EP2212469A2 - Verfahren zur zerfaserung eines fasrigen rohmaterials - Google Patents

Verfahren zur zerfaserung eines fasrigen rohmaterials

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Publication number
EP2212469A2
EP2212469A2 EP08851453A EP08851453A EP2212469A2 EP 2212469 A2 EP2212469 A2 EP 2212469A2 EP 08851453 A EP08851453 A EP 08851453A EP 08851453 A EP08851453 A EP 08851453A EP 2212469 A2 EP2212469 A2 EP 2212469A2
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EP
European Patent Office
Prior art keywords
lignin
process according
raw
cooking
pulp
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.)
Granted
Application number
EP08851453A
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English (en)
French (fr)
Other versions
EP2212469B1 (de
Inventor
Hannu Mikkonen
Soili Peltonen
Anne Kallioinen
Anna SUURNÄKKI
Vesa Kunnari
Tero Malm
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VTT Technical Research Centre of Finland Ltd
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VTT Technical Research Centre of Finland Ltd
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Publication of EP2212469A2 publication Critical patent/EP2212469A2/de
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Classifications

    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/18—Pulping cellulose-containing materials with halogens or halogen-generating compounds
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • 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
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides

Definitions

  • the present invention relates to a process for defibering a fibrous raw-material according to the preamble of claim 1.
  • a fibrous raw-material is contacted with a pulping liquor containing an organic solvent for defibering a fibrous raw-material.
  • the invention relates also to a process according to the preamble of claim 22 for recovering lignin and to a process according to the preamble of claim 28 for recovering hemicelluloses, respectively.
  • Defibering of a fibrous material, such as chips, which hereinafter also is referred to by the term "delignification”, is performed mainly by sulphate (or kraft) or sulphite cooking, wherein sulphur and sodium chemicals of a water based cooking liquor are used as an active cooking chemical.
  • defibering means the separation of fibres from each others by dissolving lignin that acts as adhesive. Yields of kraft cooking before bleaching are in the range of 50 to 53 % for hardwood and about 46 to 49 % for softwood. Both the fibrous material and residual lignin are sulphur-containing, and thus also nonreactive, after the cooking.
  • the invention is based on the idea that a raw-material is treated in an organic solvent containing a lower acid of phosphorus.
  • a fibre-containing raw-material is cooked in an organic solvent containing hypophosphoric acid or another phosphoric acid derivative having a lower degree of oxidation (lower than that of 5. orthophosphoric acid).
  • lignin that is dissolved into the cooking liquor is precipitated from the solvent with a non-solvent, in particular with water.
  • the process for recovering lignin according to the invention is, in turn, characterized by5 what is stated in the characterizing part of claim 22.
  • the process for recovering hemi- cellulose according to the invention is characterized by what is stated in the characterizing part of claim 28.
  • the fibrous material that can be obtained from cooking has interesting properties, such as good mechanical properties, reactivity with functionalizing enzymes and en excellent enzyme hydrolysability into sugars.
  • lignin can be recovered in the form of reactive nanoparticles, which have5 been found to contain ⁇ 1 % chemically bound phosphorus, which may also have significance as a fire retardant.
  • Organophosphate groups can bind metal ions and thus may serve as an ion exchanger.
  • the fibres produced according to the new cooking process from plant fibres, such as from0 wood or reed canary grass, and lignin obtainable from cooking are suitable e.g. for fibre composites and special paper applications as well as for lignin products (sizes, coatings, composite matrices). Delignification according to the invention can also be used as a pre- treatment stage in isolation of hemicellulose. Taking into account only the yield of lignin, 60 to 75 % of dry weight of the plant material is utilized as useful products. In the following the invention will be examined in more detail by means of the detailed description and working examples.
  • Figure 1 is shown a TEM-picture of lignin nanoparticles produced by means of the in- vention. Particles of less than 50 nm and respectively about 100 ran are seen from the picture,
  • FIG 2 are shown bar charts depicting enzyme hydrolysis of two pulps obtained from a cooking according to example 10.
  • Figure 3 is graphically depicted the effect of Trametes hirsuta laccase on oxygen con- sumption of lignin pulps, described as a function of time of measurement, and
  • Figure 4 is a corresponding diagram for oxygen consumption of LGF-4 lignin in the presence of laccase.
