191376.8A
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German (de)
French (fr)
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EP2727691A1 (en
Inventor
Joachim Hasch
Julia BOROWKA
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.)
Swiss Krono Tec AG
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Kronotec AG
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Application filed by Kronotec AG filed Critical Kronotec AG
Priority to HUE12191376A priority Critical patent/HUE024531T2/en
Priority to SI201230151T priority patent/SI2727691T1/en
Priority to ES12191376.8T priority patent/ES2529356T3/en
Priority to PL12191376T priority patent/PL2727691T3/en
Priority to PT12191376T priority patent/PT2727691E/en
Priority to EP12191376.8A priority patent/EP2727691B1/en
Priority to PL13792612.7T priority patent/PL2917008T3/en
Priority to ES13792612T priority patent/ES2954071T3/en
Priority to CA2886475A priority patent/CA2886475C/en
Priority to RU2015121571A priority patent/RU2661361C2/en
Priority to UAA201505465A priority patent/UA117817C2/en
Priority to US14/439,768 priority patent/US9895824B2/en
Priority to JP2015540164A priority patent/JP6293769B2/en
Priority to CN201380058064.0A priority patent/CN104781055A/en
Priority to BR112015009351A priority patent/BR112015009351A2/en
Priority to EP13792612.7A priority patent/EP2917008B1/en
Priority to HUE13792612A priority patent/HUE064134T2/en
Priority to PCT/EP2013/073090 priority patent/WO2014072304A1/en
Publication of EP2727691A1 publication Critical patent/EP2727691A1/en
Publication of EP2727691B1 publication Critical patent/EP2727691B1/en
Application granted granted Critical
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard

Definitions

  • the present application relates to a method according to claim 1 for the production of wood materials from lignocellulose-containing crushing products, in particular for the production of fiberboard or OSB boards, said wood materials for reducing or reducing the emission of volatile organic compounds (VOC) and optionally very volatile organic Compounds (VVOC), in particular terpenes and acids, the preparation of which are treated with at least one additive.
  • VOC volatile organic compounds
  • VVOC very volatile organic Compounds
  • the treatment is carried out with an additive, activated carbon.
  • the application is directed to obtainable by the process according to the invention wood materials according to claim 11 with reduced emission of volatile organic compounds, especially terpenes and acids but also aldehydes.
  • VOCs volatile organic compounds
  • VVOCs very volatile organic compounds
  • HWS wood-based materials
  • VOCs include saturated and non-volatile organic compounds unsaturated aldehydes all volatile organic substances whose retention time in the gas chromatograph between C6 (hexane) and C16 (hexadecane) is.
  • VOCs are not a homogeneous class of substances but a smorgasbord of compounds. These include, but are not limited to, organic acids, saturated and unsaturated aldehydes, alcohols, terpenes, aliphatic and aromatic hydrocarbons and many more.
  • VVOC very volatile organic compounds
  • these VVOC also occur in the production but also in the use of wood-based materials.
  • these compounds in the curing of adhesives on the other hand, these compounds may occur by reaction of compounds present in the wood material.
  • the emission of VOC is based essentially on a release of derived from the wood material compounds.
  • the release of the volatile organic compounds and very volatile organic compounds depends, inter alia, on the nature and condition of the lignocelluloses, such as the type of wood, the storage period, the storage conditions of the wood or of the comminution products of the wood, and can be in different chemical compositions and quantities occurrence.
  • the VOCs originate mainly from extractives of the Lignocelluloses, eg of wood or transformation products. Prominent representatives of these are substances such as ⁇ -pinene, ⁇ -pinene, ⁇ -3-carene. Above all, in coniferous trees, which are used as starting wood for wood-based panels, these components can be found again.
  • aldehydes such as pentanal and hexanal.
  • softwoods which mainly produce chipboard, medium-density fiberboard (MDF) or OSB boards, contain large quantities of resins and fats, which contribute to the formation of volatile organic terpene compounds and aldehydes.
  • these substances are produced by degradation of the main constituents of the wood, such as lignin, cellulose and hemicellulose.
  • volatile organic compounds and very volatile organic compounds can also arise when using certain adhesives for the production of wood-based materials.
  • the VOC emission from wood-based materials is essentially due to a wood-induced release rather than by the adhesive used.
  • the conversion of components of the wood materials e.g. by fragmentation of the resins and fats, a permanent secondary or tertiary emission of said compounds takes place.
  • OSB boards are also used in the construction sector. Since OSB panels usually have no emission-reducing coating and is installed in large quantities, in particular as the area of the panel, based on the total cubic meter number of the room or building, high releases of VOCs can occur.
  • the previously used additives can partially reduce the reactivity of the adhesives used.
  • mechanical parameters of the wood-based panels to be produced are influenced and usually worsen.
  • the adhesive is added in larger quantities in order to achieve the required and / or desired mechanical parameters.
  • the present invention is therefore based on the object of providing processes for the production of wood-based materials from lignocellulose particles, in particular processes for the production of chipboard, fiberboard or OSB boards but also plywood boards, which show a reduction or reduction of emissions of volatile organic compounds (VOC) and very volatile organic compounds (VVOC) even over a longer period.
  • VOC volatile organic compounds
  • VVOC very volatile organic compounds
  • the additives used in this case should not show any toxic properties and not adversely affect the production process itself, in particular not reduce the reactivity of the adhesives used.
  • the additives should reduce as much as possible the emission of the heterogeneous class of the volatile organic compounds as well as the very volatile organic compounds or a formation of these from constituents of the wood-based materials.
  • An essential aspect of the present invention is the use of activated carbon as an additive.
  • the expression “reduction of emission” or “reduction of emission”, which are used interchangeably, means that the total amount of a total volatile organic compound (TVOC) is lower compared with a wood material without additive according to the invention.
  • the term "avoidance of emission” includes a percentage reduction or decrease in emission compared to the control up to one that is below the measurement limit.
  • lignocellulose-containing comminution products and “lignocellulose particles” are used interchangeably.
  • Another advantage of the reduction or reduction of the emission of TVOC is that, for example, such substances are reduced in their emission, which also contribute to an unpleasant odor of wood materials, such as acetic acid, which is malodorous, but also the typical aldehyde particular formaldehyde Smell of these plates.
  • Activated carbon is understood to mean carbon structures of the smallest graphitic crystals and amorphous carbon with a porous structure and internal surfaces (BET surface area), usually in a range between 300 and 2000 m 2 / g.
  • Activated carbon can be in powder form, as a grain but also in other forms.
  • the activated carbon is preferably one with a density between 0.2 and 0.6 g / cm 3 , the preferred pore size of the activated carbon being in the range of ⁇ 1 nm up to 50 nm.
  • Activated carbon can be produced from vegetable animal or mineral raw materials. Accordingly, the activated carbon of stone, wood, lignite but also derived from vegetable ingredients, such as coconut shells, fruit seeds, etc., as well as from animal coals.
  • Activated carbon has long been known as an adsorbent, e.g. It is used to remove unwanted or harmful colors and odors from gases, vapors and liquids etc. Furthermore, they are useful in chemical cleaning processes as well as for the adsorption of e.g. Toxic substances known in the pharmaceutical field.
  • Activated carbon is known as a means of adsorbing liquids or gases for a short period of time, but not as a means of permanent use.
  • the activated carbon can be introduced in solid form as a powder preferably in a particle diameter of less than 1 mm and / or as granules with a particle size of less than 4 mm to the lignocellulose-containing comminution products.
  • the additive is, for example, in an amount in a range of 0.1 to 20 % By weight applied to atro lignocellulose.
  • a porous carbon in the form of activated carbon has several advantages. From an economic point of view, activated carbon has high availability and a low price. In the manufacturing process itself disadvantages of previous additives can be overcome. Thus, a dosage can be carried out as a solid, whereby the moisture content of the starting materials and / or the wood-based panels is not increased. An additional drying with corresponding additional costs is therefore not necessary. Furthermore, the porous carbon in the form of activated carbon has no reactivity with the adhesive used, so that the reactivity and processability of this e.g. whose curing speed is not deteriorated. As a result, it is not necessary to add larger amounts of adhesive to compensate for deterioration in the reactivity of these by the addition of additives.
  • the total emission of VOCs, if any, including VVOCs from the wood-based materials is reduced, this reduction not being limited to a class of substances, but reducing both the emission of aldehydes and of terpenes and acids.
  • the TVOC value and the R value of the wood-based materials produced, especially in the form of wood-based panels, such as OSB boards significantly reduced.
  • the additive can be added at different times in the production process.
  • the additive can be added either in solid form but optionally also in the form of a suspension or dispersion.
  • the activated carbon as powder granules in added to solid form.
  • the addition of the additive can be carried out in all areas of the wood-based materials to be produced.
  • the additive may be e.g. only in some areas of this present. In this case, it is possible to meter the additive into the cover layer and / or middle layer.
  • the additive according to the invention can be present in different proportions by weight in the topcoat or middlecoat.
  • one of the layers has a content of 5% by weight, while the other layer has 10% of the additive.
  • the proportions in both layers can be the same.
  • Porous carbon in the form of activated carbon can, in particular in powder form before the dryer and / or after the dryer in the chute of lignocellulosic crushing products for the control and / or before and / or after the gluing of these and / or in the gluing with the corresponding adhesive, such as a UF, MUF, PMDI adhesive.
  • the corresponding adhesive such as a UF, MUF, PMDI adhesive.
  • the dosage is preferably from 0.1 to 20% by weight on ator lignocellulose.
  • the adhesives commonly used can be used. These adhesives include as adhesives phenol-formaldehyde (PF) adhesives, isocyanate-based adhesives, urea-formaldehyde (UF) adhesives, melamine-urea-formaldehyde (MUF) adhesives, melamine-urea adhesives Phenol-formaldehyde (MUPF) adhesives, tannin-formaldehyde (TF) adhesives, polyurethane (PU) adhesives, or mixtures thereof.
  • PF phenol-formaldehyde
  • UF urea-formaldehyde
  • MAF melamine-urea-formaldehyde
  • MUPF melamine-urea adhesives
  • Phenol-formaldehyde (MUPF) adhesives tannin-formaldehyde (TF) adhesives
  • PU polyurethane
  • the adhesive is a non-formaldehyde-containing adhesive, such as an isocyanate-based adhesive such as PMDI.
  • Lignocelluloses are understood here to be lignocellulose-containing materials, such as wood.
  • the resulting comminution products of lignocelluloses include in particular wood strands, wood chips, wood fibers, but also wood veneers.
  • the lignocelluloses such as the wood-based materials and the comminuted products thereof, may be both conifers and hardwoods. Even mixtures of these two types of wood are possible.
  • the wood chips, strands or wood fibers come from conifers.
  • the wood materials that can be produced by the production method according to the invention, in particular wood-based panels, can be produced according to a known method.
  • the process may additionally be supplemented by other processes known to those skilled in the art for reducing the emission of volatile organic compounds, very volatile organic compounds.
  • activated carbon as an additive in the production of wood materials from lignocellulose in particular for reducing or reducing the emission of VOC, TVOC and / or VVOC is described.
  • the additive is thereby added during the manufacturing process of the lignocellulose e.g. in the form of lignocellulose-containing comminution particles (lignocellulose-containing particles) added or applied.
  • the additive can take place at least in the cover layer or the middle layer or in both layers of, for example, OSB boards.
  • the additive may be introduced or applied in an amount of from 0.1% by weight to 20% by weight of solids, based on atroscopic lignocellulose.
  • wood materials are provided, obtainable by the method according to the invention.
  • These wood-based materials are preferably a fiberboard, in particular lightweight and superlight MDF board, an OSB board.
  • the wood-based materials according to the invention are distinguished by the fact that they show a reduced or reduced emission of TVOC over a long period of time, and this in particular also includes a reduction or reduction of the terpenes and acids. Furthermore, it was found that the mechanical properties of the wood-based materials produced are not or only negligibly affected, such as. shown in Table 3 below.
  • plate 1 with 100% PMDI gluing and a thickness of 12 mm was made on the laboratory press. Subsequently, three test panels were prepared using activated carbon. In this case, plate 2 contains 5% on atro wood activated carbon powder in the top layer. Plate 3 contains 5% of atro-wood activated carbon powder in the middle layer, and plate 4 has 10% of the middle layer added to atro-wood activated carbon powder.
  • Table 1 gives an overview of the test panels produced. These were then examined for their emission behavior in a test chamber and according to the AgBB scheme over a period of 28 Days.
  • Table 1 plate thickness gluing dosage 1 12 100% PMDI "0" standard plate 2 12 100% PMDI OSB board with 5% AK in top layer 3 12 100% PMDI OSB board with 5% AK in middle layer 4 12 100% PMDI OSB board with 10% AK in middle layer
  • the emission measurements were carried out in test chambers made of glass desiccators with a volume of 23.5 liters. The tests were based on ISO 16 000 part 9 (2008). Standard conditions were therefore a temperature of 23 ° C, a relative humidity of 50% and an air velocity near the sample surface of 0.1 to 0.3 m s-2.
  • the standard load was about 720 cm 2 emitting area, ie the loading level of the chamber was 3.1 m2 m-3;
  • the air exchange with high-purity synthetic air in the test chamber was 3.1 times per hour. This resulted in a standard area-specific air exchange rate of 1 m 3 / (m 2 * h).
  • the minimum test duration was 28 days with air sampling occurring one and three days after sample introduction and weekly thereafter.
  • the sampling was carried out according to ISO 16 000 part 6 (2004) by means of a pump and tubes filled with the adsorbent Tenax TA®.
  • the respective sample volume was 0.5 to a maximum of 4 liters of test chamber air.
  • Tenax TA-filled tubes were thermally cleaned prior to each air sampling and loaded with 200 ng of deuterated toluene as an internal standard.
  • the sampled Tenax TA was thermally desorbed (TD) and the substances transferred via a cryofocusing unit to a gas chromatograph (GC) coupled to a mass spectrometer (MS).
  • GC gas chromatograph
  • MS mass spectrometer
  • VOC emission measurements show the strongest effect of reduction in the case of metering of the activated carbon powder in the middle layer.
  • a dosage of 5% on atro wood activated carbon leads to a strong reduction of VOC emission.
  • the TVOC value is reduced from 999.1 ⁇ g / m 3 to 265.6 ⁇ g / m 3 (plate 3).
  • the R value is greatly reduced in the case of the test plate 3 from 3.3 to 1 compared to the reference plate 1.
  • Activated carbon has a high adsorption capacity due to the high internal surface.
  • the high open-pore structure of the activated carbon has the ability to store large quantities of gas molecules and store them.
  • Activated carbon is one of the hydrophobic adsorbents and is particularly suitable for the adsorption of less polar VOCs, such as terpenes.
  • VOCs such as terpenes.
  • chemisorption also plays an important role here, whereby the VOC molecules are able to chemically interact with the surface molecules of the activated carbon, leading to a true formation of a surface compound.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Description

