EP4023812A1 - Procédé de fabrication de produits à base de bois en tant que matière première - Google Patents

Procédé de fabrication de produits à base de bois en tant que matière première Download PDF

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Publication number
EP4023812A1
EP4023812A1 EP20217520.4A EP20217520A EP4023812A1 EP 4023812 A1 EP4023812 A1 EP 4023812A1 EP 20217520 A EP20217520 A EP 20217520A EP 4023812 A1 EP4023812 A1 EP 4023812A1
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EP
European Patent Office
Prior art keywords
wood particles
wood
extraction
content
hexanal
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EP20217520.4A
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German (de)
English (en)
Inventor
Anton Friedl
Maximilian LEHR
Martin MILTNER
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MM Board and Paper GmbH
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MM Board and Paper GmbH
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Application filed by MM Board and Paper GmbH filed Critical MM Board and Paper GmbH
Priority to EP20217520.4A priority Critical patent/EP4023812A1/fr
Priority to EP21831039.9A priority patent/EP4271879A1/fr
Priority to PCT/EP2021/085975 priority patent/WO2022144176A1/fr
Priority to PCT/EP2021/087767 priority patent/WO2022144377A1/fr
Priority to CN202180094366.8A priority patent/CN116897233A/zh
Priority to JP2023563337A priority patent/JP2024501377A/ja
Priority to CA3203411A priority patent/CA3203411A1/fr
Priority to US18/259,700 priority patent/US20240076831A1/en
Priority to EP21836586.4A priority patent/EP4271880A1/fr
Publication of EP4023812A1 publication Critical patent/EP4023812A1/fr
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
    • D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds

Definitions

  • the invention relates to methods for the manufacture of wood-based products, in particular methods for the pre-treatment of wood.
  • Wood as a raw material for industrial processing into wood-based products contains - in addition to the main components cellulose, hemicelluloses and lignin - many different low and high molecular weight substances such as fatty acids, resin acids, phenols and terpenes. These substances are summarized as so-called extractive substances (or extractives) because they can be extracted from wood with hot water and/or organic solvents ( Koch, Raw Material for Pulp; in: Sixta (ed) Handbook of Pulp (2006), Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, p 21-68 ).
  • extractive substances are "organoleptically relevant substances" since they can lead to odor and taste interactions and impairments in wood particle-based products with the environment relevant to the respective end use (e.g. food in the case of packaging cardboard or room air in the case of wood fiber boards).
  • aldehydes which as volatile hydrocarbons naturally have characteristic odors (e.g. terpenes)
  • aldehydes are primarily responsible for this, which are formed by autocatalytic oxidation of fatty acids naturally occurring in wood ( Schreiner et al., Resolving the smell of wood-identification of odor-active compounds in Scots pine (Pinus sylvestris L.) (2016), Scientific Reports 8:8294 ).
  • wood particles contain resins that can coagulate into sticky particles during processing of the wood particles, which is intensified by the fats and waxes that also occur naturally in the wood.
  • resinous particles also known as "pitch” or “stickies”
  • itch also cause disruptive effects on the paper/cardboard surface, which can subsequently cause problems in the further processing of the paper/cardboard (e.g. printing).
  • These substances can also have a disruptive effect on the production process by causing deposits on machine parts, rollers and clothing parts, etc. cause ( Sixta et al., Chemical Pulping Processes; in: Sixta (ed) Handbook of Pulp (2006), Weinheim: Wiley-VCH Verlag GmbH & Co.
  • fatty acids are not removed from wood particles for wood particle-based products such as cardboard or fiberboard. Instead, the auto-oxidation of these fatty acids is inhibited or delayed by binding the heavy metal ions, which act as catalysts, in the wood particle products by adding complexing agents such as ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA).
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • EDTA and its metal complexes are only poorly and slowly degradable in waste water treatment and are therefore considered ecologically questionable today, which entails increasing problems, especially for waste water from production plants for wood particle-based products.
  • organoleptic properties include bleaching (e.g DE 10 2004 050 278 A1 ), delignifying (eg DE 28 18 320 A1 ), oxidizing or reducing (eg DE 33 44 239 C2 , WO 2006/039914 A1 , DE 10 2006 020 612 A1 ) chemicals used.