  • Figure 7 are shown graphically the grinding curves or a tensile index of the pulps as a function of grinding.
  • Figures 8A and 8B are shown the effect of birch pulp produced by the process according to the invention on the air permeance of the paper, and on the smoothness of the sheet surface.
  • Figure 9 are shown two diagrammatic plans from pulp treatment, wherein the upper one (1) depicts the sequence, wherein the pulp is treated with laccase and then an sheet is formed, after which the technical properties are determined from it, and the lower one depicts the sequence, wherein sheeting is followed by spraying the sheets with laccase, press- ing and drying the sheets, after which the technical properties are determined from the sheets.
  • FIG 10 are shown bar charts for tensile strengths of two samples.
  • HA to HC are shown bar charts for 15 samples, wherein "RM” represents a compound of cellulose acetate plastics and organosolv birch fibre (example 5), fibre of CA-RM reed canary grass produced according to example 10, birch cellulose I, birch cellulose II and birch cellulose III represent birch sulphate cellulose fibre taken from different process stages; birch cellulose I - after sulphate cooking, birch cellulose II - before bleaching, and birch cellulose III - bleached pulp.
  • Figure 1 IB are shown the yield strength comparisons and in Figure 11C breaking strength comparisons.
  • the cooking process according to the present invention is based on a so far unknown (unidentified) chemical reaction, wherein phosphinic acid or its derivative catalyses, in an organic solvent, the delignification process while covalently attaching to lignin.
  • phosphinic acid H 3 PO 2 , H 2 P(O)(OH), its tautomeric form HP(OH) 2 and salts thereof are strong reducing agents.
  • peroxoformic acid which is an active cooking chemical of another so-called organosolv-process, namely the MILOX process.
  • a mineral acid phosphinic acid is a monoprotic acid pKa: 1.2, but weaker than H 2 SO 4 or HCl
  • phosphinic acid and its tautomeric form and salts thereof, other derivatives of phosphorus can be used, wherein phosphorus has a lower oxidation degree than ortho- phosphoric acid.
  • the cooking process would seem to be based on acidic catalytic delignification of phosphinic acid and on the other hand on its capability chemically to attach to lignin.
  • the mechanism of delignification has not been elucidated, but it is possible that the effect of the phosphinic acid can relate to the benzyl positions of a phenyl propane unit of lignin and to reactions of acetal or ketal links of the wood structure. In that case organophosphate groups or such ester groups would seem to be formed.
  • the process according to the present invention works well on different plant-based materials. Annual and perennial plants are suitable as starting materials. According to one preferred application defibrated pulp is produced from wood. Some domestic plant species such as pine, spruce, birch, aspen or alder can serve as a starting material, but also other wood species can be used, such as eucalyptus, maple, Cottonwood, mixed tropical hardwood etc. According to another preferred embodiment, the process according to the invention is applied for annual plants, such as straw of grain crops, reed canary grass and bagasse. It should be pointed out that the fibrous raw-material, such as straw and wood, can be mechanically pre-treated (refined, sawdust, woodchips as well as mechanical pulp) or classified in various ways. Fibres of very high quality or merely fermentable sugars can be the target. Hemicellulose can be as a by-product and in all cases technically useful pure lignin.
  • the sulphur-free cooking process developed works very well on reed-stem plants, soft and hardwood trees in up to 50 to 60 % yield, in addition to which from 10 to 15 % of purified lignin is obtained as particles having particle size of from 50 to 100 nm according to the TEM description.
  • the total yield is thus from 60 to 75 % of the starting material.
  • Cooking can be carried out as well on wood at natural moisture or on dry starting material at almost anhydrous conditions.
  • the yield of the spruce cooking carried out in dry conditions can be e.g. about 54 %, in other words on the order of 10 % better than that of kraft cooking compared to the values in literature.
  • the residual lignin concentration for birch fibre corresponding to the 50 % yield was 3.35 % and the yield of isolated lignin was 11 %.
  • the glucose concentration of the fibre was 89.5 % and the concentration of xylan was 7.8 %.