Die vorliegende Anmeldung betrifft ein Verfahren gemäß Anspruch 1 zur Herstellung von Holzwerkstoffen aus Lignocellulose-haltigen Zerkleinerungsprodukten, insbesondere zur Herstellung von Faserplatten oder OSB-Platten, wobei diese Holzwerkstoffe zur Verringerung oder Verminderung der Emission von flüchtigen organischen Verbindungen (VOC) und gegebenenfalls sehr flüchtigen organischen Verbindungen (VVOC), insbesondere Terpene und Säuren, der Herstellung mit mindestens einem Additiv behandelt werden. Erfindungsgemäß erfolgt dabei die Behandlung mit einem Additiv, Aktivkohle. Schließlich richtet sich die Anmeldung auf mit dem erfindungsgemäßen Verfahren erhältliche Holzwerkstoffe gemäß Anspruch 11 mit verringerter Emission von flüchtigen organischen Verbindungen, insbesondere Terpenen und Säuren aber auch Aldehyden.The present application relates to a method according to claim 1 for the production of wood materials from lignocellulose-containing crushing products, in particular for the production of fiberboard or OSB boards, said wood materials for reducing or reducing the emission of volatile organic compounds (VOC) and optionally very volatile organic Compounds (VVOC), in particular terpenes and acids, the preparation of which are treated with at least one additive. According to the invention, the treatment is carried out with an additive, activated carbon. Finally, the application is directed to obtainable by the process according to the invention wood materials according to claim 11 with reduced emission of volatile organic compounds, especially terpenes and acids but also aldehydes.

