EP2421685A2 - Procédé amélioré de traitement d'un matériau poreux - Google Patents

Procédé amélioré de traitement d'un matériau poreux

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Publication number
EP2421685A2
EP2421685A2 EP10715087A EP10715087A EP2421685A2 EP 2421685 A2 EP2421685 A2 EP 2421685A2 EP 10715087 A EP10715087 A EP 10715087A EP 10715087 A EP10715087 A EP 10715087A EP 2421685 A2 EP2421685 A2 EP 2421685A2
Authority
EP
European Patent Office
Prior art keywords
wood
active ingredient
treatment
porous material
carrier fluid
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.)
Ceased
Application number
EP10715087A
Other languages
German (de)
English (en)
Inventor
Ole Henriksen
Anders Westh Kjellow
Joäo Luis Beja FERNANDES
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.)
Superwood Technologies Aps
Original Assignee
VKR Holding AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by VKR Holding AS filed Critical VKR Holding AS
Publication of EP2421685A2 publication Critical patent/EP2421685A2/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • 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
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • B27K3/086—Impregnating by pressure, e.g. vacuum impregnation using supercritical or high pressure fluids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/02—Staining or dyeing wood; Bleaching wood
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the present invention relates to an improved method for the treatment of a porous material, such as wood, more specifically a method in which an active ingredient to be deposited within the porous material in a first pressurisation step is kept in a mobile phase and in a second depressurisation step is kept in a stationary phase.
  • EP 1501664 discloses a method for treating wood having a certain length and being susceptible to damage using a supercritical fluid . Even though these methods have proven effective for solving the problems addressed therein they still fail, when used in combination with an active ingredient, to result in a satisfactory distribution of said active ingredient within a time span that is economically viable.
  • supercritical carbon d ioxide has repeatedly been investigated as a possible solvent for wood impregnation . The majority of the research has focused on the effects of supercritical treatment on the physical properties of wood and a wide variety of wood species have been treated with an equally wide array of organic biocides (e.g .
  • Impregnation or other treatments are often combined with the use of e.g. water repellents, biocides or other suitable active ingredients in the wood production and there is still a need for effective methods of treating wood wherein both the manufacturing time is economically feasible and the resulting piece of wood has a satisfactory distribution of active ingredient within this time span. Therefore, the aim of the present invention is to provide an improved method for treating porous materials, which will result in improved distribution of active ingredient in the material without increasing treatment times.
  • a method for the treatment of a porous material using a carrier fluid comprising the steps of pressurising and depressurising the porous material characterized in that the carrier fluid comprises at least one active ingredient and that the at least one active ingredient during the pressurisation step is kept in the mobile phase and that the at least one active ingredient during the depressurisation step is kept in the stationary phase.
  • Treatment of a porous materials using a carrier fluid e.g. a supercritical carrier fluid, can be regarded as a chromatographic process in which the fluid is considered the mobile phase and the porous material, such as wood fibre, is considered the stationary phase.
  • an active ingredients held in the mobile phase is absorbed or adsorbed in/by the stationary phase, i.e. the wood matrix.
  • Ways of doing this include increasing the gas phase concentration of active ingredient by adding more active ingredient to the system or controlling process parameters, such as flow rate, pressure and tem- perature and/or adding excipients to the carrier fluid in order to increase the affinity of the active ingredients towards the carrier fluid .
  • the carrier fluid/active ingredient system is determinative for the specific process and depends on the affinity of the active ingredient to the fluid and porous material, e.g . wood matrix, respectively. Specific determination of the process parameters is within the skill of the art once having recognized as the present inventors have that the determinative factor for a rapid even distribution is obtained by using the method of the present invention .
  • the rate at which active ingredients move through wood can be manipulated .
  • Wood is an example of a porous material behaving like a chromatographic column, any other material, which is constituted of a po- rous material such as cellulose, silica etc. will behave in the same way.
  • the partition ratio is defined as the concentration of active ingredients in the porous material/wood divided by the concentration of active ingredients in the carrier fluid .