  • the active residue lignin contained in the fibre can in principal be used to increase the enzymatic strength of the sheet. This is exemplified by a test wherein laccase treated fibres that were cooked with the new process gave 10 % higher tensile strength compared to the reference treated fibres (shown in appendix).
  • the fibres are well suited at least as fibre reinforcement for biopolymers (in an exemplifying embodiment, cellulose acetate and PLA) in fibre composites. Birch fibres produced by the process increase the module of the reinforcement by a factor of 3x.
  • the improvement in the module was 10 % higher and in yield and breaking strength was 9 % higher.
  • the strength values for a reed canary grass fibre composite were comparable to a bleached sulphate-process birch fibre reinforcement.
  • the cooking process can also be used as a pre-treatment step for biomass in the production of fermentable sugars.
  • the alkaline extraction with 0.5M NaOH is combined to the defibering, for example material, having an enzyme hydrolability of 100 % (time of ⁇ 24 h) is obtained from reed canary grass in -40 % total yield.
  • the alkali extraction is suitable for isolation of hemicellulose. Based on the sugar analysis, the alkali treatment increased the glucose concentration of the fibre by 25 % and decreased the xylan concentration by about 50 %. Alkali treatment also removed clearly the residual lignin of fibre, so it is also a pulp bleaching process.
  • acetic acid, formic acid and ethanol are suitable as an organic part of the cooking liquor (cf. below in more detail). Ratio of the solvent to the starting material can be, as has been proved, changed more preferred by recycling the cooking liquor.
  • the economical potential can be considered to be significant, since the most possible objective comparison to the main process (kraft cooking) offers an advantage in magnitude of at least 10 %, measured by almost any product characteristics.
  • Cooking process is in principal extremely gentle, and it can generally be carried on at from about 50 to about 125 °C. As it is evident hereinafter, according to the examples operation were at a temperature of about from 75-110 °C. Longer treatment times are used at lower temperatures to enhance the penetration of cooking chemicals into the fibre raw-material, for example woodchip. Reaction times could very well be increased by a pressurized process, hi case of phosphinic acid, elevating the temperature is not recommended (or it should be avoided), because risk for decomposition of reagent increases, as the temperature exceeds 110 °C.
  • the overpressure is typically about 1.1 ... 10 times normal atmospheric pressure.
  • the same cooking liquor can be recycled in the process several times, whereby a higher concentration is achieved for lignin, if it is to be isolated.
  • the amount of phosphinic acid in the cooking solution is at industrial scale operations e.g. about from 0.01 to 10 %, preferably about from 0.1 to 5 %, of hypophosphoric acid from the weight of the cooking liquor.
  • the amount of phosphinic acid can also be adjusted according to the fibrous material being brought to the cooking.
  • cooking liquor contains therefore about from 0.1 to 50 %, in particular about from 0.5 to 20 %, of hypo- phosphoric acid from the dry matter of raw-material.
  • the amount of phosphinic acid is considerably high (up to 1 : 1 for the material to be cooked).
  • the large volume required by the material has partly affected the high reagent amount (for example straw or bark).
  • the process operates excellently with dosages mentioned above.
  • a good pulp is obtained from birch at dosages of phosphinic acid in the range from about 5 to 15, e.g. at about 10 % calculated from the dry weight of birch.
  • the corresponding amount for softwood is from 5 to 25 % as calculated from the dry weight of softwood.
  • Small molecular weight carboxylic acids are suitable as solvents as well as aliphatic alcohols (alkanols) and aromatic alcohols of 6 to 10 carbon atoms.
  • hydrocarbon residue of carboxylic acid comprises 1 to 6, in particular 1 to 4 carbon atoms.
  • suitable solvents should be mentioned formic acid, acetic acid and propionic acid mentioned above.
  • alkanoic acids also corresponding peracids can be used as well as suitable hydroxy acids.
  • Aromatic alcohols can also be used.
  • Suitable alkanols contain generally 1 to 6 carbon atoms and 1 to 5 hydroxyl groups, in particular 1 to 3 hydroxyl groups.
  • Aromatic alcohols are e.g. phenol and benzyl alcohol.