Stand der TechnikState of the art

Lignocellulose oder lignocellulosehaltige Materialien, wie Holz und Holzzerkleinerungsprodukte und daraus hergestellte Holzwerkstoffe, wie Holzwerkstoff platten, enthalten unter anderem flüchtige organische Verbindungen (VOC) und sehr flüchtige organische Verbindungen (VVOC). Die Emission dieser VOC und VVOC, auch als Gesamtmenge an flüchtigen Verbindungen bezeichnet (TVOC), aus den Holzwerkstoffen (HWS) stellt unter dem Aspekt der zunehmenden Nutzung von holzartigen Produkten in Innenräumen ein gravierendes Problem dar. Zu den flüchtigen organischen Verbindungen zählen neben gesättigten und ungesättigten Aldehyden alle flüchtigen organischen Stoffe, deren Retentionszeit im Gaschromatograph zwischen C6 (Hexan) und C16 (Hexadecan) liegt. Die VOC sind keine homogene Substanzklasse, sondern ein Sammelsurium von Verbindungen. Unter anderem fallen hierunter organische Säuren, gesättigte und ungesättigte Aldehyde, Alkohole, Terpene, Aliphate und aromatische Kohlenwasserstoffe und vieles mehr. Daneben werden die sehr flüchtigen organischen Verbindungen (VVOC), unter denen z.B. Formaldehyd oder Ameisensäure fallen, angesiedelt. Diese VVOC treten ebenfalls bei der Herstellung aber auch in der Verwendung von Holzwerkstoffen auf. Einerseits können diese Verbindungen bei der Aushärtung aus Klebstoffen, andererseits können diese Verbindungen durch Umsetzung von im Holzwerkstoff vorliegenden Verbindungen auftreten. Insbesondere die Emission der VOC beruht im Wesentlichen auf eine Freisetzung von aus dem Holzwerkstoff stammenden Verbindungen.Lignocellulosic or lignocellulosic materials, such as wood and wood chippings and wood derived therefrom, such as wood-based material plates contain, among other things, volatile organic compounds (VOCs) and very volatile organic compounds (VVOCs). The emission of these VOCs and VVOCs, also referred to as Total Volatile Compounds (TVOCs), from wood-based materials (HWS) poses a serious problem from the point of view of the increasing use of wood-like products indoors. VOCs include saturated and non-volatile organic compounds unsaturated aldehydes all volatile organic substances whose retention time in the gas chromatograph between C6 (hexane) and C16 (hexadecane) is. VOCs are not a homogeneous class of substances but a smorgasbord of compounds. These include, but are not limited to, organic acids, saturated and unsaturated aldehydes, alcohols, terpenes, aliphatic and aromatic hydrocarbons and many more. In addition, the very volatile organic compounds (VVOC), which include, for example, formaldehyde or formic acid, settled. These VVOC also occur in the production but also in the use of wood-based materials. On the one hand, these compounds in the curing of adhesives, on the other hand, these compounds may occur by reaction of compounds present in the wood material. In particular, the emission of VOC is based essentially on a release of derived from the wood material compounds.

Die Emission dieser flüchtigen und sehr flüchtigen Holzinhaltsstoffe oder Bestandteile der Klebstoffe aus Holzprodukten einer dieser Holzwerkstoffplatten stellt aufgrund verschärfter Grenzwerte bzw. einer größeren Sensibilisierung der Endverbraucher mehr und mehr ein Problem dar.The emission of these volatile and very volatile wood constituents or components of the adhesives from wood products of one of these wood-based panels is becoming more and more of a problem due to stricter limits or greater sensitization of the end users.

Die Freisetzung der flüchtigen organischen Verbindungen und sehr flüchtigen organischen Verbindungen hängt unter anderem von der Art und dem Zustand der Lignocellulosen ab, wie der Holzart, der Lagerungsdauer, den Lagerungsbedingungen des Holzes bzw. der Zerkleinerungsprodukte des Holzes, und kann in unterschiedlichen chemischen Zusammensetzungen und Mengen vorkommen. Die VOC entstammen dabei im Wesentlichen aus Extraktstoffen der Lignocellulosen, z.B. des Holzes oder Umwandlungsprodukten. Prominente Vertreter hiervon sind Stoffe wie α-Pinen, β-Pinen, δ-3-Caren. Vor allen in Nadelbäumen, die als Ausgangsholz für Holzwerkstoffplatten verwendet werden, finden sich diese Bestandteile wieder. Umwandlungsprodukte, die z.B. während der Lagerung und der Bearbeitung des Holzes und der Zerkleinerungsprodukte auftreten, sind Aldehyde, wie Pentanal und Hexanal. Vor allem Nadelhölzer, aus denen vorwiegend Spanplatten, mitteldichte Faserplatten (MDF) oder OSB-Platten hergestellt werden, enthalten große Mengen Harze und Fette, die zur Bildung von flüchtigen organischen Terpen-Verbindungen und Aldehyden beitragen. Diese Stoffe entstehen dabei unter anderem durch Abbau der Hauptbestandteile des Holzes, wie Lignin, Cellulose und Hemicellulose. Flüchtige organische Verbindungen und sehr flüchtige organische Verbindungen können aber auch bei der Verwendung bestimmter Klebstoffe zur Herstellung der Holzwerkstoffe entstehen. Üblicherweise findet dabei ein Oxidationsprozess der Holzinhaltsstoffe, wie den Fettsäuren, statt, die dann zu den Sekundär- bzw. Tertiäremission von Aldehyden, wie Pentanal, oder höheren Carbonsäuren aber auch Terpenen führen.The release of the volatile organic compounds and very volatile organic compounds depends, inter alia, on the nature and condition of the lignocelluloses, such as the type of wood, the storage period, the storage conditions of the wood or of the comminution products of the wood, and can be in different chemical compositions and quantities occurrence. The VOCs originate mainly from extractives of the Lignocelluloses, eg of wood or transformation products. Prominent representatives of these are substances such as α-pinene, β-pinene, δ-3-carene. Above all, in coniferous trees, which are used as starting wood for wood-based panels, these components can be found again. Conversion products that occur, for example, during storage and processing of the wood and the crushed products are aldehydes such as pentanal and hexanal. Above all, softwoods, which mainly produce chipboard, medium-density fiberboard (MDF) or OSB boards, contain large quantities of resins and fats, which contribute to the formation of volatile organic terpene compounds and aldehydes. Among other things, these substances are produced by degradation of the main constituents of the wood, such as lignin, cellulose and hemicellulose. However, volatile organic compounds and very volatile organic compounds can also arise when using certain adhesives for the production of wood-based materials. Usually there is an oxidation process of the wood ingredients, such as the fatty acids, instead, which then lead to the secondary or tertiary emission of aldehydes, such as pentanal, or higher carboxylic acids but also terpenes.

D.h., die VOC Emission aus Holzwerkstoffen beruht im Wesentlichen auf eine holzbedingte Freisetzung und nicht eine durch den verwendeten Klebstoff. Insbesondere die in den hergestellten Holzwerkstoffen andauernde Umwandlung von Bestandteilen der Holzwerkstoffe, z.B. durch Fragmentierung der Harze und Fette, findet eine ständige Sekundär- bzw. Tertiäremission der genannten Verbindungen statt. Heutzutage werden OSB-Platten auch im konstruktiven Bereich eingesetzt. Da OSB-Platten üblicherweise keine emissionsmindernde Beschichtung aufweisen und in großen Mengen, insbesondere als Fläche der Platte, bezogen auf die Gesamtkubikmeterzahl des Raumes oder des Gebäudes verbaut wird, können hohe Freisetzungen von VOC auftreten.That is, the VOC emission from wood-based materials is essentially due to a wood-induced release rather than by the adhesive used. In particular, the conversion of components of the wood materials, e.g. by fragmentation of the resins and fats, a permanent secondary or tertiary emission of said compounds takes place. Nowadays, OSB boards are also used in the construction sector. Since OSB panels usually have no emission-reducing coating and is installed in large quantities, in particular as the area of the panel, based on the total cubic meter number of the room or building, high releases of VOCs can occur.

Auch bei dem Einsatz von leichten und superleichten MDF z.B. zur Wärmedämmung können ähnliche Probleme mit der Emission von VOC und gegebenenfalls VVOC beobachtet werden. Auch hier treten Emission von Sekundär- und Tertiärstoffen auf.Even with the use of lightweight and super-light MDF, eg for thermal insulation, similar problems with the emission of VOC and possibly VVOC can be observed. Again, emissions from secondary and tertiary substances.

Es wurden bereits vielfältige Ansätze unternommen, die Probleme der Emission von flüchtigen organischen Verbindungen und sehr flüchtigen organischen Verbindungen zu begrenzen. Die Zugabe von verschiedensten Additiven wird beschrieben. In der EP 1 852 231 wird die Verwendung von verschiedenen Additiven vorgeschlagen. Z.B. wird dort die Verwendung von Maleinsäureanhydrid oder ähnlichen Verbindungen beschrieben, um die Emission von Formaldehyd zu verringern. Aus der WO 2006/032267 sind Verfahren zur Reduktion von ungesättigten Aldehyden und fettsäurehaltigen Hölzern bekannt. Dabei wird der im Holz enthaltene Fettsäureester gespalten, inhibiert oder oxidiert. Es wird dort vorgeschlagen, Antioxidantien, alkalische Verbindungen oder Oxidationsmittel als Additiv zuzusetzen. Dokument JP 2003 080509 offenbart die Verwendung von Kohle um die Emission von flüchtigen organischen Verbindung zu begrenzen. Ein Nachteil der bisher beschriebenen Additive ist allerdings, dass häufig nur eine bestimmte Substanzklasse in ihrer Emission verringert wird, wie z.B. die Aldehyde. Dagegen sind Additive, die die Gesamtemission von flüchtigen organischen Verbindungen und gegebenenfalls der sehr flüchtigen organischen Verbindungen kaum bekannt.Many approaches have been taken to limit the problems of volatile organic compounds and volatile organic compounds. The addition of various additives is described. In the EP 1 852 231 the use of various additives is proposed. For example, it describes the use of maleic anhydride or similar compounds to reduce the emission of formaldehyde. From the WO 2006/032267 For example, methods of reducing unsaturated aldehydes and fatty acid containing woods are known. The fatty acid ester contained in the wood is split, inhibited or oxidized. It is proposed there to add antioxidants, alkaline compounds or oxidizing agents as an additive. document JP 2003 080509 discloses the use of coal to limit the emission of volatile organic compound. A disadvantage of the additives described so far, however, is that frequently only a certain substance class is reduced in its emission, such as the aldehydes. In contrast, additives which are scarcely aware of the total emission of volatile organic compounds and optionally of very volatile organic compounds.

