WO2010089604A1 - Modification chimique de matière lignocellulosique - Google Patents

Modification chimique de matière lignocellulosique Download PDF

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Publication number
WO2010089604A1
WO2010089604A1 PCT/GB2010/050184 GB2010050184W WO2010089604A1 WO 2010089604 A1 WO2010089604 A1 WO 2010089604A1 GB 2010050184 W GB2010050184 W GB 2010050184W WO 2010089604 A1 WO2010089604 A1 WO 2010089604A1
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Prior art keywords
lignocellulosic material
material product
hardened
providing
product according
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PCT/GB2010/050184
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English (en)
Inventor
Justin Martin
Peter Mcarthur
Roy Tilleard
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Kurawood Plc
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Publication of WO2010089604A1 publication Critical patent/WO2010089604A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • 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
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/156—Combined with grafting onto wood fibres

Definitions

  • the present invention relates to a method for the chemical modification of lignocellulosic material and lignocellulosic material formed from such a method.
  • the present invention relates to a method for modifying lignocellulosic material which comprises an acetic anhydride treatment step and introducing an organic material into the lignocellulosic material.
  • Lignocellulosic materials such as timber, contain an abundance of chemical groups called "free hydroxyls". Free hydroxyl groups readily absorb and release water according to changes in the climatic conditions to which they are exposed. This is the main reason why lignocellulosic material's dimensional stability is impacted by swelling and shrinking. It is also believed that the digestion of lignocellulosic material by enzymes initiates at these free hydroxyl sites, which is one of the principal reasons why, wood is prone to decay.
  • acetylation increases the lignocellulosic material's natural acetyl content through impregnation of acetic anhydride at high temperature and pressure, effectively changing the free hydroxyls within the lignocellulosic material into acetyl groups.
  • Acetic anhydride is the chemical compound with the formula (CH 3 CO) 2 O.
  • acetic anhydride is a colourless liquid that smells strongly of acetic acid, (also known as ethanoic acid), an organic chemical compound giving vinegar its sour taste and pungent smell.
  • acetic acid also known as ethanoic acid
  • the acetylation process when applied to lignocellulosic material, is known to produce significant improvements to both 'dimensional stability' (up to about 75%) by greatly reducing the lignocellulosic materials ability to absorb water and 'durability' by preventing the growth of fungi as well as to repel insects and termites, both arising from changing the free hydroxyls within the lignocellulosic material into said acetyl groups.
  • a method for providing a hardened lignocellulosic material product comprising: providing a lignocellulosic material product; impregnating the lignocellulosic material product with an acetic anhydride based formulation with an acidic pH which at least partially acetylates the lignocellulosic material product; impregnating the lignocellulosic material product with an aqueous organic based formulation; providing a pressurised environment for the lignocellulosic material product impregnated with the acetic anhydride and the aqueous organic based formulation; heating the lignocellulosic material product with the impregnated acetic anhydride and the organic based formulation to thereby cure organic material within the lignocellulosic material product; wherein the cured organic material within the lignocellulosic material product increases the strength of the lignocellulosic material
  • the present invention therefore relates to a method for treating lignocellulosic material (e.g. wood) which improves, for example, the hardness and/or strength of the lignocellulosic material.
  • the treated lignocellulosic material may substantially retain the look and feel of natural timber. It is also found that volume and/or density may also be added to the lignocellulosic material as the aqueous organic based formulation may impregnate itself within and/or onto the microstructure of the lignocellulosic material.
  • the treated lignocellulosic material may be found to have greater longevity than untreated lignocellulosic material and may resist shrinkage and/or warping.
  • the treated lignocellulosic material may therefore have improved hardness, dimensional stability, durability, machinability and/or coat ability.
  • the cured organic material within the acetylated lignocellulosic material product may chemically reduce the corrosiveness of any un-reacted acetic anhydride and residual acetic acid.
  • the present invention may therefore relate to a method for treating acetylated lignocellulosic material (e.g. wood) which may reduce, for example, the pungent smell of any un-reacted acetic anhydride and residual acetic acid.
  • acetylated lignocellulosic material e.g. wood
  • the present invention may also relate to a method for treating acetylated lignocellulosic material which reduces, for example, the corrosiveness of un- reacted acetic anhydride and residual acetic acid, in turn negating the requirement for all equipment to be made of stainless steel.
  • the lignocellulosic material may be treated with an acetic anhydride formulation with an acidic pH of about 0 to 7, about 1 to 6, about 2 to 5 or about 3.
  • the temperature of the lignocellulosic material may be elevated to about 50 Q C - 300 Q C or about 100 Q C - 200 Q C for the addition of the acetic anhydride.