  • polar organic solvent such as Ci- 6 -alkanoic acid, Q- 6 -alkanol or polyol or aromatic alcohol, hydrocarbon residue thereof containing 6 to 10 carbon atoms, or a mixture thereof.
  • Solvent can contain water, which originates e.g. from the fibrous raw-material to be treated. However, the amount of water is so small that the organic solvent serves as a solvent for lignin that is released from the fibrous material in connection with cooking (in practice during it).
  • concentration of water in moles is not over about 50 % the total mole amount of water and solvent, or the molar ratio of water and solvent is up to about 1:1, most suitably it is less than 1:1, in particular the molar ratio of water and solvent is from about 0 to about 40 %, most suitably from 0 to about 30 %.
  • at least some amount of water typically at least about 0.1 weight- % of the liquid phase, often at least about 0.2 %, enters with the raw-material or cooking chemical to the cooking.
  • the organic solvent used in the present process is most suitably water miscible, whereupon the liquid phase of the cooking stays in one phase during the treatment.
  • defibering of the raw-material is carried out at less than 20 %, preferably less than 10 % total moisture content.
  • Lignin obtainable from the cooking can be produced irrespective of the plant species into the nanoparticles with a very simple process.
  • the preparation of nanopaiticles of lignin by means of known techniques is an expensive and complicated process requiring high technology from the apparatus.
  • nanoparticles of lignin can be prepared simply by precipitating them from water solution.
  • a special feature of the particles is a high phenol functionality that is promoted by the small particle size of the particles, in general about from 50 to 100 run. Phenol functionality is well visible e.g. as a high response to the oxidative enzymes.
  • Phenol functionality is well visible e.g. as a high response to the oxidative enzymes.
  • Probably organic phosphorus bound to the lignin has a significant role in dispersing mechanism of lignin, which that seems to happen spontaneously without mechanical dispersing or auxiliary dispersing substances.
  • lignin is left deliberately into the fibres, e.g. the amount corresponding to the portion of Klason lignin (about 2 to 3 %), whereby a very high reactivity towards different chemicals that activate by oxidation is achieved for the fibre.
  • activity observed for the laccase enzyme is an order higher than for mechanical pulps.
  • laccase Since the effect of laccase is based on the oxidation reaction, along with laccase and, at least in some cases, as a substitutive chemical for it, some oxidative chemical can be used, typically alkali metal salts of peroxosulphur acid.
  • the laccase enzyme of the fibre 1000 nkat/g activity in consumption of oxygen DO > 4 mg/1, in 30 min or up to DO > 5 mg/1 in 30 minutes.
  • the shown defibering treatment is continued until an essential part of the fibre matter has been defibrated. In general this corresponds to a case, wherein a significant amount of lignin has dissolved from the starting material.
  • the starting material hardwood/softwood/grasses
  • the yield of the defibrated pulp is in general up to ca. 90 weight-%, in particular yield is about from 30 to 75 weight-% from the starting material.
  • the Kappa value is in general 10 to 150 with unbleached pulp, in particular about 15 to 120, most suitably about 20 to 110. After bleaching the kappa number is e.g. with hardwood about from 10 to 30, with softwood from 10 to 40.
  • the process can also be understood as some sort of a concept, wherein the aim is to utilize wood or reed totally by fractionating it into polymer components.
  • lignin, hemicellulose and cellulose could be separated from each others gradually.
  • An efficient exit of hemicellulose from the fibre can be concluded also by examining the sugar compositions of the fibres. Quite mild alkali treatment (0.5 M NaOH) decreases for example xylose concentration of birch fibre to a half. If an alkali treatment is carried out after removal of lignin, cellulose is obtained mainly as the end product. The removal of hemicellulose serves at the same time as a bleaching process.
  • the cooking can in principle be directed "over" in such a way that micro- crystalline cellulose or cellulose fibrils can be produced from the end product with a good yield, in other words to carry out partly the acid hydrolysis of cellulose during the cooking and/or to increase the enzyme hydrolysis rate of the polysaccharide.
  • the fibrous material produced by means of the present cooking can be used as such, or as further functionalized in fibre composites (either with synthetic or bio plastics) and in special paper and paperboard applications (filters, traceability, recognisability) or as a base paper in printed electronics (especially then, if it is accompanied with alkali sensitive conducing polymer).