Ein weiteres Problem bei den bisher beschriebenen Additiven stellt die notwendige Zugabe dieser als wässrige Lösung dar, wodurch die Feuchte innerhalb des Produktionsprozesses erhöht wird. Zusätzliche Feuchte muss allerdings durch einen aufwändigen Trocknungsprozess nachfolgend wieder entzogen werden. Weiterhin führt eine Zudosierung von additiven Lösungen vor dem Trocknungsvorgang oft zu erhöhter Verschmutzung der Trocknungseinrichtung. Dadurch ergibt sich ein erhöhter Wartungsaufwand. Schließlich wirken viele der beschriebenen Additive korrosiv auf Maschinen und Anlagenteile, da es sich häufig um anorganische oder organische Verbindungen handelt, die als Salze in Lösungen hinzugefügt werden und entsprechend korrosiv auf Maschinen und andere Anlagenteile wirken können.Another problem with the additives described so far is the necessary addition of this as an aqueous solution, whereby the moisture is increased within the production process. However, additional moisture must subsequently be removed again through a complex drying process. Furthermore, a metered addition of additive solutions before the drying process often leads to increased contamination of the drying device. This results in an increased maintenance. Finally, many of the additives described have a corrosive effect on machinery and plant components, since they are often inorganic or organic compounds that can be added as salts in solutions and corrosively affect machines and other equipment.

Andere Nachteile der bekannten chemischen Additive sind die meist hohen Kosten hierfür. Weiterhin können gesundheitsschädigende Effekte durch eineOther disadvantages of the known chemical additives are the usually high costs for this. Furthermore, harmful effects can be caused by a

Emission dieser bzw. von Reaktionsprodukten dieser mit Inhaltsstoffen der weiteren Bestandteile der Holzwerkstoffplatten im Herstellungsprozess, insbesondere im Pressprozess unter Wärmebehandlung, oder im späteren Gebrauch auftreten.Emission of this or of reaction products thereof with ingredients of the other constituents of the wood-based panels in the manufacturing process, in particular in the pressing process under heat treatment, or occur in later use.

Als besonders nachteilig zeigte sich, dass die bisher eingesetzten Additive teilweise die Reaktivität der verwendeten Klebstoffe mindern können. Dadurch werden mechanische Parameter der herzustellenden Holzwerkstoffplatten beeinflusst und verschlechtern sich üblicherweise. Zur Kompensation dieser nachteiligen Effekte durch Zugabe der Additive wird der Klebstoff in größeren Mengen zugegeben, um die geforderten und/oder gewünschten mechanischen Parameter zu erreichen.It was found to be particularly disadvantageous that the previously used additives can partially reduce the reactivity of the adhesives used. As a result, mechanical parameters of the wood-based panels to be produced are influenced and usually worsen. To compensate for these adverse effects by adding the additives, the adhesive is added in larger quantities in order to achieve the required and / or desired mechanical parameters.

Andererseits werden durch normative Vorgaben und durch die Gesetzgebung aber auch durch die Anforderungen der Verbraucher die Emissionsgrenzen immer weiter gesenkt. Der Bedarf nach ökologisch hochwertigen Holzwerkstoffen mit geringen VOC-Emissionen nimmt ständig zu und es besteht entsprechend ein Bedarf Additive bereitzustellen, die die Emission von VOC und gegebenenfalls VVOC, also die Gesamtemission aus den Holzwerkstoffen (TVOC) senkt.On the other hand, normative specifications and the legislation as well as the requirements of the consumer reduce emission limits. The demand for ecologically high-quality wood materials with low VOC emissions is constantly increasing and there is accordingly a need to provide additives which reduce the emission of VOC and possibly VVOC, ie the total emission from wood-based materials (TVOC).

Hierbei ist es insbesondere wesentlich, dass auch bei längerer Nutzung, die gewünschte Reduktion an TVOC, wie den VOC und gegebenenfalls VVOC, aus den Holzwerkstoffen möglich ist. Daher müssen neue Additive nicht nur die unmittelbare Emission von VOC bei dem Herstellungsprozess senken, sondern insbesondere auch die Emission von VOC aber auch VVOC, insbesondere von Terpenen und Säuren aber auch Verbindungen, die als Abbauprodukte von Fettsäuren aus den Holzwerkstoffen als Sekundär- oder Tertiäremission freigesetzt werden, verringern.In this case, it is particularly important that even with prolonged use, the desired reduction in TVOC, such as the VOC and optionally VVOC, from the wood materials is possible. Therefore, new additives must not only reduce the direct emission of VOCs in the manufacturing process, but in particular the emission of VOC but also VVOC, in particular of terpenes and acids but also compounds released as degradation products of fatty acids from the wood materials as secondary or tertiary emission will decrease.

Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, Verfahren zur Herstellung von Holzwerkstoffen aus Lignocellulosepartikeln bereitzustellen, insbesondere Verfahren zur Herstellung von Spanplatten, Faserplatten oder OSB-Platten aber auch Sperrholzplatten, wobei diese eine Verringerung bzw. Minderung von Emissionen von flüchtigen organischen Verbindungen (VOC) und sehr flüchtigen organischen Verbindungen (VVOC) auch über einen längeren Zeitraum aufzeigen. Das heißt, die Emission der VOC aber auch der VVOC soll sowohl bei der Herstellung als auch beim späteren Gebrauch deutlich heruntergesetzt sein. Die dabei eingesetzten Additive selbst sollen keine toxischen Eigenschaften aufzeigen und den Herstellungsprozess selbst nicht negativ beeinflussen, insbesondere nicht die Reaktivität der verwendeten Klebstoffe verringern. Andererseits sollen die Additive möglichst umfangreich die Emission der heterogenen Klasse der flüchtigen organischen Verbindungen wie auch der sehr flüchtigen organischen Verbindungen bzw. eine Bildung dieser aus Bestandteilen der Holzwerkstoffe verringern.The present invention is therefore based on the object of providing processes for the production of wood-based materials from lignocellulose particles, in particular processes for the production of chipboard, fiberboard or OSB boards but also plywood boards, which show a reduction or reduction of emissions of volatile organic compounds (VOC) and very volatile organic compounds (VVOC) even over a longer period. This means that the emission of the VOC as well as the VVOC should be significantly reduced both during production and during later use. The additives used in this case should not show any toxic properties and not adversely affect the production process itself, in particular not reduce the reactivity of the adhesives used. On the other hand, the additives should reduce as much as possible the emission of the heterogeneous class of the volatile organic compounds as well as the very volatile organic compounds or a formation of these from constituents of the wood-based materials.

Beschreibung der ErfindungDescription of the invention

Die Aufgabe der vorliegenden Erfindung wird durch ein Verfahren mit den Merkmalen des Anspruchs 1 sowie durch einen Holzwerkstoff mit den Merkmalen des Anspruchs 11 gelöst. Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung sind in den Unteransprüchen aufgeführt.The object of the present invention is achieved by a method having the features of claim 1 and by a wood-based material having the features of claim 11. Advantageous embodiments and further developments of the invention are listed in the subclaims.

Ein wesentlicher Aspekt der vorliegenden Erfindung ist die Verwendung von Aktivkohle als Additiv.An essential aspect of the present invention is the use of activated carbon as an additive.

Das heißt in einem ersten Aspekt richtet sich die vorliegende Anmeldung auf ein Verfahren zur Herstellung von Holzwerkstoffen aus Lignocellulose insbesondere zur Herstellung von Faserplatten oder OSB-Platten, umfassend die Schritte:

  1. a) Bereitstellen von lignocellulosehaltigen Zerkleinerungsprodukten
  2. b) Einbringen eines Additivs zu den lignocellulosehaltigen Zerkleinerungsprodukten, wobei das Additiv Aktivkohle ist;
  3. c) Verpressen der mit dem Additiv versetzten lignocellulosehaltigen Zerkleinerungsprodukten mit Klebstoff unter Wärmebehandlung zur Herstellung des Holzwerkstoffes; dadurch gekennzeichnet, dass durch Zusatz der Additive die Emission von flüchtigen organischen Verbindungen (VOC), insbesondere Terpene und Säuren, verringert werden.
That is, in a first aspect, the present application is directed to a process for producing lignocellulosic wood materials, in particular for producing fiberboard or OSB boards, comprising the steps:
  1. a) providing lignocellulosic crushing products
  2. b) introducing an additive to the lignocellulose-containing comminution products, wherein the additive is activated carbon;
  3. c) pressing the lignocellulose-containing comminution products mixed with the additive with adhesive under heat treatment to produce the wood-based material; characterized in that by the addition of the additives, the emission of volatile organic compounds (VOC), in particular terpenes and acids are reduced.

