DE102011104025A1 - Method for modification of wood or wood materials, involves subjecting wood of chemical and thermal treatment, where same strength properties in thermal untreated wood are achieved during reduced emission at volatile organic components - Google Patents
Method for modification of wood or wood materials, involves subjecting wood of chemical and thermal treatment, where same strength properties in thermal untreated wood are achieved during reduced emission at volatile organic components Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/0085—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/163—Compounds of boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/32—Mixtures of different inorganic impregnating agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Modifizierung von Holz oder Holzwerkstoffen, bei dem das Holz einer chemischen und thermischen Behandlung unterzogen wird, wobei bei reduzierter Emission an flüchtigen organischen Komponenten des Holzes zumindest gleiche Festigkeitseigenschaften wie bei dem thermisch unbehandelten Holz erreicht werden. Die Erfindung betrifft auch chemisch und thermisch modifiziertes Holz.The invention relates to a method for modifying wood or wood-based materials, in which the wood is subjected to a chemical and thermal treatment, wherein at reduced emission of volatile organic components of the wood at least the same strength properties are achieved as in the thermally untreated wood. The invention also relates to chemically and thermally modified wood.
Die thermische Behandlung oder thermische Modifikation von Holz hat beispielsweise zum Ziel seine Dimensionsstabilität im Gebrauch, die biologische Dauerhaftigkeit zu erhöhen, seine Wasseraufnahme zu reduzieren oder die Farbe zu verändern. Hierzu existieren eine Vielzahl von Patente und Verfahren wie zum Beispiel
Ein weiterführendes Vergütungsverfahren stellt das Waxwood dar. Nach dem thermischen Vergütungsvorgang erfolgt die Tränkung des Holzes in einem Wachsbad (
Neben der thermischen Modifikation von Holz existieren weiterhin eine Vielzahl von Verfahren zur chemischen Modifikation von Holz. Einen Überblick über die verschiedenen Verfahren liefern z. B. die Druckschriften
Ein weiterer chemischer Modifikationsansatz betrifft die Imprägnierung des Holzes mit einer Furfurylalkohol enthaltenden Lösung (
Im Bereich der Holzwerkstoffherstellung sind Verfahren zur Reduzierung von flüchtigen organischen Komponenten, die im Zuge der Holzwerkstoffherstellung sowie durch Zugabe organischer Bindemittel und weiterer organischer Hilfsstoffe entstehen, beschrieben. So beschreibt die
In der Offenlegungsschrift
In der
Die Offenlegungsschrift
Es sind weiterhin Verfahren zur Emissionsminderung von Vollholz bekannt. Die Offenlegungsschrift
Die Offenlegungsschrift
Die Aufgabe der vorliegenden Erfindung besteht darin, das Holz mittels chemischer und thermischer Behandlung so zu modifizieren, dass die genannten Nachteile des Standes der Technik einer einzelnen chemischen oder thermischen Modifikation des Holzes überwunden werden können. Dabei wird über den Stand der Technik hinaus ausschließlich die thermische Modifikation von Vollholz betrachtet, wobei die stofflichen Veränderungen erfindungsgemäß über die Stoffabbauprozesse beim Trocknen, Dämpfen oder Plastifizieren Holz und Holzhackschnitzeln hinausgehen. Verfahrensbedingt wird bei der vorliegenden Erfindung gegenüber dem Stand der Technik die Festigkeit des Vollholzes erhöht.The object of the present invention is to modify the wood by means of chemical and thermal treatment so that the stated disadvantages of the prior art of a single chemical or thermal modification of the wood can be overcome. In addition to the state of the art, only the thermal modification of solid wood is considered, the material changes according to the invention going beyond the material degradation processes during drying, steaming or plasticizing wood and wood chips. Due to the method, the strength of the solid wood is increased in the present invention over the prior art.
Erfindungsgemäß wird die Aufgabe durch ein Verfahren mit den im Anspruch 1 genannten Merkmalen gelöst. Vorteilhafte Varianten des Verfahrens sind Gegenstand von abhängigen Unteransprüchen.According to the invention the object is achieved by a method having the features mentioned in claim 1. Advantageous variants of the method are the subject of dependent subclaims.