  • bleaching e.g DE 10 2004 050 278 A1
  • delignifying e.g DE 28 18 320 A1
  • oxidizing or reducing eg DE 33 44 239 C2 , WO 2006/039914 A1 , DE 10 2006 020 612 A1
  • Another object of the present invention is a significant improvement in the organoleptic properties of the wood particles and aged wood particles that are produced by this method, so that the products produced with it have little or no odor pollution even without the use or addition of bleaching, delignifying, oxidizing or reducing chemicals.
  • the method according to the invention after aging of the wood particles (up to 6 months), an undesirable odor and taste changes occurring in the course of this aging in the foodstuffs coming into contact with them are to be prevented.
  • a preferred object of the present invention is to remove other ingredients from wood particles that are undesirable in the planned product, for example resin acids.
  • the present invention relates to a method for Manufacture of products based on wood as raw material, in which wood in the form of wood particles is subjected to an extraction treatment with an extraction agent comprising one or more organic solvents or an organic-aqueous mixture of the solvent or solvents with water, the content of fatty acids being reduced in the wood particles is reduced by at least 70% by the extraction treatment of the wood particles with the extraction agent, measured as hexanal content in % by weight after accelerated aging for 72 h at 90°C, but the content of cellulose, hemicelluloses and lignin at this Extraction treatment is essentially obtained.
  • the method according to the invention a large part of the fatty acids and other disruptive substances (resin acids, etc.) can be extracted without the substance of the wood material (cellulose, hemicelluloses and lignin) being significantly impaired. While any improvement in the removal of fatty acids from the wood raw material has benefits, a significant reduction of at least 70% for suitable large scale commercial use is readily possible with the present process.
  • the treatment according to the invention is preferably selected in such a way that the desired reduction is achieved in any case, and thus a reduction by at least 70%, preferably by at least 90%, in particular by at least 95%, is achieved.
  • the conditions to be used according to the invention can then be selected, for example on the basis of the nature of the wood or the extractant, such that the hexanal reduction according to the invention results in any case.
  • preferred maximum values in absolute contents of hexanal can also be set.
  • wood particles with a hexanal content of 2 mg/kg dry matter (DM) can also be used for certain applications, absolute values below 1 mg/kg DM are preferred.
  • a hexanal content of 0.5 mg/kgTM hexanal was marked as an empirically determined value below which experience has shown that organoleptic impairments are not sensory are more noticeable.
  • a preferred embodiment of the method according to the invention relates to extraction of the wood particles to a hexanal content of 0.5 mg/kg DM or below.
  • hexanal contents of the wood particles > 0.5 mg/kgTM it could be determined that the risk of an organoleptic impairment of the wood particles increased with increasing hexanal content.
  • HS-GC headspace gas chromatography
  • the wood particles are preferably less than 5 cm in size, preferably in the form of fibers, chips, strands, wood chips or mixtures thereof.
  • This particle feature (as "Particle size”) can preferably be determined by sieve analysis using a square mesh sieve. Accordingly, the particle characteristic of the particle size is formulated in terms of the mesh size, preferably 5 cm (other sizes (depending on practical necessity), eg 4, 3, 2 or 1 cm (or possibly larger) can also be easily set with this). According to this preferred embodiment, the particles according to this size definition essentially correspond to the undersize of the sieve with mesh size as the particle feature.
  • the wood particles are preferably in the form of fibers, chips, strands, chips or mixtures thereof.
  • the wood particles are wood that has been fiberized by mechanical and/or thermal and/or chemical digestion, in particular wood fibers with average fiber lengths between 0.5 and 2 mm and average fiber diameters between 10 and 50 ⁇ m.
  • Average fiber length and average fiber diameter relate to the average length, determined by optical measurement of the suspended fibers. This optical measurement usually leads to uniform results (regardless of the chosen methodology and analysis device), but the devices PulpEye (http://www.pulpeye.com/products/pulpeye/) and in particular MorFi Fiber Analyzer ( http://www.techpap.com/fiber-and-shive-analyzer-morfi-neo,labdevice,31.html).
  • the amount of organic compounds that can be extracted using the method according to the invention varies depending on the type of wood and the component of the tree from which the wood particles are obtained (heartwood/sapwood). For example, pine heartwood contains up to 9% extractables by weight, while fir sapwood typically has up to 1% extractables ( Björklund Jansson et al., Wood Extractives; in: Ek et al. (eds) Wood Chemistry and Wood Biotechnology, 1 (2009), Walter de Gruyter GmbH & Co.