Es zeigt sich nun überraschend, dass durch Einsatz von Aktivkohle, die Gesamtmenge an VOC und den VVOC, die durch die Holzwerkstoffe emittiert werden, gesenkt werden kann. Diese Reduzierung beinhaltet nicht nur eine der Aldehyde sondern insbesondere auch der Terpene und der Säuren. Eine solche Reduktion konnte nicht nur kurzfristig erzielt werden, sondern es zeigte sich insbesondere, dass die Reduktion auch über einen längeren Zeitraum erreicht wird.It is now surprising that by using activated carbon, the total amount of VOC and VVOC emitted by the wood-based materials can be reduced. This reduction does not only include one of the aldehydes but in particular also the terpenes and the acids. Such a reduction could not only be achieved in the short term, but in particular it was shown that the reduction is also achieved over a longer period of time.

Vorwiegend wird unter dem Ausdruck der "Verringerung der Emission" oder "Verminderung der Emission", die synonym verwendet werden, verstanden, dass im Vergleich zu einem Holzwerkstoff ohne erfindungsgemäßes Additiv die Gesamtmenge einer flüchtigen organischen Verbindung (Total Volatile Organic Compounds TVOC) geringer ist.In particular, the expression "reduction of emission" or "reduction of emission", which are used interchangeably, means that the total amount of a total volatile organic compound (TVOC) is lower compared with a wood material without additive according to the invention.

Der Ausdruck "Vermeidung von Emission" beinhaltet eine im Vergleich zur Kontrolle prozentuale Verringerung oder Verminderung der Emission bis zu einer solchen die unterhalb der Messgrenze liegt.The term "avoidance of emission" includes a percentage reduction or decrease in emission compared to the control up to one that is below the measurement limit.

Vorliegend werden die Ausdrücke "Lignocellulose-haltige Zerkleinerungsprodukte" und "Lignocellulosepartikel" synonym verwendet.In the present case, the terms "lignocellulose-containing comminution products" and "lignocellulose particles" are used interchangeably.

Ein weiterer Vorteil der Verringerung bzw. Verminderung der Emission der TVOC ist, dass z.B. auch solche Stoffe in ihrer Emission erniedrigt sind, die weiterhin auch zu einem unangenehmen Geruch der Holzwerkstoffe beitragen, wie z.B. Essigsäure, die übelriechend ist, aber auch der typische Aldehydinsbesondere Formaldehyd-Geruch dieser Platten.Another advantage of the reduction or reduction of the emission of TVOC is that, for example, such substances are reduced in their emission, which also contribute to an unpleasant odor of wood materials, such as acetic acid, which is malodorous, but also the typical aldehyde particular formaldehyde Smell of these plates.

Unter Aktivkohle versteht man Kohlenstoffstrukturen aus kleinsten Graphitkristallen und amorphem Kohlenstoff mit poröser Struktur und inneren Oberflächen (BET-Oberfläche), üblicherweise in einem Bereich zwischen 300 und 2000 m2/g. Aktivkohle kann in Pulverform, als Korn aber auch in anderen Formen vorliegen. Bevorzugt handelt es sich bei der Aktivkohle um einen mit einer Dichte zwischen 0,2 bis 0,6 g/cm3, wobei die bevorzugte Porengröße der Aktivkohle im Bereich von < 1 nm bis zu 50 nm liegt.Activated carbon is understood to mean carbon structures of the smallest graphitic crystals and amorphous carbon with a porous structure and internal surfaces (BET surface area), usually in a range between 300 and 2000 m 2 / g. Activated carbon can be in powder form, as a grain but also in other forms. The activated carbon is preferably one with a density between 0.2 and 0.6 g / cm 3 , the preferred pore size of the activated carbon being in the range of <1 nm up to 50 nm.

Aktivkohle kann aus pflanzlichen tierischen oder mineralischen Rohstoffen hergestellt werden. Entsprechend kann die Aktivkohle aus Stein-, Holz-, Braunkohle stammen aber auch aus pflanzlichen Bestandteilen, wie Kokosnussschalen, Fruchtkernen usw. wie auch aus tierischen Kohlen.Activated carbon can be produced from vegetable animal or mineral raw materials. Accordingly, the activated carbon of stone, wood, lignite but also derived from vegetable ingredients, such as coconut shells, fruit seeds, etc., as well as from animal coals.

Aktivkohle ist als Adsorptionsmittel seit langem bekannt, z.B. wird es eingesetzt, um unerwünschte oder schädliche Farb- und Geruchsstoffe aus Gasen, Dämpfen und Flüssigkeiten etc. zu entfernen. Weiterhin sind sie in chemischen Reinigungsprozessen sowie zur Adsorption von z.B. Giftstoffen im pharmazeutischen Bereich bekannt.Activated carbon has long been known as an adsorbent, e.g. It is used to remove unwanted or harmful colors and odors from gases, vapors and liquids etc. Furthermore, they are useful in chemical cleaning processes as well as for the adsorption of e.g. Toxic substances known in the pharmaceutical field.

Aktivkohle ist dabei als Mittel zur Adsorption von Flüssigkeiten oder Gasen, für einen kurzen Zeitraum bekannt, nicht aber als ein Mittel zum permanenten Einsatz.Activated carbon is known as a means of adsorbing liquids or gases for a short period of time, but not as a means of permanent use.

Die Aktivkohle kann in fester Form als Pulver bevorzugt in einem Korndurchmesser von kleiner 1 mm und/oder als Granulat mit einer Korngröße von kleiner 4 mm zu den lignocellulosehaltigen Zerkleinerungsprodukten eingebracht werden.The activated carbon can be introduced in solid form as a powder preferably in a particle diameter of less than 1 mm and / or as granules with a particle size of less than 4 mm to the lignocellulose-containing comminution products.

Dabei wird das Additiv z.B. in einer Menge in einem Bereich von 0,1 bis 20 Gew. % auf atro Lignocellulose eingebracht.In this case, the additive is, for example, in an amount in a range of 0.1 to 20 % By weight applied to atro lignocellulose.

Die Verwendung eines porösen Kohlenstoffs in Form von Aktivkohle hat verschienste Vorteile. Vom wirtschaftlichen Standpunkt aus gesehen weist Aktivkohle eine hohe Verfügbarkeit und einen günstigen Preis auf. Im Herstellungsprozess selbst können Nachteile der bisherigen Additive überwunden werden. So kann eine Dosierung als Feststoff erfolgen, wodurch die Feuchte der Ausgangsstoffe und/oder der Holzwerkstoffplatten nicht erhöht wird. Eine zusätzliche Trocknung mit entsprechenden zusätzlichen Kosten ist daher nicht notwendig. Weiterhin weist der poröse Kohlenstoff in Form von Aktivkohle keine Reaktivität mit dem verwendeten Klebstoff auf, so dass die Reaktivität und Verarbeitbarkeit dieser z.B. deren Aushärtegeschwindigkeit, nicht verschlechtert wird. Dadurch ist es nicht notwendig, größere Mengen an Klebstoff hinzuzufügen, um Verschlechterungen in der Reaktivität dieser durch Zugabe von Additiven auszugleichen.The use of a porous carbon in the form of activated carbon has several advantages. From an economic point of view, activated carbon has high availability and a low price. In the manufacturing process itself disadvantages of previous additives can be overcome. Thus, a dosage can be carried out as a solid, whereby the moisture content of the starting materials and / or the wood-based panels is not increased. An additional drying with corresponding additional costs is therefore not necessary. Furthermore, the porous carbon in the form of activated carbon has no reactivity with the adhesive used, so that the reactivity and processability of this e.g. whose curing speed is not deteriorated. As a result, it is not necessary to add larger amounts of adhesive to compensate for deterioration in the reactivity of these by the addition of additives.

Die Gesamtemission der VOC gegebenenfalls einschließlich der VVOC aus den Holzwerkstoffen wird reduziert, wobei diese Reduktion nicht auf eine Substanzklasse beschränkt ist, sondern sowohl die Emission von Aldehyden als auch von Terpenen und Säuren verringert. Somit wird der TVOC-Wert und der R-Wert der hergestellten Holzwerkstoffe insbesondere in Form von Holzwerkstoffplatten, wie OSB-Platten, signifikant herabgesetzt. Der R-Wert wird dabei vom AgBB wie folgt beschrieben: R ist die Summe aller R für die einzelnen Verbindungen (Rl). Rl ist dabei der Quotient aus der Stoffkonzentration der Verbindung cl in der Kammerluft der Prüfkammer und dem NIK-Wert (niedrigste interessierende Konzentration Wert) der jeweiligen Verbindung, Ri = ci/NIKi. Gemäß dem AgBB sollte der R-Wert bei 1 oder kleiner liegen.The total emission of VOCs, if any, including VVOCs from the wood-based materials is reduced, this reduction not being limited to a class of substances, but reducing both the emission of aldehydes and of terpenes and acids. Thus, the TVOC value and the R value of the wood-based materials produced, especially in the form of wood-based panels, such as OSB boards, significantly reduced. The R value is described by the AgBB as follows: R is the sum of all R for the individual compounds (R l ). R l is the quotient of the substance concentration of the compound c l in the chamber air of the test chamber and the NIK value (lowest concentration of interest value) of the respective compound, R i = c i / NIK i . According to the AgBB, the R value should be 1 or less.