  • Lignin can be used directly to replace the present lignin product in existing applications (sizes, adhesives, wood preservatives, fertilizers, etc.) to bring added value, such as fire resistance or microbiological durability of wood surface.
  • lignin could bring new properties, among others to fibre composite products and as an additive and possibly also as a matrix material.
  • the amount of chemically bound phosphorus being >1 % the polymeric derivative serves in principle as an ion exchange resin or as a metal cation trap.
  • lignin is dissolved into the cooking liquor, from which it is separated, whereby lignin dissolved into the cooking liquor can preferably be precipitated from the solvent e.g. with water.
  • the pH of lignin to be precipitated is set to a value of 4.5 to 6.0, in particular about to a value of 5.0 to 5.5.
  • the fibrous raw- material is treated with the presented cooking solution to dissolve lignin, whereby cooking is most suitably continued, until at least about 20 % of the raw-material has been dissolved.
  • Fibrous raw-material, from which a significant part of lignin has been removed, can be separated from the cooking liquor, after which it is treated separately with an alkali to dissolve hemicellulose. From the alkali solution hemicellulose can for its part be isolated by precipitation, e.g. by using water, or with membranes or other corresponding means.
  • a significant part is separated from the fibrous raw-material, typically about 25 to 35 of dry weight, whereby most of lignin is removed from it, after which at least about 50 weight- % of hemicellulose contained therein is extracted with an alkali solution from the treated fibrous raw-material.
  • alkali an aqueous solution of alkali or earth alkali metal hydroxide is used, having molality such as above noted, relatively low, e.g. about 0.1 to 5 M, most suitably about 0.1 to 1 M.
  • the solution was dyed to reddish brown, but the sticks were not dispersed into fibre.
  • the sticks were purified with a process according to example 1 and the acetic acid solutions, 400 ml, were spared for further analyses.
  • Klason's soluble lignin 0.54 %
  • Klason's gravimetric lignin 3.52 % rhamnose ⁇ 0.10 arabinose ⁇ 0.10 galactose ⁇ 0.10 glucose 86.9 % xylose 7.89 % mannose 0.50 % methyl glucuronic acid (MeGIcA) 0.15 % galacturonic acid (GlIA) ⁇ 0.10
  • Yield was 195 g of pulp having dry matter concentration of 25.1 %. This corresponds to 48.1 % yield if birch fibre calculated from dry weight of wood.
  • the following composition was determined for birch fibre:
  • Klason's soluble lignin 0.59 % Klason's gravimetric lignin: 3.40
  • Example 5 Production of birch fibre with acetic acid-phosphinic acid cooking, from fresh birch wood
  • Yield was 186 g of pulp, having dry matter concentration of 26.6 %. This corresponds to 50.3 % yield of fibre calculated from dry weight of wood.
  • the obtainable fibre is suitable for example for reinforcement of plastics (in particular thermoplastics).
  • Example 6 Production of spruce fibre from classified needlesticks (pin chips) with acetic acid-phosphinic acid cooking
  • Example 7 Production of spruce fibre from woodchips with phosphinic acid-acetic acid cooking
  • Fresh spruce chips 267 g dry matter concentration of 37.2 %, corresponding to 100 g calculated as dry wood of spruce, were immersed into the cooking liquor containing 302 g of acetic acid, 30 g of 100 % calculated of phosphinic acid and 30 g of water. Woodchips were cooked in the solution for 88 h at temperature of 105 0 C, whereupon wood softened and degraded into fibres as lignin dissolved in acetic acid. After reaction time mother liquor was aspirate with vacuum from the pulp, giving a yield of 231 g, after this the fibre cake was rinsed part by part with 70 % acetic acid to remove lignin and cooking chemicals.
  • the yield of washing solution was 246 g, which was combined to the previous filtrate (mother liquor). After this the fibre was washed with water in 5 % slurry, filtered onto the wire and the filtrate was sucked once through the fibre cake. Finally the pulp was washed on the filter with water and concentrated with vacuum suction.