  • a low partition ratio for a specific active ingredient is defined as a value, which is lower than the partition ratio of the same active ingredient using the prior art method .
  • the partition ratio should only be low as defined in the present context during the pressurisation step.
  • the magnitude of the partition ratio is dependent on the physical conditions.
  • the partition ratio decreases as the affinity of the actives to the solvent increases. To ensure a rapid movement of the active ingredients through e.g.
  • the pressure and tempera- ture cond itions during the pressurization and treatment parts of the treatment cycle must be chosen so that the corresponding partition ratios favour rapid active ing redient movement, and at the end of the treatment cycle, the process conditions are altered in a way that shifts the affinity of the actives towards the porous material, i.e. increasing the partition ratio.
  • the conditions should be chosen in such a way that the thermodynamic equilibrium favour the interaction between the active ingredients and the fluid rather than with the porous material.
  • This represents pressure and temperature conditions where the partition ratios show their lowest values i.e. conditions where the solubility of the active ingredients in the fluid is high.
  • the active ingredients will be less retained by the material, and the chromatographic effect will be diminished. Therefore, according to the present invention an even distribution of active ingredient in the porous material is obtained within a shorter period of time as compared to the prior art methods.
  • the present invention provides an even deposition of each of the ingredients within a shorter treating time.
  • the prior art methods would either use a longer treatment time or add more of the low affinity ingredients in order to obtain a 1 : 1 deposition, such measures may be avoided when using the method of the present invention.
  • the partition ratio was proportional to the fluid density. For other fluids/active ingredients/ substrate combinations there might be other relations.
  • a porous material is in this context defined as a solid (often called frame or matrix) permeated by an interconnected network of pores (voids) filled with a fluid (liquid or gas), and more specifically the porous material is selected from cellulose, wood, cork, silica, membranes and polymers.
  • a presently preferred porous material is wood, cork or cellulose.
  • the treatment may be any type of treatment and is preferably selected among deposition of active ingredients, impregnation, extrac- tion, dying, drying and any combination thereof.
  • the active ingredient is selected from the group consisting of water repellents, modifiers of the building blocks of the porous wood matrix and biocides or a combi- nation thereof.
  • Preferred water repellents are oils, co-polymers, waxes and silicones.
  • the modifier of the building blocks of the porous wood matrix is selected from the group consisting of polymers or copolymers having bulky functional groups.
  • the polymers/co polymers react with the porous media eliminating e.g. any free hydroxyl groups in the cellulose and filling the open spaces.
  • Specific examples of wood modifiers are, fire retar- dants, inorganic salts, aromas, colorants, etc.
  • the purpose of modifying the porous material is to enhance preferred properties of the material, such as moisture and dimensional sta- bility, or adding new properties to the material, such as adding fire re- tardants, to increase the resistance against fire, thermal insulating agents to improve the insulation power of the material etc.
  • Preferred of the at least one active ingredient(s) are selected from the group of water repellents, modifiers of the building blocks of the porous material, organic and inorganic biocides, aromas, colorants and organic or inorganic salts, such as salts of organic acids and combinations of all of the above. Any other active ingredient suitable for being deposited in a porous material using the method of the invention is con- templated .
  • the biocide is an organic biocide selected from the group consisting of triazoles, pyrotroides, carbamates, organic or inorganic salts, salts of organic acids, essential oils having disinfectant properties and combinations of one or more of these.
  • Examples of specific active ingredients are selected from but not limited to the triazoles propiconazole and tebuconazole, iodopropynylbu- tylcarbamate (in the following IPBC), carbon dioxide, chlotianidin, di- chlofluanid, difenacoum, difethialone, etofenprox, K-HDO, slufuryl fluo- ride, thiabendazole, thiamethoxam and any conmbination of thereof.
  • the ratio of active ingredient to carrier fluid is typically in the range of 1 ppm to 30 % (weight/weight) depending on the active ingredient.
  • the carrier fluid is a supercritical fluid having a critical point at a temperature of 20-50 0 C and a pressure of 5-100 bar under a pressure of at least 20 bar and a temperature below 65°C.