Das Additiv kann dabei zu verschiedenen Zeiten im Produktionsprozess hinzugefügt werden. Dabei kann das Additiv sowohl in fester Form gegebenenfalls aber auch in Form einer Suspension oder Dispersion, hinzugefügt werden. Bevorzugt wird die Aktivkohle, als Pulvergranulat in fester Form hinzugefügt.The additive can be added at different times in the production process. In this case, the additive can be added either in solid form but optionally also in the form of a suspension or dispersion. Preferably, the activated carbon, as powder granules in added to solid form.

Das Hinzufügen des Additivs kann dabei in allen Bereichen der herzustellenden Holzwerkstoffe erfolgen. Bei Holzwerkstoffplatten, wie OSB-Platten oder Faserplatten kann das Additiv z.B. nur in einzelnen Bereichen dieser vorliegen. Es kann dabei eine Dosierung des Additivs in die Deckschicht und/oder Mittelschicht erfolgen.The addition of the additive can be carried out in all areas of the wood-based materials to be produced. For wood-based panels, such as OSB panels or fiberboards, the additive may be e.g. only in some areas of this present. In this case, it is possible to meter the additive into the cover layer and / or middle layer.

Das Additiv kann erfindungsgemäß dabei in verschiedenen Gewichtsanteilen in der Deckschicht oder Mittelschicht vorhanden sein. So kann z.B. eine der Schichten einen Anteil von 5 Gew. % aufweisen, während die andere Schicht 10 % des Additivs aufweist. Natürlich können die Anteile in beiden Schichten auch gleich sein.The additive according to the invention can be present in different proportions by weight in the topcoat or middlecoat. Thus, e.g. one of the layers has a content of 5% by weight, while the other layer has 10% of the additive. Of course, the proportions in both layers can be the same.

Poröser Kohlenstoff in Form von Aktivkohle kann insbesondere in Pulverform vor dem Trockner und/oder nach dem Trockner im Fallschacht der lignocellulosehaltigen Zerkleinerungsprodukte für die Steuerung und/oder vor und/oder nach der Beleimung dieser und/oder in der Beleimung mit den entsprechendem Klebstoff, wie einem UF, MUF, PMDI-Klebstoff, erfolgen.Porous carbon in the form of activated carbon can, in particular in powder form before the dryer and / or after the dryer in the chute of lignocellulosic crushing products for the control and / or before and / or after the gluing of these and / or in the gluing with the corresponding adhesive, such as a UF, MUF, PMDI adhesive.

Je nach Einsatz des Additivs in der Deck- und/oder Mittelschicht, erfolgt die Zugabe des Additivs. Wie ausgeführt beträgt die Dosierung dabei bevorzugt 0,1 bis 20 Gew. % auf atro Lignocellulose.Depending on the use of the additive in the top and / or middle layer, the addition of the additive takes place. As stated, the dosage is preferably from 0.1 to 20% by weight on ator lignocellulose.

Als Klebstoffe können die üblicherweise eingesetzten Klebstoffe verwendet werden. Diese Klebstoffe umfassen als Klebstoffe Phenol-Formaldehyd-Klebstoffe (PF-Klebstoffe), Klebstoffe auf Basis von Isocyanaten, Harnstoff-Formaldehyd-Klebstoffe (UF-Klebstoffe), Melamin-Harnstoff-Formaldehyd-Klebstoffe (MUF-Klebstoffe), Melamin-Harnstoff-Phenol-Formaldehyd-Klebstoffe (MUPF-Klebstoffe), Tannin-Formaldehyd-Klebstoffe (TF-Klebstoffe), Polyurethan-Klebstoff (PU-Klebstoff) oder Gemische hiervon.As adhesives, the adhesives commonly used can be used. These adhesives include as adhesives phenol-formaldehyde (PF) adhesives, isocyanate-based adhesives, urea-formaldehyde (UF) adhesives, melamine-urea-formaldehyde (MUF) adhesives, melamine-urea adhesives Phenol-formaldehyde (MUPF) adhesives, tannin-formaldehyde (TF) adhesives, polyurethane (PU) adhesives, or mixtures thereof.

In einer bevorzugten Ausführungsform ist der Klebstoff ein nicht Formaldehydhaltiger Klebstoff, wie ein Klebstoff auf Basis von Isocyanaten, wie PMDI.In a preferred embodiment, the adhesive is a non-formaldehyde-containing adhesive, such as an isocyanate-based adhesive such as PMDI.

Unter Lignocellulosen werden vorliegend lignocellulosehaltige Materialien, wie Holz, verstanden. Daraus erhaltene Zerkleinerungsprodukte von Lignocellulosen umfassen insbesondere Holzstrands, Holzspäne, Holzfasern, aber auch Holzfurnieren.Lignocelluloses are understood here to be lignocellulose-containing materials, such as wood. The resulting comminution products of lignocelluloses include in particular wood strands, wood chips, wood fibers, but also wood veneers.

Bei den Lignocellulosen, wie den Holzwerkstoffen und den Zerkleinerungsprodukten hiervon, kann es sich sowohl um Nadelhölzer als auch um Laubhölzer handeln. Auch Mischungen dieser beiden Holzarten sind möglich. Bevorzugt stammen die Holzspäne, Strands oder Holzfasern von Nadelhölzern. Die mit dem erfindungsgemäßen Herstellungsverfahren herstellbaren Holzwerkstoffe, insbesondere Holzwerkstoffplatten, können gemäß einem bekannten Verfahren hergestellt werden. Gegebenenfalls kann das Verfahren zusätzlich auch andere, dem Fachmann bekannte Verfahren zur Verminderung der Emission von flüchtigen organischen Verbindungen, sehr flüchtigen organischen Verbindungen, ergänzt werden.The lignocelluloses, such as the wood-based materials and the comminuted products thereof, may be both conifers and hardwoods. Even mixtures of these two types of wood are possible. Preferably, the wood chips, strands or wood fibers come from conifers. The wood materials that can be produced by the production method according to the invention, in particular wood-based panels, can be produced according to a known method. Optionally, the process may additionally be supplemented by other processes known to those skilled in the art for reducing the emission of volatile organic compounds, very volatile organic compounds.

Weiterhin wird die Verwendung von Aktivkohle, als Additiv in der Herstellung von Holzwerkstoffen aus Lignocellulose insbesondere zur Verringerung bzw. von Minderung der Emission von VOC, TVOC und/oder VVOC beschrieben. Das Additiv wird dabei während des Herstellungsprozesses der Lignocellulose z.B. in Form von lignocellulosehaltigen Zerkleinerungspartikeln (lignocellulosehaltigen Partikeln) eingetragen bzw. aufgetragen.Furthermore, the use of activated carbon, as an additive in the production of wood materials from lignocellulose in particular for reducing or reducing the emission of VOC, TVOC and / or VVOC is described. The additive is thereby added during the manufacturing process of the lignocellulose e.g. in the form of lignocellulose-containing comminution particles (lignocellulose-containing particles) added or applied.

Die entsprechende Verwendung des Additivs kann dabei zumindest in der Deckschicht oder der Mittelschicht oder in beiden Schichten von z.B. OSB-Platten erfolgen. Erfindungsgemäß kann dabei das Additiv in einer Menge von 0,1 Gew. % bis 20 Gew. % Feststoff bezogen auf atro Lignocellulose eingebracht oder aufgebracht werden.The corresponding use of the additive can take place at least in the cover layer or the middle layer or in both layers of, for example, OSB boards. In accordance with the invention, the additive may be introduced or applied in an amount of from 0.1% by weight to 20% by weight of solids, based on atroscopic lignocellulose.

Schließlich werden Holzwerkstoffe bereitgestellt, erhältlich mit dem erfindungsgemäßen Verfahren. Bei diesen Holzwerkstoffen handelt es sich bevorzugt um eine Faserplatte, insbesondere leichte und superleichte MDF-Platte, eine OSB-Platte.Finally, wood materials are provided, obtainable by the method according to the invention. These wood-based materials are preferably a fiberboard, in particular lightweight and superlight MDF board, an OSB board.

Die erfindungsgemäßen Holzwerkstoffe zeichnen sich dadurch aus, dass sie über einen langen Zeitraum eine verringerte oder verminderte Emission von TVOC aufzeigen, wobei diese insbesondere auch eine Verringerung bzw. Verminderung der Terpene und Säuren einschließt. Weiterhin zeigte sich, dass die mechanischen Eigenschaften der hergestellten Holzwerkstoffe nicht oder nur in geringem Umfang negativ beeinflusst werden, wie z.B. in der Tabelle 3 unten dargestellt.The wood-based materials according to the invention are distinguished by the fact that they show a reduced or reduced emission of TVOC over a long period of time, and this in particular also includes a reduction or reduction of the terpenes and acids. Furthermore, it was found that the mechanical properties of the wood-based materials produced are not or only negligibly affected, such as. shown in Table 3 below.