Bei dem erfindungsgemäßen Verfahren werden die während eines thermischen Holzmodifikationsprozesses entstehenden flüchtigen organischen Komponenten durch eine chemische Substanz in situ aufgefangen und chemisch gebunden. Dadurch entsteht ein Produkt mit reduzierten Emissionen an flüchtigen organischen Komponenten. Es wird eine vernetzende Wirkung sowie eine nahezu vollständige Umsetzung der flüchtigen Holzkomponenten erzielt. Es unterscheidet sich von den bisherigen Verfahren der kombinierten thermischen und chemischen Modifikation dadurch, dass keine Reaktion mit den Hauptkomponenten des Holzes stattfindet, sondern chemische Abbauprodukte infolge der thermischen Modifikation gefangen, chemisch umgewandelt und gebunden werden.In the method according to the invention, the volatile organic components formed during a thermal wood modification process are captured by a chemical substance in situ and chemically bound. This creates a product with reduced emissions of volatile organic compounds. It is achieved a crosslinking effect as well as a nearly complete conversion of the volatile wood components. It differs from the previous methods of combined thermal and chemical modification in that no reaction takes place with the main components of the wood, but chemical degradation products due to the thermal modification are caught, chemically converted and bonded.
Hierzu wird das Holz zunächst mit einer organischen oder anorganischen Lösung oder Kombination aus beiden imprägniert, die aufgrund ihrer chemischen Struktur geeignet ist Reaktionen mit den flüchtigen Komponenten einzugehen. Zu diesen Reaktionen zählen beispielsweise Kondensation, Veresterung oder Addition. Die organische oder anorganische Lösung kann auch als Puffer für die entstehende Essigsäure wirken, um die Katalyse des weiteren Abbaus zu unterbinden.For this purpose, the wood is first impregnated with an organic or inorganic solution or combination of the two, which is suitable due to their chemical structure to react with the volatile components. These reactions include, for example, condensation, esterification or addition. The organic or inorganic solution may also act as a buffer for the resulting acetic acid to inhibit catalysis of further degradation.
An die chemische Behandlung schließt eine thermische Behandlung unter erhöhter Temperatur an. Diese liegt vorteilhaft im Bereich von 160 bis 250°C. Vorteilhaft wird die thermische Behandlung unter Inertgasatmosphäre (Wasserdampf, Stickstoff, Edelgase) über einem Zeitraum von 2 bis 24 Stunden durchgeführt.The chemical treatment is followed by a thermal treatment at elevated temperature. This is advantageously in the range of 160 to 250 ° C. The thermal treatment is advantageously carried out under an inert gas atmosphere (steam, nitrogen, noble gases) over a period of 2 to 24 hours.
Zur Imprägnierung können folgende chemischen Substanzen, einzeln oder in Kombination eingesetzt werden: Harnstoff in Ethanollösung sowie wässrigen Lösungen aus Borsäure und Natriumhydroxid.For impregnation, the following chemical substances can be used, individually or in combination: urea in ethanol solution and aqueous solutions of boric acid and sodium hydroxide.
Die Imprägnierung mit Harnstoff und die folgende thermische Modifikation führen zu einer Umsetzung des Furfurals. Der Einsatz von wässrigen Lösungen aus Borsäure und Natriumhydroxid führt zur Unterdrückung der Essigsäurebildung und damit verbunden zu einer Reduzierung der katalytischen Abbaureaktionen der Holzpolyosen. The impregnation with urea and the following thermal modification lead to a conversion of the furfural. The use of aqueous solutions of boric acid and sodium hydroxide leads to the suppression of the formation of acetic acid and thus to a reduction in the catalytic degradation reactions of wood polyols.