  • a presently preferred carrier fluid is carbon dioxide however other suitable carrier fluids, without limitation, encompass pro- pane, ethane and R134a.
  • Carbon dioxide is a fluid, which has a relatively low critical pressure, low cost, is non-toxic and non-flammable. Additionally, carbon dioxide is easy to recover again from the treatment process for repeated use in the method .
  • Carbon dioxide is particularly preferred when the active ingredient is a non-polar chemical .
  • Another aspect of the present invention is a piece of wood obtainable by the method of the present invention characterised in an even distribution of the active ingredient throughout the wood .
  • Figures Figure 1 is a diagram showing the estimated partition ratios for propiconazole in a wood/CO 2 system at 4O 0 C and varying pressures (referred to in example 1) .
  • Figure 2 is a diagram showing the estimated partition ratios for propiconazole in a wood/CO 2 system at 50 0 C and varying pressures. Experiments at 80 bar were done but the retention time could not be recorded at this pressure (referred to in example 1).
  • Figure 3 is a graph showing the partition ratios of propiconazole as a function of CO 2 density (referred to in example 1).
  • Figures 4a - c are the time/temperature/pressure curves for three treatment processes (referred to in example 2).
  • Figure 5 is a schematic illustration of sample collection from a treated wood piece (referred to in example 2).
  • Figure 6 is a graph showing deposition of active ingredient in the wood.
  • Diamond/short-dotted line is an active ingredient with a low partition ratio a high feed
  • the square/long-dotted line is an active ingredient with a low partition ratio
  • a triangle/solid line is an active ingredient with a high partition ratio, i.e. a wood prepared according to the prior art method (referred to in example 2).
  • Figure 7 is a graph showing the ratio of deposition of two active ingredients (propiconazole and tebuconazole) in the wood.
  • Diamond/short-dotted line is an active ingredient with a low partition ratio
  • the square/long-dotted line is an active ingredient with a low partition ratio
  • a triangle/solid line is an active ingredient with a high partition ratio, i.e. a wood prepared according to the prior art method (referred to in example 3).
  • Figure 8 is a graph showing the partition ratio of tebuconazole, propiconazole and IPBC respectively as a function of carbon dioxide den- sity.
  • a porous medium or a porous material is defined as a solid (often called frame or matrix) permeated by an interconnected network of pores (voids) filled with a fluid (liquid or gas).
  • voids pores
  • a fluid liquid or gas
  • both the solid matrix and the pore network are assumed to be continuous, so as to form two interpenetrating continua such as in a sponge.
  • Many natural substances such as rocks, soils, biological tissues (e.g. bones), and man made materials such as cements, foams and ceramics can be considered as porous media.
  • porous media is used in many areas of applied science and engineering : mechanics (acoustics, geomechanics, soil mechanics, rock mechanics), engineering (petroleum engineering, construc- tion engineering), geosciences (hydrogeology, petroleum geology, geophysics), biology and biophysics, material science, etc. Fluid flow through porous media is a subject of most common interest and has emerged a separate field of study. The study of more general behaviour of porous media involving deformation of the solid frame is called poro- mechanics.
  • Preferred porous materials in the context of the present invention are selected from the group of silica, cellulose, gels, aerogels, cork and wood.
  • a presently preferred porous material is wood, cork or cellulose.
  • the partition ratio is defined as the ratio of the active compound concentration in the porous material to its concentration in the fluid phase at equilibrium. The value of the partition ratio depends on the material treated, the active ingredient and on the carrier fluid. In the applications shown in the experiments, the partition ratio for propiconazole can be as high as 38.3 or as low as 2.6. While for tebuconazole, the partition ratio can be as high as 80.4 or as low as 5.9. The same values are seen for IPBC, presenting partition ratios as high as 16 or as low as 2.9.
  • partition ratios given as examples above are for supercritical carbon dioxide and wood. If the carrier fluid is changed to another fluid, tebuconazole and propiconazole and IPBC are changed to another active ingredient(s) and/or the wood exchanged with another porous medium, the partition ratios would have completely different absolute values. But the principle remains the same.