  • the concentration of the acetic anhydride formulation may be about 0.001 - 10 M, about 0.01 - 10 M, about 0.1 - 10 M, about 1 - 10 M or about 5 - 10 M.
  • the lignocellulosic material may be treated with the acetic anhydride for at least about 5 minutes, at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes or at least about 60 minutes.
  • the acetic anhydride may convert at least some or substantially all of the free hydroxyl groups in the lignocellulosic material into acetyl groups. Typically, about 20%, 40%, 60%, 80% or about 100% of the free hydroxyl groups in the lignocellulosic material may be converted into acetyl groups.
  • the lignocellulosic material may be any type of wood based material wherein the cured organic material may, for example, be crosslinked within the lignocellulosic material product.
  • a further advantage of the present invention is that the lignocellulosic material pre- and post-modification may retain substantially the same dimensions. This is an advantage as prior art treatments result in shrinkage of the lignocellulosic material which may lead to inconsistencies and/or weak areas being formed in the treated lignocellulosic material.
  • the present invention also provides for the advantageous feature that the organic material trapped within the lignocellulosic material product does not adversely affect the lignocellulosic material such as causing rot as would be done by a sugar based material (e.g. maltodextrin) if that were left in the lignocellulosic material.
  • a sugar based material e.g. maltodextrin
  • the cured organic material is also not edible by wood-destroying material such as fungi and insects.
  • the present invention may therefore not use sugars, for example, maltodextrin or oligosaccharides.
  • the present invention may not use an external catalyst such as from the group consisting of ammonium salts, metal salts, organic acids, inorganic acids and mixtures thereof.
  • the present invention may also not use a setting agent (e.g. 2,2-bis(t-butyl peroxy) butane, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, 2,5-dimethyl-2,5-di(t- butyl peroxy) hexyne-3, n-butyl-4,4-bis(t-butyl peroxy) valerate, 1 ,1 -bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane, and mixtures thereof) which again reduces complexity and cost in the manufacture of the formulation.
  • a setting agent e.g. 2,2-bis(t-butyl peroxy) butane, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, 2,5-dimethyl-2,5-di(t- butyl peroxy) hexyne-3, n-butyl-4,4
  • the present invention also preferably uses water as a solvent for the aqueous organic based formulation and preferably does not use toxic and/or volatile solvents.
  • the solvent may be in an ionic or a non-ionic form.
  • Many prior art methods use toxic materials (e.g. styrenes and polyesters) or gamma radiation which leads to a complex and dangerous treatment procedure.
  • Using a water based system also makes the system much more cost effective and efficient to use industrially.
  • Other prior art methods also use an argon or nitrogen gas based atmosphere system which again leads to a costly complicated process.
  • the present invention preferably does not use an inert gas atmosphere such as argon and avoids using toxic materials (e.g. styrenes and polyesters).
  • the present invention therefore preferably uses standard atmospheric air.
  • the aqueous organic based formulation may react with the lignocellulosic material to produce a biopolymer within said lignocellulosic material.
  • the resulting product retains the visual appearance of the lignocellulosic material but however contains a significant quantity of the new biopolymer which has a beneficial effect on a number of characteristics of the lignocellulosic material.
  • improved features are noted as any one of or combination of the following: increased density; increased hardness; increased strength; increased stiffness; increased fire resistant properties; and improved performance when machined, coated with surface coating materials including surface stains, lacquers, paints and powder coatings of all types.
  • the lignocellulosic material product may be a soft lignocellulosic material such as lignocellulosic material selected from any one of or combination of the following: Pines; Hemlocks; Aspen; Beach; Birch; Albizzia; Balsa; lroko (chlorophora excelsa); Jelutong (dyera costulata); Merbau (intsia palembacia); Tawa (beilschmiedia tawa); Radiata Pine (pinus radiate); European Beech (gagus syivatica); Eucalyptus (eucalyptus deglupta); Cotton Wood (populusdeltoids); Rubber Wood (hevea brasiliensis); Baltic Pine (pinus sylvestris); Ponderosa Pine (pinus ponderosa); Hoop Pine (araucaria cunninghamii); Carribbean Pine (pinus caribaea); Loblolly Pine (pinus taed
  • lignocellulosic material product is also intended to cover timber or lumber, which is either standing or which has been processed for use.
  • timber is a term also used for sawn lignocellulosic material products (that is, planks or boards), whereas generally in the United States and Canada, the product of timber cut into planks or boards is referred to as "lumber”.
  • the lignocellulosic material for the present invention may be lignocellulosic material obtained directly from cutting from a felled tree.
