EP0623433B1 - Verfahren zur Verbesserung von Holz niedriger Qualität - Google Patents

Verfahren zur Verbesserung von Holz niedriger Qualität Download PDF

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Publication number
EP0623433B1
EP0623433B1 EP94201159A EP94201159A EP0623433B1 EP 0623433 B1 EP0623433 B1 EP 0623433B1 EP 94201159 A EP94201159 A EP 94201159A EP 94201159 A EP94201159 A EP 94201159A EP 0623433 B1 EP0623433 B1 EP 0623433B1
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Prior art keywords
temperature
range
sections
aqueous medium
stage
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Expired - Lifetime
Application number
EP94201159A
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English (en)
French (fr)
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EP0623433A1 (de
Inventor
Herman Petrus Ruyter
Peter Arnoldy
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Plato Beheer BV
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Shell Internationale Research Maatschappij BV
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/06—Softening or hardening of wood
    • 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

Definitions

  • the invention relates to a process for upgrading low-quality wood to high-quality wood in an environmentally sound way, and to high-quality wood obtained by means of this process.
  • Such a process is known from EP-A-0373726.
  • a cellulosic fibrous aggregate is formed from a cellulosic fibrous material by a process which comprises: a softening stage comprising exposing a section of cellulosic fibrous material to the action of an aqueous softening agent at a temperature in the range of from 150 °C to 220 °C at a pressure of at least the equilibrium vapour pressure of the softening agent at the operating temperature, thereby at least partially disproportionating and hydrolysing the hemicellulose and lignin present in the cellulosic fibrous material; and a curing stage comprising drying the product of the softening stage at a temperature in the range of from 100 °C to 220 °C to yield a cross-linked cellulosic matrix.
  • additives such as acids, alkali metal or earth alkali metal hydroxides or carbonates, ammonia or lower alcohols to facilitate softening.
  • This process uses traditional ways of heating and drying the wood. These methods rely on thermal conduction to raise the temperature of the wood and evaporate water contained therein. The poor thermal conductivity of wood and the sensitivity of the process chemistry to extended heating times, result in limitations on product thickness and quality for such process. Furthermore, it has been found that gradients in temperature, pressure and moisture concentration induce stresses in wood, which may result in the formation of cracks and consequent loss of mechanical strength. Hence it can be concluded that there is need for a process for upgrading low-quality wood which allows the processing of sizable sections of low-quality wood.
  • the invention relates to a process for upgrading low-quality wood to high-quality wood, comprising:
  • the pH of the buffered aqueous medium is preferably in the range of from 4.0 to 6.5, and more preferably from 4.5 to 6.
  • the buffering agent preferably comprises a mixture of an acid or base and a salt, more preferably a mixture of an organic acid and a salt of an organic acid.
  • the organic acid is suitably an optionally substituted alkanoic acid, especially an alkanoic acid containing up to 6 carbon atoms, or benzoic acid.
  • the acid is preferably a mono-, di- or tri- carboxilic acid, substituted by up to three hydroxy groups, especially one hydroxy group as the sole substituent, or is not substituted at all.
  • the buffering agent is especially a mixture of acetic acid and an ammonium or alkali metal salt thereof, or a mixture of citric acid and an ammonium or an alkali metal salt of citric acid.
  • the alkali metal component of said salt is preferably sodium or potassium.
  • Earth alkaline metal salts such as magnesium and/or calcium salts may also be used.
  • the buffering agent is dissolved in the aqueous medium wherein the concentration of the buffering agent is suitably in the range of from 0.01 to 2 mol/litre and preferably from 0.05 to 1.0 mol/litre.
  • the concentration of the buffering agent is considered to be the concentration of the acid (or base), together with the concentration of the salt.
  • the aqueous medium is water.
  • air-dry low quality wood is impregnated with the aqueous medium containing at least the salt component of the buffering agent in advance of the softening.
  • the impregnation is carried out by immersion of the air-dry sections in the aqueous buffer solution at a temperature ⁇ 100 °C.
  • the air-dry wood has a moisture content in the range of from 5 to 25 %w, and preferably from 10 to 22.5 %w (i.e. 10 to 22.5 parts of moisture and 90 to 77.5 parts of solids).
  • the wood suitably contains more than 40 %w of moisture, preferably more than 45 %w and more preferably in the range of from 47 to 50 %w of moisture.
  • the buffering agent preferably comprises a mixture of an organic acid and salt of an organic acid.
  • the salt component e.g. the ammonium or alkali metal salt of the organic acid
  • the acid component the acid which is generated in situ during the hydrolysis of the hemicellulose, i.e. acetic acid.
  • the buffering agent will be complete as soon as some of the generated acetic has dissolved in the aqueous medium containing the salt component of the buffering agent.
  • the initial pH of the aqueous medium will be governed by the concentration and nature of said salt component.
  • the softening of the low-quality wood is preferably conducted at a temperature in the range of from 170 to 220 °C, and at a pressure which higher than the equilibrium vapour pressure of the aqueous medium at the operating temperature.
  • steam is a preferred source of heat for use in the process of the present invention.
  • the actual heating is effected by allowing steam to condense on the surface of the sections of the low-quality wood.
  • the ultimate temperature difference between the outside and centre of a section is not more than 20 °C and preferably not more than 10 °C.
  • the time required, to achieve such a temperature equilibrium will be largely determined by the dimensions of the sections i.e. the shortest distance to the centre of a section, over which the heat has to be transferred. For regularly shaped sections, e.g. sections having a circular or rectangular cross-section, said distance will correspond with 50% of the diameter or 50% of the shortest side of said cross-section respectively.
  • any acidic compound formed within the lignocellulosic material i.e. the low-quality wood will be neutralized, thereby preventing the acid catalysed degradation of the cellulosic fibres. Consequently the residence time of the low-quality wood sections at the softening temperature will be less critical and in general may be up to 2 hours longer compared to the situation in the absence of a pH buffer, while with very high concentrations of said buffer, it is anticipated that residence times far in excess of the hereinbefore mentioned 2 hours are also permissible.
  • the low-quality wood which may be employed as starting material in the process of the present invention will generally comprise sections of lightwood, i.e. materials characterised by a low density, relatively poor mechanical performance properties and poor moisture resistance.