  • Control of the process parameters during the movement through the wood is preferably done by increasing the pressure or lower- ing the temperature, this increases the density of the carrier fluid, such as carbon dioxide, and consequently the solubility of active ingredients in the carrier fluid . This will ensure that the active ingredient is maintained in the mobile phase.
  • the relationship between carbon dioxide density and the partition ratio of three active ingredients is illustrated in figure 8. This clearly shows that a means for obtaining a low partition ratio is increasing the density of the carrier fluid, in this figure illustrated with carbon dioxide.
  • excipients are alcohols, preferably with low volatil- ity, for example, propylene glycol or triethylene glycol .
  • the excipients are preferably used as a formulation adjuvant and facilitates the loading of the active compounds to the process.
  • Other purposes of the excipient can be to facilitate flowability of the active ingredient in the carrier fluid or simply to handle the active ingredient in liquid form for safety rea- sons.
  • the treatment may be an impregnation process where one or more active compounds are deposited in the wood .
  • active com- pounds may be biocides, fungicides, insecticides, colorants, fire retarding compounds, strength improving compounds etc.
  • the treatment may also be an extraction process where particular compounds are extracted from the wood, such as resin, terpenes etc., or it may be toxic compounds that have to be removed from wood before disposal of the wood .
  • carrier fluids are carbon dioxide, ethane, ethylene, propane, propylene, cyclohexane, isopropylene, benzene, toluene, p- xylene, chlorotrifluoromethane, trichlorofluoromethane, ammonia and water.
  • a presently preferred carrier fluid is carbon dioxide.
  • the method of the present invention may comprise but is not limited to the following steps : a) a vessel is loaded with wood to be treated; b) the required amount of active ingredient is placed in a mix- ing vessel c) the vessel is pressurised using the carrier fl u id u ntil the treatment pressure is reached; d) a holding period where the pressure is essentially constant or the pressure changes at a low rate; e) depressurising the vessel to ambient pressure followed by removal of the treated wood .
  • the partition ratio is lowered i.e. the active ingredient equilibrium mobile phase ⁇ -> stationary phase is kept to the left, and d uring step e) the partition ratio is increased, i.e. the equilibrium is forced to the right.
  • step b) may be omitted and the active ingredient added either during or after step c) when the solubility in the solvent is high enough to ensure that the active ingredient is maintained in the carrier fluid .
  • a treatment wherein the supercritical treatment pressure in step c) is in the range of 85-300 bar, preferably in the range of 100-200 bar, more preferred in the range of 120-170 bar and most preferred in the range of 140-160 bar.
  • a treatment wherein the temperature of the carrier fluid in the wood is above 1O 0 C, preferably above 2O 0 C, preferably above 25 0 C, preferably above 3O 0 C, more preferred above 32.5 0 C and most preferred above 35 0 C.
  • a treatment wherein the temperature of the carrier in the wood is in the range of 25-65 0 C, preferably in the range of 31-55 0 C in step b) and d) when the pressure is above 30 bar.
  • Treatment periods vary with the properties of the porous me- dia, such as porosity, permeability, affinity of the carrier fluid and the porous material to the active ingredients.
  • properties of the porous me- dia such as porosity, permeability, affinity of the carrier fluid and the porous material to the active ingredients.
  • the treatment can take between 2 and 9 hours, such as 2.5-4 hours, depending on the actual dimensions and properties.
  • other wood species such as birch ⁇ Betula
  • Example 1 Interaction of propiconazole and wood in a supercritical carbon dioxide atmosphere was examined by measuring the retention times of propiconazole in a wood filled column mounted on a supercritical chro- matograph.
  • Propiconazole >96% purity was supplied by Janssen Pharmaceutical, Belgium .
  • Sawdust with a particle size ⁇ 125 ⁇ m was prepared from boards of Norway spruce ⁇ Picea abies) supplied by Vida Wood, Sweden.
  • the supercritical chromatog raph was a HP G 1850A ChemStation equipped with a HP 1050 UV detector. Carbon dioxide was from a pressurized bottle, Air Liquide E290.
  • a column was built by filling a metal cylinder with sawdust.