  • the member of lignocellulosic material may be of any dimension but may preferably be constituted of entirely saplignocellulosic material from the felled tree, being the newly formed outer lignocellulosic material located just inside the vascular cambium of a tree trunk and active in the conduction of water.
  • the hardened lignocellulosic material product may be used in a variety of uses where timber products are used externally such as soffets, window frames, cills, doors and door frames, conservatories, barge boards, fascia boards, garden sheds, decking and timber framed buildings and the like.
  • the hardened lignocellulosic material product may be used for indoor products as well such as furniture, for joinery products and for food items such as food bowls.
  • the member of lignocellulosic material used in the present invention may be a soft lignocellulosic material but after treatment according to the present invention the member of lignocellulosic material may have many of the properties of a hard lignocellulosic material.
  • the use of hard lignocellulosic materials is restricted due to their expense and time to grow such trees.
  • the present invention therefore also provides significant conservation benefits as it reduces the use of hard lignocellulosic materials.
  • any type of lignocellulosic material product may be used so long as it is capable of absorbing the aqueous organic based formulation.
  • about 1 m 3 of the lignocellulosic material product may absorb greater than about 100 litres, 200 litres, 300 litres, 400 litres, 500 litres, 600 litres, 700 litres, 800 litres, 900 litres or 1 ,000 litres of the aqueous organic based formulation.
  • about 1 m 3 of the lignocellulosic material product may absorb greater than about 500 litres of the aqueous organic based formulation. By being absorbed is also meant to cover impregnation.
  • the acetic anhydride formulation and/or the aqueous organic based formulation may be absorbed and/or impregnated separately or as a mixture into lignocellulosic material product such as into and/or onto the microstructure of the lignocellulosic material containing the cells, cell walls and/or pores.
  • the acetic anhydride formulation may be impregnated first and then the aqueous organic based formulation.
  • the acetic anhydride formulation and the aqueous organic based formulation may be mixed together and then added to the lignocellulosic material product as a mixture.
  • the pressurised environment may be a pressure vessel within which the lignocellulosic material product may be placed and sealed. The pressurised environment may be used to reduce and/or increase the air pressure around the lignocellulosic material product.
  • the lignocellulosic material product may be placed in the pressure vessel.
  • the pressure may, for example, be increased during the addition of the acetic anhydride.
  • the pressure may be increased to over atmospheric pressure, over about 2 atmospheres, over about 3 atmospheres, over about 4 atmospheres or over about 10 atmospheres.
  • the temperature may be elevated to about 50 Q C - 300 Q C or about 100 Q C - 200 Q C.
  • the lignocellulosic material product may be impregnated with the acetic anhydride for about 5 - 60 minutes, about 1 - 2 hours or more if necessary.
  • the pressure inside the pressure vessel may, for example, be reduced below atmospheric pressure and preferably down to a vacuum or substantially a vacuum.
  • Typical pressures may, for example, be below about 100 kPa, below about 80 kPa, below about 60 kPa, below about 40 kPa, below about 20 kPa or below about 10 kPa.
  • Any suitable type of pump such as a vacuum pump may be used for such a process.
  • a vacuum of, for example about -20 to -200 kPa or typically about -80 kPa may be drawn from the pressure vessel for a period of time such as, for example, about 10 minutes to 2 hours or typically about 30 minutes.
  • reducing the pressure has the effect that cells and/or pores in the microstructure within the lignocellulosic material product may be evacuated of air.
  • the reduction in pressure may be stopped or continued (i.e. the vacuum pump may be left running).
  • the aqueous organic based formulation may then be introduced into the reduced pressure environment such as the pressure vessel.
  • the organic based formulation may be introduced at a slow rate or preferably may be flooded as quickly as possible.
  • the aqueous organic based formulation may be fed into the reduced pressure environment until the environment is full or substantially full with the organic based formulation.
  • the reduced pressure such as the vacuum may therefore be used to draw the organic based solution into the reduced pressure environment. Although it is not essential to initially reduce the pressure, this simply facilitates the feeding of the aqueous organic based formulation into the pressure vessel due to the negative pressure.
  • the aqueous organic based solution may have about a neutral pH of about 7, a pH of about 6 - 8 or typically about 7.2.
  • the pressure pump may be used to increase the pressure. Pressures above about 200 kPa, above about 500 kPa, above about 1 ,000 kPa or above about 1 ,500 kPa may be used. Typically, a pressure of about 1 ,400 kPa may be used.
  • the pressure vessel with the fluid of the aqueous organic based formulation therein may then be kept at this increased pressure for a period of time such as at least about 5 minutes, at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes or at least about 60 minutes.