  • Nisula Wood Extractives in Conifers A Study of Stemwood and Knots of Industrially Important Species (2018), ⁇ bo Akademi University Press, ⁇ bo ).
  • types of wood such as pine, birch, lime or poplar contain higher amounts of fatty acid esters (birch 2315 mg/kg, lime 7544 mg/kg or pine 5807 mg/kg of fatty acids; DE 10 2009 046 127 A1 ) obtained through the manufacture of products from these Wood can be broken down into aldehydes and organic acids without this being able to be prevented by changing technological parameters.
  • there are larger fluctuations in the content of fatty acids and triglycerides depending on the location, tree age, height section of the individual tree and between heartwood and sapwood.
  • the present invention thus brings decisive advantages over a mere chemical-thermo-mechanical digestion (CTMP) known per se, in which wood chips are mixed with sodium sulfite and EDTA, both with regard to environmental aspects and with regard to the inventive effect in the efficient depletion of fatty acids from the raw material.
  • CMP chemical-thermo-mechanical digestion
  • the US 5,698,667A discloses a pretreatment of a lignocellulosic material by extraction with an organic solvent (e.g., acetone) to remove wood extractives such as volatile organic compounds (VOC) and higher molecular weight pitch components without significantly affecting the integrity of the lignocellulosic components of the material.
  • an organic solvent e.g., acetone
  • VOC volatile organic compounds
  • the maximum depletion of pitch and VOCs was 54.4 and 65% (after two extractions for acetone in water (80/20) and 100% acetone)
  • the methodology used cannot ensure that volatile components pass into the gas phase when the solvent is removed from the extract and thus the depletion when determined by the evaporation residue of the extract are to be set even lower.
  • the method according to the invention using an extractive pretreatment of wood particles (such as wood fibers) with organic solvents or organic-aqueous mixtures of the solvent or solvents with water, a large part of the fatty acids naturally occurring in the wood are removed before further processing (e.g. to cardboard or wood fiber boards).
  • other extractives such as resin acids, phenols and terpenes in the mechanical pulp are greatly reduced by this pre-treatment.
  • the hexanal content has proven itself as an indicator for the auto-oxidation of naturally occurring fatty acids in wood, especially when it is determined after accelerated aging of the wood particles (72 h at 90° C.).
  • this hexanal content is reduced by at least 70%, based on the potential of the starting raw material (as well as--in absolute contents), preferably down to below 0.5 mg/kg DM.
  • odor and taste interactions of wood particle-based products with the environment relevant to the respective end use for example food in the case of packaging board or room air in the case of wood fiber boards
  • the pretreatment does not significantly change the composition of the wood particles, i.e.
  • cellulose, hemicelluloses and lignin are not reduced to any significant extent (at least by no more than 10%, preferably by no more than 6%, in particular by no more than 4% reduced) extracted and/or degraded, this reduction preferably being determined as the extracted solid mass, based on the starting material, the wood particles.
  • Pitch stickies, resins, etc.
  • the present invention results in other important product and process advantages, especially for paper and cardboard production: Pitch (stickies, resins, etc.) are removed from the process and can therefore not have a disruptive effect on the production process, so that there are no or reduced deposits on machine parts, rollers and clothing parts, etc. comes.
  • interference effects on the paper/cardboard surface can also be reduced with the present invention, which subsequently also causes problems in the further processing of the Paper/cardboard (e.g. printing) can be significantly reduced. Due to the significantly lower proportion of these components on the surface and also inside the paper/cardboard, there is also increased product quality and, surprisingly, an increase in mechanical strength.
  • the above-mentioned improved product properties of products made from the wood particles extracted according to the invention can also open up new areas of application that can currently only be covered with paper/cardboard whose fiber components are cellulose and/or treated BCTMP (bleached chemi-thermo-mechanical pulp) (e.g. high-quality packaging boxes) or for particularly delicate applications that can only be served with cellulose today.
  • BCTMP bleached chemi-thermo-mechanical pulp
  • the COD loads of the waste water of the process are also greatly reduced by the extractive pretreatment according to the present invention, as a result of which larger production capacities are made possible with the same COD load in the waste water.
  • the release of odor- and taste-active aldehydes in wood particle-based products such as cardboard or wood fiber boards by auto-oxidation of fatty acids naturally occurring in wood can also be achieved entirely without the addition of complexing agents.