Als Ergebnis wird ein modifiziertes Holz erzeugt, welches nach dem thermischen Modifikationsschritt gegenüber klassisch thermisch modifizierten Hölzern eine stark reduzierte Emission typischer flüchtiger organischer Komponenten wie Essigsäure und Furfural aufweisen, die teilweise unter dem Niveau nativer, unbehandelter Hölzer liegen. Weiterhin haben sich aber auch verbesserte mechanische Eigenschaften, charakterisiert durch eine teilweise deutlich verbesserte Biegefestigkeit eingestellt. Überraschend lag diese Biegefestigkeit sogar über dem Festigkeitsniveau des verwendeten nativen Ausgangsmaterials.As a result, a modified wood is produced, which after the thermal modification step compared to classically thermally modified woods have a greatly reduced emission of typical volatile organic compounds such as acetic acid and furfural, which are partially below the level of native, untreated woods. Furthermore, but also improved mechanical properties, characterized by a partially significantly improved flexural strength set. Surprisingly, this flexural strength even exceeded the strength level of the native starting material used.
Der Vorteil der Erfindung besteht somit in der Möglichkeit zur Herstellung von Holz oder Produkten aus Holz, die die Vorteile thermisch modifizierter Hölzer, wie Dimensionsstabilität, biologische Dauerhaftigkeit, reduzierte Feuchtesorption aufweisen. Gleichzeitig sind die bekannten Nachteile bezüglich Emissionen und reduzierten Festigkeitseigenschaften kompensiert und liegen sogar über dem Niveau der Ausgangsmaterialien.The advantage of the invention thus lies in the possibility of producing wood or products made of wood, which have the advantages of thermally modified woods, such as dimensional stability, biological durability, reduced moisture absorption. At the same time, the known disadvantages in terms of emissions and reduced strength properties are compensated and are even above the level of the starting materials.
Die Erfindung wird nachfolgend an Hand von Ausführungsbeispielen noch näher erläutert.The invention will be explained in more detail with reference to exemplary embodiments.
Ausführungsbeispiele 1)Exemplary embodiments 1)
Ein Probekörper der Holzart Ahorn wurden mit einer 0,5 molaren ethanolischen Harnstofflösung unter Vakuum bei Raumtemperatur bis zur Sättigung imprägniert. Nach einem Trocknungsschritt zur Entfernung der ethanolischen Lösungskomponente bei 80°C folgte eine thermische Modifikation unter Stickstoffatmosphäre über einem Zeitraum von 5 Stunden bei 180°C. Die so vergüteten Hölzer wiesen, nachgewiesen durch GC-MS Analysen, eine deutlich reduzierte Emission typischer Thermoholzemissionen wie Furfural und Essigsäure auf. Der typische Geruch thermisch modifizierter Hölzer wurde durch Probanden für derartig modifizierte Hölzer nicht festgestellt. Überraschend lagen die Werte der Biegefestigkeit dieser modifizierten Hölzer im höheren Wertebereich als die der unbehandelten, nativen Probekörper. So lag die durchschnittliche Biegefestigkeit nativer Ahomproben bei 125 N/mm2, rein thermisch modifizierten Ahornproben bei 98 N/mm2 sowie die mit 0,5 molaren ethanolischer Harnstofflösung imprägnierten und nachträglich thermisch modifizierten Proben bei 155 N/mm2. Das heißt der typische Festigkeitsverlust thermisch modifizierter Hölzer konnte durch die kombinierte Behandlung nicht nur ausgeglichen sonder deutlich und signifikant über das Niveau nativer und unbehandelter Hölzer verbessert werden.A test specimen of maple wood was impregnated with a 0.5 molar ethanolic urea solution under vacuum at room temperature until saturation. After a drying step to remove the ethanolic solution component at 80 ° C followed by a thermal modification under a nitrogen atmosphere over a period of 5 hours at 180 ° C. The thus tempered woods had, as evidenced by GC-MS analyzes, a significantly reduced emission of typical thermo-wood emissions such as furfural and acetic acid. The typical smell of thermally modified woods was not detected by volunteers for such modified woods. Surprisingly, the values of the flexural strength of these modified woods were in the higher value range than those of the untreated, native test specimens. Thus, the average flexural strength of native Ahom samples was 125 N / mm 2 , purely thermally modified maple samples at 98 N / mm 2, and the samples impregnated with 0.5 molar ethanolic urea solution and subsequently thermally modified at 155 N / mm 2 . That is, the typical loss of strength of thermally modified woods could not only be compensated for by the combined treatment but also significantly and significantly improved over the level of native and untreated woods.