  • Maintaining the high pressure increases the absorption and/or impregnation of the aqueous organic based formulation into the microstructure of the lignocellulosic material product.
  • the increased pressure in the pressure vessel may be released and any excess aqueous organic based formulation may be drained and/or removed.
  • the method of the present invention may then include a further step of once again reducing the pressure inside the pressure vessel again using a vacuum pump pumping at, for example, about -80 kPa. The pressure may be reduced down to a vacuum or substantially a vacuum.
  • the pressure may be maintained at the reduced pressure for a period of time such as at least about 5 minutes, at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes or at least about 60 minutes.
  • This further reduction of pressure may be used to remove any surplus organic based formulation from the surface of the lignocellulosic material product and may also facilitate the impregnation and/or absorption of the aqueous organic based formulation into the microstructure of the lignocellulosic material product.
  • the pressure may then be allowed to return to normal atmospheric pressure. This return to normal atmospheric pressure may be allowed to occur quickly by opening a relief valve quickly. This sudden change of pressure may also facilitate the impregnation and/or absorption of the aqueous organic based formulation into the microstructure of the lignocellulosic material product.
  • any one of or combination of the above steps relating to the impregnation of the aqueous organic based formulation may be performed at room temperature.
  • all of the above steps relating to the impregnation of the aqueous organic based formulation may be performed at room temperature. This is a significant improvement over prior art techniques which usually use high elevated temperatures.
  • the present invention therefore does not use above room temperature or elevated temperatures during the impregnation of the aqueous organic based formulation. This has significant cost benefits as this provides lower energy consumption and allows less complex apparatus to be used.
  • the lignocellulosic material product may then be removed from the pressure vessel and a heat treatment applied. Any suitable type of heat treatment may be used such as an oven, hot air drying or treatment with a laser. In particular embodiments a kiln may be used.
  • the lignocellulosic material product may be heated to about 50 Q C - 200 Q C or about 60 Q C - 80 Q C with an airflow of, for example, about 8 m/s. By heating the lignocellulosic material product with the impregnated organic based formulation may cure the aqueous organic based formulation within the lignocellulosic material product.
  • Organic material may therefore be cured and/or set and/or fused within and/or onto the microstructure of the lignocellulosic material product.
  • the cured organic material within the lignocellulosic material product may increase the strength of the lignocellulosic material product and provides a hardened lignocellulosic material product.
  • the amount of organic material that can be deposited into the microstructure of the lignocellulosic material may be varied by increasing the solids content of the organic aqueous formulation.
  • the organic aqueous formulation may have a solids content of about 10% by weight (67 kg/m 3 ), about 20% by weight (134 kg/m 3 ), about 30% by weight (201 kg/m 3 ), about 40% by weight (268 kg/m 3 ), about 50% by weight (335 kg/m 3 ) or about 60% by weight (402 kg/m 3 ).
  • cure includes polymerisation, etc. or other chemical reformation, irrespective of whether or not to completion.
  • the aqueous organic based formulation may be a solution comprising an organic material of high molecular weight polymer or resin with an average molecular weight of between any of the following: 100 - 10,000; 150 - 5,000; 200 - 1 ,000; 250 - 750; 250 - 500; or 290 - 470.
  • the aqueous organic based formulation may substantially use water as the solvent although any other suitable solvents may also be used.
  • the molecular weight of the organic material in the aqueous organic based formulation relates to the rate and ability for the organic material to penetrate into the lignocellulosic material and also stay there once the pressure has been returned to atmospheric pressure.
  • the organic material may be a high molecular weight polymeric based material such as a condensation polymer or an amide, an amine, an ester, aldehyde, ketone, anhydride or an alkyd based material.
  • the alkyd based material may be an alkyd resin.
  • An alkyd resin may be a synthetic resin formed by the condensation of polyhydric alcohols with polybasic acids. The most common polyhydric alcohol used may be glycerol, and polybasic acid may be phthalic anhydride. Modified alkyds may be those in which the polybasic acid may be substituted in part by a monobasic acid, of which the vegetable oil fatty acids are typical.
  • the aqueous organic based formulation and/or organic material may be based on a coconut alkyd such as high-solids, short oil alkyds with a viscosity measure of, for example, Z 5 to Z 6 on the Gardner- Holdt Viscometer Scale at 30 s C.
  • a coconut alkyd such as high-solids, short oil alkyds with a viscosity measure of, for example, Z 5 to Z 6 on the Gardner- Holdt Viscometer Scale at 30 s C.
  • the molecular weight of the aqueous organic based formulation may be sufficiently low to enable the organic based solution to pass through the lignocellulosic material surface, cell walls and/or pores of the lignocellulosic material product. As indicated above this process may be achieved (i.e. catalysed) through pressure and/or heat.