  • the use of said lightwood starting material in the present process will result in a product showing significantly improved mechanical performance properties and moisture resistance.
  • Examples of trees yielding such lightwood include spruce, poplar, willow beech pine and eucalyptus, i.e. trees which generally have a high growth rate.
  • Sections of heavywood may suitably also be upgraded in the present process, however, with these materials the most important improvement will be found in the moisture resistance.
  • the maximum size of the smallest dimension of the sections which can be successfully upgraded in the process of the present invention will be also dependent on the nature of the lignocellulosic material to be used, as it can be expected that the heat transfer through a low density wood from surface to centre will require less time than would be the case for a section of similar dimensions having a higher density.
  • the smallest dimension of a lightwood section for use in the present process may be considerably larger than for one based on heavywood.
  • the starting materials are preferably trunks or boards of wood, i.e. elongated sections of wood.
  • the minimum length is preferably at 25 cm, more preferably at least 50 cm, still more preferably least 1 m.
  • the starting material usually will have a width and thickness of at least 2 x 2 cm (especially when heavy wood is used), preferably 3 x 3 cm, more preferably 4 x 4 cm.
  • the length of the different pieces of starting material are the same or almost the same.
  • the starting material may have a square or rectangular diameter, but also a circular, hemicircular or even irregular diameter is possible.
  • the reactor contents are cooled to temperature below 100 °C before the reactor is opened.
  • the softened material is submitted to a dewatering treatment to remove most of the aqueous medium, if not all.
  • Dewatering may be effected, for example, by the application of pressure to the material by means of rollers and/or a press, by vacuum evaporative drying techniques or via chemical means, e.g. by contacting with a suitable adsorbent or absorbent.
  • the temperature should not exceed 100 °C and preferably not exceed 80 °C, in order to prevent premature cure or cross-linking occurring in the softened material.
  • the dewatering stage is conducted after having cooled the softened material to a temperature below 10 °C.
  • the reactive compounds formed during the hydrolysis of the hemicellulose and/or disproportionation of the lignin have a low solubility or are insoluble in the aqueous medium. This will thus reduce the loss of said reactive compounds during the dewatering stages, which compounds play a vital part in the subsequent curing stage.
  • the product of the softening stage and the dewatering stage is a soft material capable of being easily moulded. Accordingly, a most convenient method of effecting the process of the invention is to cure the material being processed in a heated mould. This enables the aggregate product to be formed in any desired shape. Sufficient pressure is applied during curing in the mould to achieve a product of the required density and shape, such pressures typically ranging from 10 5 Pa to 5.10 6 Pa (1 bar to 50 bar), often pressures in the range of from 3.10 5 Pa to 2.10 6 Pa (3 to 20 bar) being sufficient for most purposes. Curing is effected at a temperature in the range of from 100 °C to 220 °C, typically from 140 °C to 200 °C.
  • the duration of the curing stage will vary according to the material being cured and the prevailing temperature. Complete curing will require a residence time of from 10 minutes to, in some cases, up to 10 hours. In most cases a cure time in the range of from 1 to 3 hours will be sufficient to obtain a high-quality wood material.
  • Any aqueous medium present in the softened lignocellulosic material after the dewatering stage will almost certainly be removed via evaporation during the subsequent curing stage.
  • the term "mould”, wherein the dewatered softened wood is to be cured, should be interpreted to also include a platen press equipped with spacers and further auxiliary equipment, wherein regularly shaped, softened sections are placed next to one another for curing. Should the dimensions of the ultimate desired composite be such that it can not be directly obtained from a single softened section, this can be remedied by employing a mould having the required dimensions and introducing therein a sufficient number of softened sections and cure them together to provide the desired composite.
  • the sections of high-quality wood prepared according to the process of the present invention have maintained the typical wood-appearance characteristics of the starting material, i.e. the presence of a grain.
  • the presence of said grain in the ultimate composites confirms that the elongate cellulosic structure of the starting material has been maintained, and allows the obtained composites to be worked by the same techniques as untreated wood, e.g. sawing and planing.
  • Sections of air-dry sawn poplar having the following dimensions: length 2 m, width 20 cm and thickness 5 cm, were soaked overnight in an aqueous solution containing 0,6 g or 6 g sodium acetate / litre water respectively, and having a temperature of 95 °C. Subsequently the soaked wooden sections were heated in a closed vessel by means of steam of 200 °C condensing on the surface of the sections, until the temperature in the centre of the sections was 185 °C while the temperature at the outside was 200 °C, which temperatures were reached in 1.5 hours.
  • the contents of the vessel were cooled to 10 °C before opening the vessel, whereupon the softened sections were transferred to a press and compressed for 5 minutes during which the pressure was gradually increased from 1 to 3 bar, to stimulate the removal of the aqueous phase.
  • the dewatered and softened sections were placed next to one another in a platen press, having a temperature of 195 °C, of which both plates were provided with a dewatering screen.
  • the outside sections were supported with a piece of untreated light wood having a somewhat higher thickness than the softened sections, to prevent excessive deformation during the subsequent compression.
  • two stainless steel spacers having thickness of 3 cm were placed on the lower plate which thickness corresponded with the ultimate thickness of the desired composites (planks).
  • the press was closed for which a pressure of 5.10 5 Pa (5 bar) was required, and the samples were held at 195 °C for 1.5 hours. Subsequently the material was allowed to cool to ambient temperature before being evaluated.
  • the evaluation results have been collected in Table 1 hereinafter.
  • Table 1 Na acetate g/l 6 0.6 - Initial pH 7.9 7 6.6 Ultimate pH 5 4 3 Density, g/cm 3 ( ⁇ ) 0.7 0.7 0.7 Shore D hardness units 70 65 30 Bending strength, MPa ( ⁇ ) 125 115 60 Specific bending strength ( ⁇ / ⁇ ) 175 165 85 From the data collected in Table 1 it can be observed that the mechanical performance properties of the composites prepared according to the process of the present invention are far superior to those prepared according to a process outside the scope of the present invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Claims (10)