  • a complexing agent such as EDTA or DTPA in the manufacture of wood particle-based products to reduce the odor and taste load of these products thus becomes superfluous, eliminating the EDTA/DTPA load in the waste water and thus the (ground)water-related environmental impact of the wood particle production -based products are reduced and the EDTA/DTPA contamination of the products themselves is avoided.
  • extractives are also significantly reduced and thus removed from the process, which reduces the extractive loading of the process water in the production of the wood particles and thus results in lower demands on the waste water cleaning/treatment.
  • the reduced extractive load of the process water also has the advantage that problems in the manufacturing process of wood particle-based products can be reduced and the quality of the products can be increased (e.g. avoidance of pitch/stickies problems in cardboard production). This variant is therefore a particularly environmentally friendly embodiment of the present invention.
  • the present invention can be integrated relatively easily into existing production plants or operated with existing plants.
  • the choice of the liquid phase of the extract according to the invention also depends on the relevant type of wood (and its natural content of extractives).
  • the solvent or solvent mixture in the extraction agent must also be chosen in such a way that there is no significant loss of cellulose, hemicelluloses and lignin and the treatment time is not excessively long.
  • Mixtures according to the invention of ethanol, acetone and water with 0-95% by weight ethanol, preferably 50-90% by weight ethanol, and 0-99% by weight acetone have proven to be particularly advantageous. preferably 30-90% by weight of acetone, identified as the organic-aqueous solvent in the extractant.
  • organic solvents which can be used instead of (or, for certain purposes, optionally also together with) ethanol or acetone in the extractant with a view to an industrial scale are, for example, methanol, n-propanol and isopropanol.
  • preferred ratios of extractant to solid dry matter are 5:1-25:1 (w/w), preferably 8:1-17:1 (w/w).
  • 100% extractant always means the total amount of extractant present after extraction, namely the extractant, including the materials extracted from the wood particles and that in the wood raw material (in the wood particles) contained water.
  • the ratios before extraction essentially correspond (just + /- 1%) also the conditions after the extraction (the possibly existing water content in the wood starting material, which is usually given in the economic utilization, is accordingly always already included in the extraction agent).
  • the extraction temperatures can also be determined based on the other wood and process parameters, in particular taking into account the energy consumption that higher temperatures require.
  • the treatment preferably takes place at an extraction temperature of 20-150.degree. C., preferably 40-120.degree. C., in particular 50-110.degree.
  • the process according to the invention is operated at atmospheric pressure; in certain cases, extraction under pressure can be advantageous (despite the additional energy expenditure of the pressure application). Therefore, according to a preferred embodiment, the treatment according to the invention takes place at an absolute extraction pressure of 1-5 bar, preferably 1-1.49 bar.
  • the duration of the extraction process according to the invention can also be determined on the basis of the other process parameters, which duration is necessary for the depletion of fatty acids to be achieved.
  • the treatment according to the invention preferably takes place during an extraction time of 10 minutes to 8 hours, preferably 30 minutes to 7 hours, in particular 1 to 5 hours.
  • the present method is suitable for all wood-based products in which organoleptic properties play a role.
  • the method according to the invention is particularly suitable for products that are in use for a long time, for packaging foodstuffs or are used indoors. Therefore, the method according to the invention is particularly suitable for the (large-scale) production of cardboard, paper, wood fiber boards, chipboard, commodities (for example (or in case of doubt) according to the definition of the Austrian Food Safety and Consumer Protection Act (LMSV, Federal Law Gazette I No. 13/2006, idFv 01.10.2020)), medical devices (e.g. (or in case of doubt) according to the definition of the Austrian Medical Devices Act (MPG, Federal Law Gazette No. 657/1996, idFv 01.10.2020)), in particular for the production of cardboard.
  • LMSV Austrian Food Safety and Consumer Protection Act
  • MPG Federal Law Gazette No. 657/1996, idFv 01.10.2020
  • the dry substance content of the wood particles used is reduced by less than 10%, preferably by less than 5%, in particular by less than 4%, this reduction preferably being related to the extracted solid mass on the starting material, namely the wood particles, is determined.
  • the wood particles can preferably be selected from the industrially relevant types of wood, e.g. from coniferous wood particles, preferably spruce wood particles, fir wood particles, pine wood particles, or larch wood particles; Deciduous wood particles, in particular beech wood particles, poplar wood particles, birch wood particles, or eucalyptus wood particles; or mixtures thereof.