Im Folgenden wird die Erfindung mit Hilfe von Beispielen näher erläutert, ohne dass sie auf diese beschränkt sind.In the following, the invention will be explained in more detail by means of examples, without being limited to these.

Beispiel 1example 1 Herstellung von Emissionsarmen OSBProduction of emission arms OSB Versuchergebnisse OSBTest results OSB

Es wurde zunächst eine Referenzplatte (Platte 1) mit 100% PMDI Beleimung und einer Dicke von 12 mm an der Laborpresse erstellt. Anschließend wurden drei Versuchsplatten unter Verwendung von Aktivkohle hergestellt. Dabei enthält Platte 2 5% auf atro Holz Aktivkohlepulver in der Deckschicht. Platte 3 enthält 5% auf atro Holz Aktivkohlepulver in der Mittelschicht und bei der Platte 4 wurde der Mittelschicht 10% auf atro Holz Aktivkohlepulver beigegeben.First, a reference plate (plate 1) with 100% PMDI gluing and a thickness of 12 mm was made on the laboratory press. Subsequently, three test panels were prepared using activated carbon. In this case, plate 2 contains 5% on atro wood activated carbon powder in the top layer. Plate 3 contains 5% of atro-wood activated carbon powder in the middle layer, and plate 4 has 10% of the middle layer added to atro-wood activated carbon powder.

Die nachfolgende Tabelle 1 enthält eine Übersicht der hergestellten Versuchsplatten. Diese wurden anschließend auf ihr Emissionsverhalten in einer Prüfkammer untersucht und nach dem AgBB-Schema über einen Zeitraum von 28 Tagen bewertet. Tabelle 1 Platte Dicke Beleimung Dosierung 1 12 100%PMDI "0"-Standard Platte 2 12 100%PMDI OSB Platte mit 5% AK in Deckschicht 3 12 100%PMDI OSB Platte mit 5% AK in Mittelschicht 4 12 100%PMDI OSB Platte mit 10% AK in Mittelschicht Table 1 below gives an overview of the test panels produced. These were then examined for their emission behavior in a test chamber and according to the AgBB scheme over a period of 28 Days. Table 1 plate thickness gluing dosage 1 12 100% PMDI "0" standard plate 2 12 100% PMDI OSB board with 5% AK in top layer 3 12 100% PMDI OSB board with 5% AK in middle layer 4 12 100% PMDI OSB board with 10% AK in middle layer

Durchführung der VOC-EmissionsmessungCarrying out the VOC emission measurement

Die Emissionsmessungen erfolgten in Prüfkammern aus Glasexsikkatoren mit einem Volumen von 23,5 Litern. Die Prüfungen fanden auf Grundlage von ISO 16 000 Teil 9 (2008) statt. Standardbedingungen waren demnach eine Temperatur von 23 °C, eine relative Luftfeuchte von 50 % und eine Luftgeschwindigkeit nahe der Probenoberfläche von 0,1 bis 0,3 m s-2. Die Standardbeladung betrug rund 720 cm2 emittierende Fläche, d. h. der Beladungsgrad der Kammer betrug 3,1 m2 m-3; der Luftaustausch mit hochreiner synthetischer Luft in der Prüfkammer erfolgte 3,1 mal pro Stunde. Daraus ergab sich eine standardmäßige flächenspezifische Luftwechselrate von 1 m3/(m2*h). Die Mindestprüfdauer betrug 28 Tage, wobei die Luftprobennahme nach einem und drei Tagen nach Probeneinbringung und im weiteren Verlauf wöchentlich erfolgte. Die Beprobung erfolgte nach ISO 16 000 Teil 6 (2004) mittels einer Pumpe und mit dem Adsorbens Tenax TA® gefüllten Röhrchen. Das jeweilige Probenaufnahmevolumen betrug 0,5 bis maximal 4 Liter Prüfkammerluft. Die mit Tenax TA gefüllten Röhrchen wurden vor jeder Luftprobenahme thermisch gereinigt und mit 200 ng deuterisiertem Toluol als internem Standard beaufschlagt. Zur Identifizierung und Quantifizierung der in der Probenluft enthaltenen VOCs wurde das beprobte Tenax TA thermisch desorbiert (TD) und die Substanzen über eine Kryofokussiereinheit in einen Gaschromatographen (GC), gekoppelt mit einem Massenspektrometer (MS), überführt.The emission measurements were carried out in test chambers made of glass desiccators with a volume of 23.5 liters. The tests were based on ISO 16 000 part 9 (2008). Standard conditions were therefore a temperature of 23 ° C, a relative humidity of 50% and an air velocity near the sample surface of 0.1 to 0.3 m s-2. The standard load was about 720 cm 2 emitting area, ie the loading level of the chamber was 3.1 m2 m-3; The air exchange with high-purity synthetic air in the test chamber was 3.1 times per hour. This resulted in a standard area-specific air exchange rate of 1 m 3 / (m 2 * h). The minimum test duration was 28 days with air sampling occurring one and three days after sample introduction and weekly thereafter. The sampling was carried out according to ISO 16 000 part 6 (2004) by means of a pump and tubes filled with the adsorbent Tenax TA®. The respective sample volume was 0.5 to a maximum of 4 liters of test chamber air. Tenax TA-filled tubes were thermally cleaned prior to each air sampling and loaded with 200 ng of deuterated toluene as an internal standard. To identify and quantify the VOCs contained in the sample air, the sampled Tenax TA was thermally desorbed (TD) and the substances transferred via a cryofocusing unit to a gas chromatograph (GC) coupled to a mass spectrometer (MS).

Ergebnisse: VOC-Emissionsergebnisse nach 1, 3, 7, 14, 21 und 28 Tagen sind in der Tabelle 2 dargestellt: Tabelle 2 TVOC µg/m3 Hexanal µg/m3 R-Wert Platte Tag 1 3 7 14 21 28 1 28 1 3354,6 1299,9 1122,3 999,1 807,0 399,1 3,3 2 3330,2 2164,0 1742,0 1321,6 1040,0 980,8 811,6 360,7 2,4 3 665,4 553,2 445,4 441,1 351,7 265,5 131,1 79,4 1 4 980,3 659,5 567,6 522,5 410,8 382,9 216,4 107,3 1 Results: VOC emission results after 1, 3, 7, 14, 21 and 28 days are shown in Table 2: Table 2 TVOC μg / m 3 Hexanal μg / m 3 R-value plate day 1 3 7 14 21 28 1 28 1 3,354.6 1,299.9 1,122.3 999.1 807.0 399.1 3.3 2 3,330.2 2,164.0 1,742.0 1,321.6 1040.0 980.8 811.6 360.7 2.4 3 665.4 553.2 445.4 441.1 351.7 265.5 131.1 79.4 1 4 980.3 659.5 567.6 522.5 410.8 382.9 216.4 107.3 1

Die mechanischen Parameter einer OSB mit 12mm Dicke und 5% Aktivkohle in der MS in Vergleich zu der Referenzplatte ohne Zugabe von Aktivkohle ist in der Tabelle 3 dargestellt: Tabelle 3: Parameter Referenzplatte 5% Aktivkohle in MS Rohdichte 687 671 Biegefestigkeit [MPa] 43,46 37,33 E-Modut [MPa] 6322 6615 Querzug [MPa] 0,62 0,45 Quellung [%] 26,6 29,5 The mechanical parameters of an OSB with 12mm thickness and 5% activated carbon in the MS compared to the reference plate without addition of activated carbon is shown in Table 3: Table 3: parameter reference plate 5% activated carbon in MS density 687 671 Bending strength [MPa] 43.46 37.33 E-Modut [MPa] 6322 6615 Transverse train [MPa] 0.62 0.45 Swelling [%] 26.6 29.5

Es zeigt sich, dass die mechanischen Parameter durch Zugabe der Aktivkohle kaum verändert werden.It turns out that the mechanical parameters are hardly changed by adding the activated carbon.