  • the column had a length of 294 mm and an inside diameter of 6.4 mm .
  • the column was mounted on the chromatograph and subjected to a flow of carbon dioxide at various supercritical conditions. For each run the propiconazole was dissolved in ethanol and the ethanol- propiconazole mixture was injected into the pre-column flow path of the carbon dioxide. The propiconazole was then moved downstream through the column to the detector. The retention time was then established from the resulting chromatogram and the procedure was repeated . All system parameters i.e. pressure, temperature, flow rate, injection vo- lume, and detector wavelength were controlled via system software (HP ChemStation). Temperature was set to either 40 or 5O 0 C and the pressures were set to 80, 100 or 150 bar when running at 40 0 C, and 100, 110 or 150 bar when running at 5O 0 C.
  • k ' is the retention factor
  • t R is the recorded retention time
  • t M is the hold-up time
  • K D is the partition ratio (IUPAC has discontinued the term partition coefficient)
  • V M is the volume of the mobile phase (i.e. the hold-up volume)
  • V 5 is the volume of the solid phase (i.e. the volume of the sawdust).
  • K D is essentially a measure of the relationship between biocide concentration in the solid phase and the fluid phase. A value higher than 1, would signify a higher affinity of propiconazole for wood than for CO 2 .
  • the table also lists the hold-up times i.e. the retention times of the carbon dioxide.
  • the hold-up times were calculated under the assumption that the CO 2 did not interact with the sawdust. Under this assumption the hold-up time can be calculated from the flow rate into the pump (F IN ) and the volume of the mobile phase (V M ) taking into account the difference in fluid specific volume at either side of the pump ( ⁇ IN and ⁇ OUT) :
  • the pump input was liquid CO 2 at 57 bars cooled to 5°C so ⁇ IN was a constant 1.09 cm 3 /g- ⁇ 0U ⁇ varied depending on the physical conditions of the run between 1.28 cm 3 /g and 3.60 cm 3 /g- Table Ia. Retention times of propiconazole in the wood column under the indicated physical conditions. Corresponding retention factors and partition ratios are shown together with the calculated hold-up times of CO 2 .
  • Fig. 1 and Fig. 2 show the estimated partition ratios at the examined physical conditions.
  • experiments were run at a constant temperature of 4O 0 C and three different pressures 80, 100 and 150 bar.
  • the temperature was increased to 50 0 C and the measurements were repeated at the same pressures.
  • a retention time at 80 bar was not recordable, because the affinity of propiconazole to wood at these conditions was so large that a peak could not be established from the chromatogram.
  • the efficiency of the sawdust column was very low meaning that peak broadening increased considerably with time.
  • the chromatogram did not show a peak but rather a very long low hill, which made a correct establishment of the retention time impossible.
  • a measurement was made at 110 bar instead.
  • a piece of wood was treated according to the Super- wood TM process, i.e. generally comprising the steps:
  • Carbon dioxide is added, and the pressure and temperature are adjusted to the desired condition, whereby the active ingredients are dissolved in the carbon dioxide and maintained in the fluid phase
  • Carbon dioxide together with active ingredients is circulated through the impregnation vessel for a suitable period of time, thus ensuring an even distribution of the active ingredients in the wood
  • the vessel is depressurised and the conditions are adjusted so that the active ingredient is forced into the wood phase, whereby any excess active ingredients are deposited from the gas, enabling both carbon dioxide and the active ingredients to be recycled •
  • the wood is removed from the impregnation vessel and is ready to be used.
  • Each subdivided sample is grinded in a rotary grinder with a 0.5 mm mesh, and extracted with methanol.
  • Duplicates of approximately 1 g of grinded wood samples were extracted with 20 ml_. methanol and treated for about 30 minutes in an ultrasonic bath followed by extraction on a rotary table for additional 16 hours.
  • the extract was filtered through a 0.45 ⁇ m disposable filter and analysed using gas chromatography using a FID-detector (flame ionization detector) for determination of propiconazole and tebuconazole con- tents and an ECD-detector (electron capture detector) for determination of the IPBC content.