  • the wood particles are mixed with the extractant during the treatment.
  • a preferred embodiment of the method according to the invention is that the wood particles are pressed after treatment with the extractant in order to remove the extractant.
  • the wood particles can preferably be treated one or more times with an extractant, even more preferably with an organic-aqueous solvent a concentration similar or equal to that of the extractant.
  • the extractant used in the extraction and/or washing can be removed from the wood particles by repeated washing with water or drying, with drying being particularly preferred. Both the extraction agent and the washing water are preferably regenerated for reuse after the process according to the invention.
  • the extractives especially fatty acids and resin acids, can be separated from the extractant and used as by-products.
  • extraction of the wood particles with the extraction agent preferably reduces the content of fatty acids in the wood particles by at least 75%, preferably by at least 80%, in particular by at least 90%, measured as the hexanal content in % by weight of the wood particles in the starting material in comparison to the extracted wood particles after accelerated aging for 72 h at 90°C.
  • the wood particles obtained in this way preferably have a fatty acid content in the wood particles of less than 2 mg/kg dry matter, preferably less than 1 mg/kg dry matter, in particular less than 0.5 mg/kg dry matter, measured as hexanal content as mass fraction of the extracted wood particles after accelerated aging for 72 h at 90°C.
  • the method according to the invention to reduce the mechanical strength of the extracted wood particles, measured as Tensile Index of test sheets in Nm/g, by at least 10%, preferably by at least 15%, in particular by at least 25%. , whereby the freeness, measured in °SR, changes by less than 10%.
  • no complexing agents in particular complexing agents selected from polybasic and polyfunctional carboxylic acids, aminomethyl carboxylic acids, aminomethyl phosphonic acids and their compounds, EDTA, DTPA EGTA, EDDS and their salts, polyphenols, tannins, amino acids, peptides, proteins, polycarboxylates, Added to phosphates, polyphosphates, phosphonic acids, polyphosphonates, phosphated, phosphonylated, sulfated and sulfonated polymers during the extraction process, particularly throughout the manufacturing process for the products made from the wood particles.
  • the method according to the invention represents an extremely advantageous and practice-relevant variant, if only for ecological reasons.
  • the aim of the process developed in this patent is a significant improvement in the organoleptic properties of the wood particles and aged wood particles produced by this process.
  • the undesirable odor that occurs, especially after the wood particles have aged (up to 6 months), and the taste of the food that comes into contact with them, is mainly caused by aldehydes (especially hexanal), which are caused by autocatalytic oxidation of in the wood naturally occurring fatty acids are formed.
  • aldehydes especially hexanal
  • this autocatalytic oxidation is currently prevented or greatly slowed down industrially by complexing the metal ions present in the wood particles, which act as a catalyst, by adding complexing agents such as ethylenediaminetetraacetic acid (EDTA).
  • EDTA ethylenediaminetetraacetic acid
  • Hexanal (relative to dry wood) marks the empirically determined value below which experience has shown that organoleptic impairments are no longer perceptible to the senses.
  • the hexanal content can be determined using headspace gas chromatography (HS-GC) by filling a headspace vial with approx. 0.2 g of air-dried wood particles (90-95 wt% TSG). In these vials, the sealed wood particles must then be aged for six months at room temperature (approx. 20 °C) in order to oxidize the fatty acids to hexanal. Since this takes a lot of time and therefore does not allow a timely assessment of the extraction success, accelerated aging according to DIN ISO 5630-2 was carried out for the present experiments (unless explicitly stated otherwise). The wood particles were sealed in HS-GC vials, aged at 90 °C for 72 h and then the hexanal content was determined by HS-GC.
  • HS-GC headspace gas chromatography
  • Table 1 Analyzed wood particles Hexanal content accelerated aged 72 h at 90 °C in mg/kgDM Hexanal content naturally aged 6M at 20°C in mg/kgTM raw material 11:37 10.62 Extracted wood particles 1 2:14 1.41 Extracted wood particles 2 2:17 1.52 Extracted wood particles 3 2.80 1.74 Extracted wood particles 4 3.32 2.57 Extracted wood particles 5 3.64 2.75 Extracted wood particles 6 1.34 2.72 Extracted wood particles 7 2.35 1.69 Extracted wood particles 8 2.86 2.83
  • Table 2 solvent Hexanal content of the starting material in mg/kgDM Hexanal content of the extracted wood particles in mg/kgDM Determined extractive substance content of the extracted wood particles in wt% based on the starting material Average STAFF DEV Average STAFF DEV ethanol 14.07 1:13 ⁇ 0.20 - 3.4 ethanol 14.07 1:13 ⁇ 0.20 - 3.0 acetone 14.07 1:13 0.32 0.02 3.0 acetone 14.07 1:13 0.27 0.01 2.6
  • the Soxhlet extractions with ethanol differ significantly from those with acetone in the hexanal content, but not significantly in the extractive content.