  • the aqueous organic based formulation may comprise a solvent used in which may be driven and/or evaporated off leaving behind an organic material that binds and cures to the microstructure of the lignocellulosic material product (e.g. inside the lignocellulosic material product) such as the cell walls and/or pores.
  • the organic material remains within the microstructure once it is forced into the microstructure under increased pressure. This is facilitated by the relatively high molecular weights of the organic material.
  • the increased pressure and/or heat helps to start a chemical reaction of the aqueous organic based formulation and starts a curing process.
  • the hardened lignocellulosic material product formed may have a Janka hardness of: at least about 5,000 N/mim 2 ; at least about 6,000 N/mim 2 ; at least about 7,000 N/mim 2 ; at least about 8,000 N/mim 2 ; at least about 8,000 N/mim 2 ; at least about 9,000 N/mim 2 or at least about 10,000 N/mm 2 .
  • the hardened lignocellulosic material product formed may have a Janka hardness of: about 4,000 N/mm 2 - 20,000 N/mm 2 ; about 4,000 N/mm 2 - 15,000 N/mm 2 ; about 4,000 N/mm 2 - 12,000 N/mm 2 or about 7,000 N/mm 2 - 10,000 N/mm 2 .
  • the hardness of the initial lignocellulosic material product may be increased by at least about 10%, at least about 30%, at least about 50%, at least about 70%, at least about 100% or at least about 200%.
  • the Janka Hardness is based on lignocellulosic material conditioned at 65% relative humidity and 200 Q C. Values are heavily influenced by local growth conditions.
  • the hardened lignocellulosic material product formed may have a density of: at least about 500 kg/m 3 ; at least about 600 kg/m 3 ; at least about 700 kg/m 3 ; at least about 800 kg/m 3 ; at least about 900 kg/m 3 or at least about 1 ,000 kg/m 3 .
  • the hardened lignocellulosic material product formed may have a density of: about 400 - 2,000 kg/m 3 ; about 400 - 1 ,500 kg/m 3 ; about 500 - 1 ,000 kg/m 3 ; about 600 - 2,000 kg/m 3 ; about 700 - 2,000 kg/m 3 .
  • the density of the initial lignocellulosic material product may be increased by at least about 10%, at least about 30%, at least about 50%, at least about 70%, at least about 100% or at least about 200%.
  • a method for providing a hardened lignocellulosic material product comprising: providing a lignocellulosic material product; impregnating the lignocellulosic material product with an acetic anhydride based formulation which at least partially acetylates the lignocellulosic material product; impregnating the lignocellulosic material product with an aqueous organic based formulation; providing a pressurised environment for the lignocellulosic material product impregnated with the acetic anhydride and the aqueous organic based formulation; heating the lignocellulosic material product with the impregnated acetic anhydride and the organic based formulation to thereby cure organic material within the lignocellulosic material product; wherein the cured organic material within the lignocellulosic material product increases the strength of the lignocellulosic material product and provides a
  • a method for providing a hardened lignocellulosic material product comprising: providing a lignocellulosic material product; impregnating the lignocellulosic material product with an acetic anhydride based formulation which at least partially acetylates the lignocellulosic material product to form acetylated lignocellulosic material product; impregnating the lignocellulosic material product with an aqueous organic based formulation; providing a pressurised environment for the lignocellulosic material product impregnated with the acetic anhydride and the aqueous organic based formulation; heating the lignocellulosic material product with the impregnated acetic anhydride and the organic based formulation to thereby cure organic material within the lignocellulosic material product; wherein the acetylated lignocellulosic material product is
  • a hardened lignocellulosic material product which has acetylated hydroxyl groups formed by adding acetic anhydride and organic material cured within the lignocellulosic material product which increases the strength of the lignocellulosic material product and provides a hardened lignocellulosic material product.
  • the hardened lignocellulosic material product may be formed using the method as described in the first aspect.
  • a fifth aspect of the present invention there is provided use of the hardened lignocellulosic material product as defined in the first aspect in soffets, window frames, window sills, doors and door frames, conservatories, barge boards, fascia boards, garden sheds, decking and timber framed buildings and the like and indoor products as well such as furniture, for joinery products and for food items such as food bowls.
  • the present invention resides in the provision of introducing acetic anhydride and organic material into a lignocellulosic material product and curing the organic material within the microstructure of the lignocellulosic material product.
  • the acetic anhydride at least partially acetylates the lignocellulosic material to form acetylated lignocellulosic material.
  • the lignocellulosic material may be fully or substantially acetylated.