Ausführungsbeispiel 2)Embodiment 2)
Ein Probekörper der Holzart Ahorn wurden mit einem 0,4 molaren wässrigen Boratpuffer, bestehend aus Borsäure und Natriumhydroxid unter Vakuum bei Raumtemperatur bis zur Sättigung imprägniert. Nach einem Trocknungsschritt zur Entfernung der wässrigen Lösungskomponente bei 80°C folgte eine thermische Modifikation unter Stickstoffatmosphäre über einem Zeitraum von 5 Stunden bei 180°C.A test specimen of maple wood was impregnated with a 0.4 molar aqueous borate buffer consisting of boric acid and sodium hydroxide under vacuum at room temperature to saturation. After a drying step to remove the aqueous solution component at 80 ° C, a thermal modification under a nitrogen atmosphere followed for a period of 5 hours at 180 ° C.
Der typische Geruch thermisch modifizierter Hölzer wurde durch Probanden für derartig modifizierte Hölzer nicht festgestellt. Auch hier lagen überraschend die Werte der Biegefestigkeit dieser modifizierten Hölzer im höheren Wertebereich als die der unbehandelten, nativen Probekörper. So lag die durchschnittliche Biegefestigkeit nativer Ahornproben bei 125 N/mm2, rein thermisch modifizierten Ahomproben bei 98 N/mm2 sowie die mit 0,4 molaren wässrigen Boratpuffer imprägnierten und nachträglich thermisch modifizierten Proben bei 133 N/mm2. Das heißt, der typische Festigkeitsverlust thermisch modifizierter Hölzer konnte durch die kombinierte Behandlung nicht nur ausgeglichen sondern deutlich und signifikant über das Niveau nativer und unbehandelter Hölzer verbessert werden.The typical smell of thermally modified woods was not detected by volunteers for such modified woods. Again, the values of the bending strength of these modified woods were surprisingly higher in the value range than those of the untreated, native test specimens. Thus, the average bending strength of native maple samples was 125 N / mm 2 , purely thermally modified Ahom samples at 98 N / mm 2, and the samples with 0.4 molar aqueous borate buffer and subsequently thermally modified samples at 133 N / mm 2 . This means that the typical loss of strength of thermally modified woods could not only be compensated for by the combined treatment but also significantly and significantly improved over the level of native and untreated woods.
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
Zitierte PatentliteraturCited patent literature
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Zitierte Nicht-PatentliteraturCited non-patent literature
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- L. Nordstierna, S. Lande, M. Westin, O. Karlsson, und I. Furó, ”Towards novel wood-based materials: Chemical bonds between lignin-like model molecules and poly(furfuryl alcohol) studied by NMR,” Holzforschung, vol. 62, 2008, S. 709–713 [0005] L. Nordstierna, S. Lande, M. Westin, O. Karlsson, and I. Furó, "Towards novel wood-based materials: chemical bonds between lignin-like model molecules and poly (furfuryl alcohol) studied by NMR," Holzforschung, vol. 62, 2008, p. 709-713 [0005]
Claims (8)
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DE102011104025A DE102011104025A1 (en) | 2010-06-11 | 2011-06-08 | Method for modification of wood or wood materials, involves subjecting wood of chemical and thermal treatment, where same strength properties in thermal untreated wood are achieved during reduced emission at volatile organic components |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3778159A1 (en) | 2019-08-05 | 2021-02-17 | Volkswagen AG | Method for treating wood |
CN115219702A (en) * | 2022-07-15 | 2022-10-21 | 安徽农业大学 | Prediction method and prediction model for hemicellulose content after wood heat treatment |
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Cited By (2)
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EP3778159A1 (en) | 2019-08-05 | 2021-02-17 | Volkswagen AG | Method for treating wood |
CN115219702A (en) * | 2022-07-15 | 2022-10-21 | 安徽农业大学 | Prediction method and prediction model for hemicellulose content after wood heat treatment |
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