  • the detection limits were as follows: Using a FID- detector with a probe having a net weight of 1 g the detection limit was 1 - 2 mg/kg depending on the active ingredient. Using a ECD-detector with a probe having a net weight of 1 g the detection limit was 0.1 - 0.2 mg/kg IPBC. Each extract was analyzed twice and the average of these results was used.
  • the values for each depth were determined as an average value taken from a series of batches of the same wood type and origin impregnated with the same impregnation program. In batch #314 96 samples were used, in batch #338 28 samples were used and in batch #335 7 samples were used. The number of samples were chosen based on experience with homogeneity of the results.
  • the active ingredient content (AI) gradient was extrapolated and the equations describing the linear relationships clearly showed a substantially steeper gradient in the prior art method wood as compared to wood prepared according to the present invention . Additionally, it was noted that comparing the methods according to the present invention a longer treatment time resulted in a gradient with a lower inclination. The most important observation is that two samples impregnated in comparable time spans using the prior art (314) and the present invention method (335) differs significantly in the distribution of active ingredient.
  • Example 3 A piece of wood was treated according to the present invention both with a short impregnation time (approximately 1 hour) denoted 335, and a long impregnation time (approximately 2 hours) denoted 338 and another piece of wood was treated according to the prior art method for approximately IVi hour, and was denoted 314. All wood pieces were treated with a 1 : 1 mixture of two fung icides (propiconazole and tebu- conazole) and were analyzed for an even distribution of the two fungicides in the wood piece.
  • Test samples were taken from the wood pieces as described in example 2. The results can be seen in figure 7 where the relationship between depth of the wood piece and the ratio propiconazole:tebuconazole content is depicted . The measurement points were extrapolated and the resulting equations are as follows :
  • Kang, S M, Ra, J B, Levien, K L, Morrell, J J (2006) Developing diffusion coefficients for SCF impregnation of douglas fir heartwood with cyproconazole. Journal of Wood Chemistry and Technology, 26(2), 111- 124. Lucas, S, Gonzalez, E, Calvo, M P, Palencia, C, Alonso, E, Co- cero, M J (2007) : Supercritical CO2 impregnation of Radiata pine with organic fungicides - Effect of operating conditions and two -para meters modeling . Journal of Supercritical Fluids, 40(3), 462-469. Sahle-Demessie, E, Levien, K L, Morrell, J J (1995) : Impregnation of Wood with Biocides Using Supercritical Fluid Carriers. ASC Symposium Series, 608, 415-428.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Fertilizers (AREA)

Abstract

L'invention concerne des procédés améliorés de traitement d'un matériau poreux, tel que du bois, plus spécifiquement un procédé dans lequel un ingrédient actif à déposer dans un matériau poreux dans une première étape est maintenu en phase mobile et dans une seconde étape est maintenu en phase stationnaire.
EP10715087A 2009-04-22 2010-04-21 Procédé amélioré de traitement d'un matériau poreux Ceased EP2421685A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200900520 2009-04-22
PCT/DK2010/050089 WO2010121624A2 (fr) 2009-04-22 2010-04-21 Procédé amélioré de traitement d'un matériau poreux

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EP2421685A2 true EP2421685A2 (fr) 2012-02-29

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WO2013070196A2 (fr) * 2011-11-08 2013-05-16 Empire Technology Development Llc Procédés de traitement du bois par des conservateurs à l'aide de gaz rares sur-critiques
WO2015067275A1 (fr) 2013-11-06 2015-05-14 Superwood A/S Procédé de traitement d'essence forestière à l'aide d'un liquide
CN114670299B (zh) * 2022-03-11 2023-05-23 华南理工大学 一种高强度各向异性气凝胶型木材结构及其制备方法

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Publication number Priority date Publication date Assignee Title
US4992308A (en) * 1988-09-16 1991-02-12 University Of South Florida Supercritical fluid-aided treatment of porous materials
WO2000027547A1 (fr) * 1998-11-10 2000-05-18 Fls Miljø A/S Procede permettant de realiser un traitement d'impregnation ou d'extraction sur un substrat de bois contenant de la resine

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