  • the acetylated lignocellulosic material may chemically reduce the corrosiveness of any un-reacted acetic anhydride and residual acetic acid. This is advantageous as this may reduce, for example, the pungent smell of any un-reacted acetic anhydride and residual acetic acid. Moreover, in the present invention as the cured organic material may reduce or fully reduce the corrosiveness of any un-reacted acetic anhydride this negates the need for the requirement of all manufacturing equipment to be made of stainless steel.
  • the lignocellulosic material product may be a soft lignocellulosic material product (e.g. Pines; Hemlocks; Aspen; Beach; Birch Wood; Albizzia; Balsa; lroko (chlorophora excelsa); Jelutong (dyera costulata); Merbau (intsia palembacia); Tawa (beilschmiedia tawa); Radiata Pine (pinus radiate); European Beech (gagus syivatica); Eucalyptus (eucalyptus deglupta); Cotton Wood (populusdeltoids); Rubber Wood (hevea brasiliensis); Baltic Pine (pinus sylvestris); Ponderosa Pine (pinus ponderosa); Hoop Pine (araucaria cunninghamii); Carribbean Pine (pinus caribaea); Loblolly Pine (pinus taeda); Hemlock (tsuga canadensis
  • An acetic anhydride formulation at about 1 M and a pH of about 3 is then added at over atmospheric pressure to the lignocellulosic material product.
  • the lignocellulosic material product is then heated to about 100 Q C for about 30 minutes.
  • the pressure within the pressure vessel is then be reduced using a vacuum pump operating at about -80 kPa for about 30 minutes.
  • the pressure is reduced down to a vacuum or substantially a vacuum.
  • a vacuum pump is used for this process.
  • an aqueous organic based formulation is then quickly flooded into the pressure vessel.
  • the reduced pressure in effect, sucks the aqueous organic based formulation of a pH of about 7 into the pressure vessel and into the lignocellulosic material product.
  • the lignocellulosic material product therefore starts to become impregnated and/or absorbed with the aqueous organic based formulation.
  • the aqueous organic based formulation is therefore absorbed and/or impregnated into the lignocellulosic material product such as into the microstructure of the lignocellulosic material containing the cells, cell walls and/or pores.
  • About 1 m 3 of the lignocellulosic material product is capable of absorbing about 670 litres of the aqueous organic based formulation.
  • the pressure in the pressure vessel is then increased to above, for example, atmospheric pressure.
  • the pressure pump is used to increase the pressure to about 1 ,400 kPa. Maintaining the high pressure increases the absorption and/or impregnation of the aqueous organic based solution into the microstructure of the lignocellulosic material product.
  • the increased pressure in the pressure vessel is released and any excess aqueous organic based formulation is drained and/or removed.
  • the pressure inside the pressure vessel is then reduced again using a vacuum pump pumping at, for example, about -80 kPa.
  • the pressure may be reduced down to a vacuum or substantially a vacuum.
  • the pressure is then allowed to return to normal atmospheric pressure. This return to normal atmospheric pressure is allowed to occur quickly by opening a relief valve quickly.
  • a heat treatment is then applied to the lignocellulosic material product with the aqueous organic material impregnated into the microstructure of the lignocellulosic material product.
  • a kiln is used for the heat treatment.
  • the lignocellulosic material product is heated to about 60 Q C - 80 Q C with an airflow of, for example, about 8 m/s.
  • By heating the lignocellulosic material product with the impregnated organic based formulation cures the aqueous organic based formulation within the lignocellulosic material product.
  • Organic material is therefore cured within the microstructure of the lignocellulosic material product.
  • the cured organic material within the lignocellulosic material product increases the strength of the lignocellulosic material product and provides a hardened lignocellulosic material product.
  • the final formed product via the addition of acetic anhydride and aqueous organic based formulation is capable of forming a treated lignocellulosic material product wherein the cured organic material within the acetylated lignocellulosic material product chemically reduces the corrosiveness of at least some or substantially all of the un-reacted acetic anhydride and residual acetic anhydride.
  • any suitable type of aqueous organic based formulation may be used.
  • the aqueous organic based formulation may also be cured within the microstructure of the lignocellulosic material product using any suitable means.
  • any suitable form of acetic anhydride may be used.