  • the hexanal content of the wood particles after aging is therefore a much stronger and more accurate indicator of the organoleptic impairment than the extractive content, and was therefore used for the extraction success according to the present invention.
  • the hexanal content of the starting material and the resulting reduction in the hexanal content were specified for all experiments, since the starting materials are snapshots and the hexanal content can therefore vary greatly from time to time.
  • the extracted extractive substance mass (determined as the evaporation residue of the extract) is an important indicator for the solids mass loss of the extractions, since it includes almost the entire extractively removed solids mass - with the exception of a few very volatile compounds.
  • the evaporation residue of the extract together with the hexanal content of the extracted wood particles is an important measure for assessing the selectivity of the extraction.
  • groundwood samples were extracted with three different solvents. In each case 3 g of air-dried groundwood were extracted for 24 hours using the Soxhlet method according to the NREL procedure NREL/TP-510-42619. The results are shown in Table 3.
  • Table 3 shows that even with higher hexanal contents in the starting material, ethanol extracts best, followed by acetone. Cyclohexane extracts by far the worst, which means that completely non-polar solvents are unsuitable for the extraction of fatty acids.
  • Reichardt and Welton Reichardt and Welton, Solvents and Solvent Effects in Organic Chemistry4 (2011), Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, pp 550-552
  • the empirically determined polarity of cyclohexane is 0 (very non-polar) compared to 0.355 of acetone and 0.654 of ethanol. Nevertheless, extraction with cyclohexane was also able to reduce the hexanal content by 79%.
  • the Figures 1 to 3 show that the extraction success with 70 or 90 wt% ethanol is significantly better than that with 50 wt% - especially at lower temperatures.
  • Ethanol concentrations of 70 or 90 wt% ethanol reduce the hexanal content to a comparable level. With the extraction temperatures, it is apparent that 90 and 110°C reduce the hexanal content approximately equally, while it is not reduced as much at 70°C. With 90 wt% ethanol, the hexanal content can even drop below the 0.5 mg/kgTM mark from 90°C, which means that the groundwood extracted under these conditions no longer has any organoleptic impairments, according to experience.
  • Table 4 shows that despite the high hexanal content reductions achieved in this test series, the extracted solids mass is max. 7 wt% (based on the starting material) - but usually significantly lower. With a determined extractive content of the starting material of approx. 3 wt%, this means that neither hemicelluloses nor lignin are extracted to any significant extent.
  • Table 5 shows the results of these extractions.
  • EtOH concentration in wt% extraction conditions Hexanal content of the starting material in mg/kgDM Hexanal content of the extracted wood substance in mg/kgDM Reduction of the hexanal content in relation to the starting material
  • Temperature in °C time in h Average STAFF DEV Average STAFF DEV 60 70 2 11:37 0.18 3.06 1:18 73% 60 70 4 11:37 0.18 2:15 1.00 81% 60 90 2 11:37 0.18 2.60 0.88 77% 60 90 4 11:37 0.18 2.49 1.50 78%
  • Experiment 3 was carried out to test three different technically relevant solvents under real extraction conditions. Approx. 450 gTM mechanically dewatered groundwood (approx. 25 wt% TSG) in a solvent-water mixture with a solids:extractant ratio of 1:10 w/w and a solvent concentration of 70 wt% extracted in an autoclave at a temperature of 70°C for 4 hours. After extraction, the groundwood was pressed, washed with extraction agent, pressed again and washed again with deionized water before it was dried, aged and analyzed. Table 6 shows the results of these extractions.
  • acetone extracts the unsaturated fatty acids responsible for hexanal formation significantly better than undenatured ethanol.
  • the best extraction results were achieved with ethanol that was incompletely denatured with butanone.
  • the hexanal content of 2.77 mg/kgDM achieved with 70 wt%, 70°C and 4 h extraction time is still well above the 0.5 mg/kgDM limit, but corresponds to a reduction of 80%.