  1. Verfahren zur Veredelung von Holz mit niedriger Qualität zu Holz mit hoher Qualität, das folgendes umfaßt:
    a) einen Erweichungsschritt, worin ein oder mehrere Abschnitte von Holz niedriger Qualität auf eine Temperatur im Bereich von 160 bis 240°C in Gegenwart eines wäßrigen Mediums und bei einem Druck erhitzt werden, der wenigstens dem Gleichgewichtsdampfdruck dieses wäßrigen Mediums bei der Betriebstemperatur entspricht, wodurch die Hemicellulose wenigstens partiell hydrolysiert und das in dem Holz vorliegende Lignin disproportioniert wird,
    b) einen Entwässerungsschritt und
    c) einen Härtungsschritt bei einer Temperatur im Bereich von 100°C bis 220°C, dadurch gekennzeichnet, daß der Erweichungsschritt in Gegenwart eines gepufferten wäßrigen Mediums mit einem pH-Wert im Bereich von 3,5 bis 8 ausgeführt wird.
  2. Verfahren nach Anspruch 1, worin der pH-Wert des gepufferten wäßrigen Mediums im Bereich von 4 bis 6,5 liegt.
  3. Verfahren nach Anspruch 1 oder 2, worin das Puffermittel ein Gemisch aus einer organischen Säure und einem Salz einer organischen Säure ist.
  4. Verfahren nach Anspruch 3, worin das Puffermittel ein Gemisch aus Essigsäure und einem Ammonium- oder Alkalimetallsalz hievon oder ein Gemisch aus Zitronensäure und einem Ammonium- oder Alkalimetallsalz hievon ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, worin die Konzentration des Puffers im Bereich von 0,01 bis 2 Mol/l liegt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, worin ein oder mehrere Abschnitte von lufttrockenem Holz niedriger Qualität mit dem wäßrigen Medium, das zumindest die Salzkomponente des Puffermittels enthält, imprägniert werden.
  7. Verfahren nach einem der Ansprüche 3 bis 6, worin die Säurekomponente des Puffermittels in situ während des Erweichungsschrittes gebildet wird und die Salzkomponente zu dem wäßrigen Medium vor diesem Erweichungsschritt zugesetzt wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, worin das Erweichen bei einer Temperatur im Bereich von 170 bis 220°C ausgeführt wird und das Härten bei einer Temperatur im Bereich von 140 bis 200°C vorgenommen wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, worin die letzten Endes vorliegende Temperaturdifferenz zwischen dem Inneren und der Außenseite der Abschnitte im Erweichungsschritt nicht mehr als 20°C und vorzugsweise nicht mehr als 10°C beträgt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, worin die erweichten Abschnitte auf eine Temperatur unter 100°C abgekühlt werden, bevor sie aus dem Reaktor entnommen werden.
EP94201159A 1993-04-29 1994-04-27 Verfahren zur Verbesserung von Holz niedriger Qualität Expired - Lifetime EP0623433B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP93201237 1993-04-29
EP93201237 1993-04-29