  • the acetic anhydride and aqueous organic based formulation may be added in a two-step or single-step process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Wood Science & Technology (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

La présente invention porte sur un procédé de traitement de matière lignocellulosique et sur une matière lignocellulosique formée à partir d'un tel procédé. Plus particulièrement, l'invention porte sur un procédé qui permet de traiter une matière lignocellulosique avec de l'anhydride acétique et également d'introduire une matière organique dans la matière lignocellulosique et qui produit une matière lignocellulosique modifiée présentant l'une quelconque des propriétés suivantes ou une association de celles-ci : une dureté améliorée, une stabilité dimensionnelle améliorée, une durabilité améliorée, une aptitude à l'usinage améliorée et/ou une aptitude au couchage améliorée. La matière lignocellulosique modifiée conserve également en grande partie l'aspect et le toucher de la matière lignocellulosique naturelle.
PCT/GB2010/050184 2009-02-06 2010-02-05 Modification chimique de matière lignocellulosique WO2010089604A1 (fr)

Applications Claiming Priority (2)

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GB0901910A GB0901910D0 (en) 2009-02-06 2009-02-06 Chemical modification of lignocellulosic material
GB0901910.0 2009-02-06

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WO2010089604A1 true WO2010089604A1 (fr) 2010-08-12

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WO2014195860A1 (fr) 2013-06-03 2014-12-11 Chemconserve B.V. Fibres de bois modifiées pour la fabrication de composites
CN107322741A (zh) * 2017-08-10 2017-11-07 马鞍山市谷庆门业有限公司 一种杉木木板门加工工艺
DE102016222292A1 (de) * 2016-11-14 2018-05-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Acetyliertes Lignocellulose-Material mit autoadhäsiven Eigenschaften
WO2018224598A1 (fr) 2017-06-07 2018-12-13 Boitouzet Timothee Procédé de délignification partielle par voie supercritique ou subcritique et de remplissage d'un matériau ligno-cellulosique
US10260232B1 (en) 2017-12-02 2019-04-16 M-Fire Supression, Inc. Methods of designing and constructing Class-A fire-protected multi-story wood-framed buildings
US10290004B1 (en) 2017-12-02 2019-05-14 M-Fire Suppression, Inc. Supply chain management system for supplying clean fire inhibiting chemical (CFIC) totes to a network of wood-treating lumber and prefabrication panel factories and wood-framed building construction job sites
US10311444B1 (en) 2017-12-02 2019-06-04 M-Fire Suppression, Inc. Method of providing class-A fire-protection to wood-framed buildings using on-site spraying of clean fire inhibiting chemical liquid on exposed interior wood surfaces of the wood-framed buildings, and mobile computing systems for uploading fire-protection certifications and status information to a central database and remote access thereof by firefighters on job site locations during fire outbreaks on construction sites
US10332222B1 (en) 2017-12-02 2019-06-25 M-Fire Supression, Inc. Just-in-time factory methods, system and network for prefabricating class-A fire-protected wood-framed buildings and components used to construct the same
US10430757B2 (en) 2017-12-02 2019-10-01 N-Fire Suppression, Inc. Mass timber building factory system for producing prefabricated class-A fire-protected mass timber building components for use in constructing prefabricated class-A fire-protected mass timber buildings
US10538012B2 (en) 2015-12-07 2020-01-21 Timothee Boitouzet Process for partial delignification and filling of a lignocellulosic material, and composite material structure able to be obtained by this process
US10653904B2 (en) 2017-12-02 2020-05-19 M-Fire Holdings, Llc Methods of suppressing wild fires raging across regions of land in the direction of prevailing winds by forming anti-fire (AF) chemical fire-breaking systems using environmentally clean anti-fire (AF) liquid spray applied using GPS-tracking techniques
US10814150B2 (en) 2017-12-02 2020-10-27 M-Fire Holdings Llc Methods of and system networks for wireless management of GPS-tracked spraying systems deployed to spray property and ground surfaces with environmentally-clean wildfire inhibitor to protect and defend against wildfires
US11395931B2 (en) 2017-12-02 2022-07-26 Mighty Fire Breaker Llc Method of and system network for managing the application of fire and smoke inhibiting compositions on ground surfaces before the incidence of wild-fires, and also thereafter, upon smoldering ambers and ashes to reduce smoke and suppress fire re-ignition
US11656756B2 (en) 2018-02-09 2023-05-23 Sas Woodoo Touch detection device with touch interface made of composite material
US11826592B2 (en) 2018-01-09 2023-11-28 Mighty Fire Breaker Llc Process of forming strategic chemical-type wildfire breaks on ground surfaces to proactively prevent fire ignition and flame spread, and reduce the production of smoke in the presence of a wild fire
US11836807B2 (en) 2017-12-02 2023-12-05 Mighty Fire Breaker Llc System, network and methods for estimating and recording quantities of carbon securely stored in class-A fire-protected wood-framed and mass-timber buildings on construction job-sites, and class-A fire-protected wood-framed and mass timber components in factory environments