In einer weiteren Versuchsreihe wurden die Referenzplatte und eine Platte mit 5% Aktivkohle in der Mittelschicht (MS) gemäß den Maßgaben der AgBB untersucht. Die Ergebnisse wurden dabei bestätigt, wie in der Tabelle 4 gezeigt. Tabelle 4: Probe Aktivkohle [%] MS Beladung [m2/m3] Lüftungs rate [h-1] q [m3/(m2*h)] TVOC 28d [µg/m3] R 28d 1 0 1 1 1 565 1.563 2 5 1 1 1 242 0.838 In another series of experiments, the reference plate and a 5% activated carbon plate in the middle layer (MS) were tested according to the requirements of AgBB. The results were confirmed as shown in Table 4. Table 4: sample Activated carbon [%] MS Load [m 2 / m 3 ] Ventilation rate [h -1 ] q [m 3 / (m 2 * h)] TVOC 28d [μg / m 3 ] R 28d 1 0 1 1 1 565 1563 2 5 1 1 1 242 0838

Diskussion der Ergebnissediscussion of the results

Die VOC-Emissionsmessungen zeigen den stärksten Effekt einer Reduktion im Fall der Dosierung des Aktivkohlepulvers in der Mittelschicht. Insbesondere eine Dosierung von 5% auf atro Holz Aktivkohle führt zu einer starken Reduktion der VOC-Emission. Im Vergleich zur Referenzplatte (Platte 1) wird der TVOC-Wert von 999,1 µg/m3 auf 265,6 µg/m3 herabgesetzt (Platte 3). Auch der R-Wert wird im Fall der Versuchsplatte 3 im Vergleich zur Referenzplatte 1 von 3,3 auf 1 stark reduziert.The VOC emission measurements show the strongest effect of reduction in the case of metering of the activated carbon powder in the middle layer. In particular, a dosage of 5% on atro wood activated carbon leads to a strong reduction of VOC emission. In comparison to the reference plate (plate 1), the TVOC value is reduced from 999.1 μg / m 3 to 265.6 μg / m 3 (plate 3). Also, the R value is greatly reduced in the case of the test plate 3 from 3.3 to 1 compared to the reference plate 1.

Aktivkohle besitzt durch die hohe innere Oberfläche eine hohe Adsorptionsfähigkeit. Durch die hohe offenporige Struktur besitzt die Aktivkohle die Fähigkeit, große Mengen an Gasmolekülen einzulagern und diese zu speichern. Aktivkohle zählt zu den hydrophoben Adsorbentien und eignet sich insbesondere für die Adsorption von weniger polaren VOCs, wie Terpenen. Neben der Physiosorption spielt hier auch die Chemisorption eine große Rolle, wobei die VOC-Moleküle fähig sind mit den Oberflächenmolekülen der Aktivkohle in chemische Wechselwirkungen zu treten, wobei es zu einer echten Bildung einer Oberflächenverbindung kommt.Activated carbon has a high adsorption capacity due to the high internal surface. The high open-pore structure of the activated carbon has the ability to store large quantities of gas molecules and store them. Activated carbon is one of the hydrophobic adsorbents and is particularly suitable for the adsorption of less polar VOCs, such as terpenes. In addition to physiosorption, chemisorption also plays an important role here, whereby the VOC molecules are able to chemically interact with the surface molecules of the activated carbon, leading to a true formation of a surface compound.

Claims (11)

  1. Process for production of wood-base materials from lignocellulose, in particular flakeboard panels, fibreboard panels or OSB panels, comprising the steps of:
    a) providing lignocellulosic comminution products,
    b) introducing an additive into the lignocellulosic comminution products,
    c) compression moulding the additive-admixed lignocellulosic comminution products with adhesive under heat treatment to produce the wood-base material, characterized in that the additive is activated carbon and its addition reduces the emission of volatile organic compounds (VOCs), in particular terpenes and acids.
  2. Process according to the preceding claim, characterized in that the activated carbon is introduced into the lignocellulosic comminution products in solid form as a powder preferably with a particle diameter of < 1 mm and/or as granules with a particle size of preferably up to 4 mm.
  3. Process according to either preceding claim, characterized in that the internal surface area of the activated carbon is between 300 and 2000 m2/g and/or the density is between 0.2 to 0.6 g/cm3 and the pore size is on average between 1 mm and 50 nm.
  4. Process according to any preceding claim, characterized in that the additive is introduced in an amount of 0.1 to 20 wt% on absolutely dry lignocellulose.
  5. Process according to any preceding claim, characterized in that the adhesive used is a formaldehyde-free adhesive such as an adhesive which is based on isocyanates, or is a formaldehyde-containing adhesive especially a phenol-formaldehyde adhesive, a urea-formaldehyde adhesive, a melamine-urea-formaldehyde adhesive, a melamine-urea-phenol-formaldehyde adhesive, a tannin-formaldehyde adhesive or a mixture thereof.
  6. Process according to any preceding claim, characterized in that the lignocellulosic comminution products are selected from wood flakes, wood strands or wood fibres.
  7. Process according to any preceding claim, characterized in that the activated carbon is at least introduced as additive into the lignocellulosic comminution products forming the outer layer.
  8. Process according to some of Claims 1 to 8, characterized in that the activated carbon is at least introduced as additive into the lignocellulosic comminution products forming the middle layer.
  9. Process according to any preceding claim, characterized in that the additive is added upstream of the dryer and/or downstream of the dryer and/or during resination and/or upstream or downstream of resination.
  10. Process according to any preceding claim, characterized in that the activated carbon is admixed as powder, granules, suspension and/or dispersion preferably as pulverulent granules in solid form.
  11. Wood-base material obtainable with a process according to any of Claims 1 to 10, preferably a fibreboard panel, in particular a light or superlight MDF panel, or an OSB panel.
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UAA201505465A UA117817C2 (en) 2012-11-06 2013-11-06 Method for reducing the emission of volatile organic compounds from wood materials, and wood materials
EP13792612.7A EP2917008B1 (en) 2012-11-06 2013-11-06 Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material
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PL13792612.7T PL2917008T3 (en) 2012-11-06 2013-11-06 Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material
US14/439,768 US9895824B2 (en) 2012-11-06 2013-11-06 Process for production of wood based materials from lignocellulose
JP2015540164A JP6293769B2 (en) 2012-11-06 2013-11-06 Method for reducing the emission of volatile organic compounds from wood materials and wood materials
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DE102005031486A1 (en) 2005-07-04 2007-01-11 Hülsta-Werke Hüls Gmbh & Co. Kg Floor, wall or ceiling panel
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DE102006020612B4 (en) 2006-05-02 2019-03-14 SWISS KRONO Tec AG Process for the production of wood-based materials with reduced emission of volatile organic compounds, wood-based materials obtainable therewith and the use of certain additives for reducing the release of volatile organic compounds from wood-based materials and wood-pulp products of lignocelluloses
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DE102007050935A1 (en) 2007-10-23 2009-04-30 Kronotec Ag A method for reducing the emission of aldehydes and other volatile organic compounds from wood-based materials and compositions therefor
DE102007055415C5 (en) * 2007-11-19 2018-11-29 SWISS KRONO Tec AG Method for reducing the emission of saturated and unsaturated aldehydes from wood-based materials
KR101054095B1 (en) 2008-12-18 2011-08-09 대한민국 Method of manufacturing functional charcoal board
CN101585204A (en) 2009-01-24 2009-11-25 东北林业大学 Fiberboard with formaldehyde self-absorbing function and manufacturing method thereof
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EP2615126B1 (en) * 2012-01-16 2013-08-28 Kronotec AG Use of modified nanoparticles in wood materials for reducing the emission of volatile organic compounds (VOCs)
EP2727691B1 (en) * 2012-11-06 2014-12-10 Kronotec AG Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material
US20140259890A1 (en) * 2013-03-18 2014-09-18 Robert Beadles Manufactured charcoal briquette using Diatomaceous Earth, Organic Fibers, and Aromatic and Non-Aromatic Woods.

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US20150298346A1 (en) * 2012-11-06 2015-10-22 Kronotec Ag Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material
US9895824B2 (en) * 2012-11-06 2018-02-20 SWISS KRONO Tec AG Process for production of wood based materials from lignocellulose
EP3147093A1 (en) 2015-09-24 2017-03-29 SWISS KRONO Tec AG Method for reducing the emissions of volatile organic compounds from wooden materials and wooden material
WO2017050949A1 (en) 2015-09-24 2017-03-30 SWISS KRONO Tec AG Method for reducing the emission of volatile organic compounds made of wood materials, and wood materials

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US9895824B2 (en) 2018-02-20
PT2727691E (en) 2015-03-20
RU2661361C2 (en) 2018-07-16
EP2727691A1 (en) 2014-05-07
CN104781055A (en) 2015-07-15
ES2529356T3 (en) 2015-02-19
WO2014072304A1 (en) 2014-05-15
BR112015009351A2 (en) 2017-07-04
HUE024531T2 (en) 2016-01-28
PL2917008T3 (en) 2023-10-16
US20150298346A1 (en) 2015-10-22
JP2015533353A (en) 2015-11-24
CA2886475C (en) 2020-10-06
EP2917008B1 (en) 2023-06-07
SI2727691T1 (en) 2015-04-30
UA117817C2 (en) 2018-10-10
EP2917008A1 (en) 2015-09-16
PL2727691T3 (en) 2015-04-30
ES2954071T3 (en) 2023-11-20
EP2917008C0 (en) 2023-06-07
RU2015121571A (en) 2016-12-27
JP6293769B2 (en) 2018-03-14
CA2886475A1 (en) 2014-05-15
HUE064134T2 (en) 2024-03-28

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