Publications (2)

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EP0623433A1 EP0623433A1 (de) 1994-11-09
EP0623433B1 true EP0623433B1 (de) 1996-08-28

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EP94201159A Expired - Lifetime EP0623433B1 (de) 1993-04-29 1994-04-27 Verfahren zur Verbesserung von Holz niedriger Qualität

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EP (1) EP0623433B1 (de)
AT (1) ATE141851T1 (de)
DE (1) DE69400417T2 (de)
DK (1) DK0623433T3 (de)
ES (1) ES2091087T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011104025A1 (de) 2010-06-11 2011-12-15 Technische Universität Dresden Verfahren zur Modifizierung von Holz oder Holzwerkstoffen sowie chemisch und thermisch modifiziertes Holz

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2751580B1 (fr) * 1996-07-26 1998-10-16 N O W New Option Wood Procede de retification du bois
DE20112599U1 (de) * 2001-08-01 2002-12-19 Kronospan Tech Co Ltd MDF-Platte nebst Herstellung
NL2000405C2 (nl) * 2006-12-22 2008-06-24 Willems Holding B V W Werkwijze voor het verduurzamen van hout, houtproduct en inrichting daarvoor.
DE102009047137A1 (de) 2009-11-25 2011-05-26 Institut Für Holztechnologie Dresden Gemeinnützige Gmbh Verfahren zur thermischen Modifizierung oder Vergütung von Holz und Holzprodukten
WO2012153183A1 (en) * 2011-05-10 2012-11-15 Stora Enso Oyj A process for the treatment of wood comprising impregnating with citric acid followed by curing at high temperature.
CN103753661B (zh) * 2014-01-17 2016-06-15 华南农业大学 一种桉木指接地板的制备方法
CN104960052A (zh) * 2015-05-28 2015-10-07 阜南县金威工艺品有限公司 一种柳条软化方法
DE102015013450A1 (de) 2015-10-16 2016-04-14 Daimler Ag Verfahren zum Herstellen eines Holzzierteils
CN105946068A (zh) * 2016-05-19 2016-09-21 安徽德润工艺品有限公司 一种藤条软化处理方法
CN106272815A (zh) * 2016-08-27 2017-01-04 安徽省阜南志峰工艺品有限公司 一种用于编织狗舍的杞柳处理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0373726A2 (de) * 1988-12-16 1990-06-20 Shell Internationale Researchmaatschappij B.V. Zellulosefaser-Aggregat und Verfahren zu dessen Herstellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1236255A (en) * 1985-03-15 1988-05-10 Peter Favot Process for densifying low density woods
ATE124736T1 (de) * 1988-12-16 1995-07-15 Shell Int Research Zellulosefaser-aggregat und verfahren zu dessen herstellung.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0373726A2 (de) * 1988-12-16 1990-06-20 Shell Internationale Researchmaatschappij B.V. Zellulosefaser-Aggregat und Verfahren zu dessen Herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011104025A1 (de) 2010-06-11 2011-12-15 Technische Universität Dresden Verfahren zur Modifizierung von Holz oder Holzwerkstoffen sowie chemisch und thermisch modifiziertes Holz

Also Published As

Publication number Publication date
EP0623433A1 (de) 1994-11-09
DE69400417D1 (de) 1996-10-02
DE69400417T2 (de) 1997-02-13
ES2091087T3 (es) 1996-10-16
DK0623433T3 (da) 1996-09-16
ATE141851T1 (de) 1996-09-15

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