US11865394B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean biodegradable water-based concentrates for producing fire inhibiting and fire extinguishing liquids for fighting class A and class B fires
US11865390B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean water-based fire inhibiting biochemical compositions, and methods of and apparatus for applying the same to protect property against wildfire
US11911643B2 (en) 2021-02-04 2024-02-27 Mighty Fire Breaker Llc Environmentally-clean fire inhibiting and extinguishing compositions and products for sorbing flammable liquids while inhibiting ignition and extinguishing fire

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WO2014195860A1 (fr) 2013-06-03 2014-12-11 Chemconserve B.V. Fibres de bois modifiées pour la fabrication de composites
US10538012B2 (en) 2015-12-07 2020-01-21 Timothee Boitouzet Process for partial delignification and filling of a lignocellulosic material, and composite material structure able to be obtained by this process
US11254026B2 (en) 2015-12-07 2022-02-22 Timothée BOITOUZET Process for partial delignification and filling of a lignocellulosic material, and composite material structure able to be obtained by this process
EP3656520A1 (fr) 2015-12-07 2020-05-27 Boitouzet, Timothée Procede de delignification partielle et de remplissage d'un materiau ligno cellulosique, et structure de materiau composite susceptible d'etre obtenue par ce procede
DE102016222292A1 (de) * 2016-11-14 2018-05-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Acetyliertes Lignocellulose-Material mit autoadhäsiven Eigenschaften
WO2018224598A1 (fr) 2017-06-07 2018-12-13 Boitouzet Timothee Procédé de délignification partielle par voie supercritique ou subcritique et de remplissage d'un matériau ligno-cellulosique
US11820041B2 (en) 2017-06-07 2023-11-21 Sas Woodoo Process for supercritical or subcritical partial delignification and filling of a lignocellulosic material
CN107322741A (zh) * 2017-08-10 2017-11-07 马鞍山市谷庆门业有限公司 一种杉木木板门加工工艺
US11400324B2 (en) 2017-12-02 2022-08-02 Mighty Fire Breaker Llc Method of protecting life, property, homes and businesses from wild fire by proactively applying environmentally-clean anti-fire (AF) chemical liquid spray in advance of wild fire arrival and managed using a wireless network with GPS-tracking
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US10653904B2 (en) 2017-12-02 2020-05-19 M-Fire Holdings, Llc Methods of suppressing wild fires raging across regions of land in the direction of prevailing winds by forming anti-fire (AF) chemical fire-breaking systems using environmentally clean anti-fire (AF) liquid spray applied using GPS-tracking techniques
US10311444B1 (en) 2017-12-02 2019-06-04 M-Fire Suppression, Inc. Method of providing class-A fire-protection to wood-framed buildings using on-site spraying of clean fire inhibiting chemical liquid on exposed interior wood surfaces of the wood-framed buildings, and mobile computing systems for uploading fire-protection certifications and status information to a central database and remote access thereof by firefighters on job site locations during fire outbreaks on construction sites
US10814150B2 (en) 2017-12-02 2020-10-27 M-Fire Holdings Llc Methods of and system networks for wireless management of GPS-tracked spraying systems deployed to spray property and ground surfaces with environmentally-clean wildfire inhibitor to protect and defend against wildfires
US10899038B2 (en) 2017-12-02 2021-01-26 M-Fire Holdings, Llc Class-A fire-protected wood products inhibiting ignition and spread of fire along class-A fire-protected wood surfaces and development of smoke from such fire
US10919178B2 (en) 2017-12-02 2021-02-16 M-Fire Holdings, Llc Class-A fire-protected oriented strand board (OSB) sheathing, and method of and automated factory for producing the same
US10290004B1 (en) 2017-12-02 2019-05-14 M-Fire Suppression, Inc. Supply chain management system for supplying clean fire inhibiting chemical (CFIC) totes to a network of wood-treating lumber and prefabrication panel factories and wood-framed building construction job sites
US11395931B2 (en) 2017-12-02 2022-07-26 Mighty Fire Breaker Llc Method of and system network for managing the application of fire and smoke inhibiting compositions on ground surfaces before the incidence of wild-fires, and also thereafter, upon smoldering ambers and ashes to reduce smoke and suppress fire re-ignition
US10267034B1 (en) 2017-12-02 2019-04-23 M-Fire Suppression, Inc. On-job-site method of and system for providing class-A fire-protection to wood-framed buildings during construction
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US10430757B2 (en) 2017-12-02 2019-10-01 N-Fire Suppression, Inc. Mass timber building factory system for producing prefabricated class-A fire-protected mass timber building components for use in constructing prefabricated class-A fire-protected mass timber buildings
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