  • the evaporation residue of the extract is only between 2.2 and 2.4 wt% based on the starting material dry mass, which means that with a determined extractive substance content of 3.6 wt%, the main wood components are cellulose, hemicelluloses and In fact, lignin was not attacked and the extractions were therefore very were selective.
  • the abietic acid content of the extractions in this experiment was reduced by 41-55%, based on the starting material. Since abietic acid was chosen here as the key substance for the content of resin acids, a reduction in the content by around 50% is an indication of the clear reduction in resin through the process of this patent.
  • Table 7 Solid: extractant ratio w/w Extraction s time in h Hexanal content of the starting material in mg/kgDM Hexanal content of the extracted wood substance in mg/kgDM Reduction of the hexanal content in relation to the starting material Evaporation residue of the extract in wt% based on the starting material dry matter Reduction of the abietic acid content in relation to the starting material Average STAB W Average STAB W 1:10 4 14.07 1:13 5.83 0.18 59% 2.0 31% 1:15 4 14.07 1:13 2.76 0.15 80% 2.5 54% 1:15 2 7.24 0.03 1:19 0.72 84% - 38% 1:25 2 7.24 0.03 0.94 0.23 87% - 52% 1:10 1 2.44 0.11 0.40 0.04 84% 2.2 - 1:10 2 2.44 0.11 0.40 0.05 84% 1.5 - 1:15 2 2.44 0.11 0.39 0.01 84% 2.5 - 1:25 2 2.44 0.11 0.33 0.01 86% 2.8 -
  • the hexanal content is reduced by over 80% in all extractions (except for the solid:extractant ratio of 1:10 (w/w) at a starting material hexanal content of 14.07 mg/kgDM). reduced.
  • extraction agent-solids ratios of more than 10:1 (w/w)
  • the evaporation residue of the extract is less than 3%, which, given the extractive substance content of the starting material of 3.4 - 3.7 wt%, is proof of the quantitative preservation of the lignocellulose components in this process.
  • Solvent-medium ratio temp time Stiffness index according to Nm 7 /kg 3
  • the degree of grinding and thus the dewatering of the ground wood pulp hardly changes as a result of the extraction, which, with regard to any further processing (e.g. into cardboard), has the advantage that existing production plants do not have to be converted or converted Need to become.
  • the stiffness index also changes only slightly as a result of the extraction, whereas the tensile index, as a measure of the breaking force, rises sharply and reproducibly.
  • the mass loss due to the evaporation residue of the extract is around 2% very low. This means that the wood particles gain disproportionately strong strength through the extraction with little mass loss, which is of great importance for the lightweighting trend in the packaging sector in particular.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Paper (AREA)
  • Processing Of Solid Wastes (AREA)
EP20217520.4A 2020-12-29 2020-12-29 Procédé de fabrication de produits à base de bois en tant que matière première Pending EP4023812A1 (fr)

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EP20217520.4A EP4023812A1 (fr) 2020-12-29 2020-12-29 Procédé de fabrication de produits à base de bois en tant que matière première
EP21831039.9A EP4271879A1 (fr) 2020-12-29 2021-12-15 Procédé de production de produits à base de bois en tant que matière première
PCT/EP2021/085975 WO2022144176A1 (fr) 2020-12-29 2021-12-15 Procédé de production de produits à base de bois en tant que matière première
PCT/EP2021/087767 WO2022144377A1 (fr) 2020-12-29 2021-12-29 Procédé de production de produits à base de bois en tant que matière première
CN202180094366.8A CN116897233A (zh) 2020-12-29 2021-12-29 以木料为原材料生产产品的方法
JP2023563337A JP2024501377A (ja) 2020-12-29 2021-12-29 木材を原料とする製品の製造方法
CA3203411A CA3203411A1 (fr) 2020-12-29 2021-12-29 Procede de production de produits a base de bois en tant que matiere premiere
US18/259,700 US20240076831A1 (en) 2020-12-29 2021-12-29 Method for producing products based on wood as a raw material
EP21836586.4A EP4271880A1 (fr) 2020-12-29 2021-12-29 Procédé de production de produits à base de bois en tant que matière première

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CA3203411A1 (fr) 2022-07-07
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EP4271880A1 (fr) 2023-11-08
WO2022144176A1 (fr) 2022-07-07

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