  • composition was determined for treated inner bark of birch rhamnose ⁇ 0.10 galactose ⁇ 0.1 % glucose 48.6 % xylose 3.8 % mannose 0.64 % fructose ⁇ 0.1 %
  • Birch wood (119 g, dry matter concentration 84 %, corresponding to 100.0 g of dry wood) was combined with a pulping liquor containing 251 g of formic acid, 25 g of phosphinic acid and 25 g of water.
  • the cooking time was 19 h 30 min, during which time wood degraded totally into fibres.
  • Lignin-containing cooking liquor was removed from fibre by means of vacuum suction and the yield was 268 g. After this the pulp was rinsed with 70 % formic acid to remove the dissolved lignin.
  • the rinsing solution was recovered while amount thereof was 266 g, after which the lignin solutions were combined.
  • the fibre was washed with water according to example 1.
  • Straw of reed canary grass amount of which was 55.3 g (dry matter concentration 90.3 %), or 50.0 g calculated as dry matter, was mixed with 904 g of cooking liquor, having a composition of 604 g of acetic acid, 60 g of phosphinic acid, and 240 g of water. The mixture was cooked for 13 h at temperature of 105 0 C, whereupon straw softened and degraded into fibres. The fibre was purified by a process according to example 1. Yield 134 g of wet pulp, dry matter concentration 20.3 %, corresponding to 54.0 % yield. The wet pulp was dried in a convection oven at a temperature of 60 0 C.
  • Example 11 Production of reed canary grass with acetic acid-phosphinic acid cook- ing
  • Pulp corresponding to an amount of 30.0 g of dry weight, was treated with alkali extraction according to example 10, whereby yield of cellulose rich pulp as dry weight was 23.3 g, corresponding to 77.6 % yield from the ethanol cooked fibre and 57 % yield from the straw raw-materials of the starting situation.
  • Example 13 Production of nanoparticles of lignin from the cooking liquor by water dilution
  • Acetic acidic lignin solution (376 g), obtained from example 1, was diluted with water to a volume of 3000 ml, whereupon a precipitation of lignin is formed, that can at least once sedimented and to separate dissolved acetic acid by decanting.
  • a new water dilution is carried out after this to a volume of from 2000 to 3000 ml, the lignin precipitation does not anymore sediment by gravitation, but water dispersion is formed, that can be concen- trated by centrifuging with high speed 3000 to 5000 r.p.m/ 15 min.
  • Thermoplasticity of nanoparticles of lignin produced from different starting materials was studied by means of DSC analysis.
  • Protobind 1000 a commercial lignin, was used as a reference sample.
  • DSC analysis was run as two from 0 to 125 0 C cycles using 10 °C/min temperature increasing and decreasing speed.
  • Table 3 The glass transition temperature of organosolv lignin nanoparticle produced from different starting materials, determined by DSC. Analytical samples were made by drying a lignin dispersion sample in a convection oven/ 60 0 C.
  • Table 3 shows that the glass transition temperature of lignins produced with an organic solvent was at about 100 °C and that the lignins act thermoplastically.
  • the molecular masses of lignins are assayed by GPC techology and the results are expected to explain some of the observed differences between different examples.
  • Lignin-containing formic acid solution amount of which was 664 g, was diluted with wa- ter to 3000 ml, and prepared with a centrifuging wash at pH value of 5 to a nanoparticle dispersion of lignin, giving a yield of 16 g (dry matter concentration 20.14 %) corresponding to 6.4 % yield of purified lignin nanoparticles calculated from the dry weights of straw.
  • the flax fibre pulp (27 g of dry matter) was mixed to a volume of 1000 ml of 0.5 M NaOH-solution and extracted for 24h at a temperature of 20 °C to separate hemicellulose. After the extraction the pulp was filtered through a wire and the filtrate was sucked once through the fibre cake. The solution containing the alkali soluble polysaccharides was stored and finally the fibres were rinsed on the filter with cold water.
  • Yield was 116.46 g of wet cellulose pulp, dry matter concentration was assayed to be 19.34 %. This corresponds to 45 % yield calculated from the dry matter of straw at starting situation.
  • Flax could be fractionated by the process as follows: Biomass divided into either in 54 % yield of corresponding amount of fibre and in 6.4 % yield of corresponding amount of lignin nanoparticles, or in 45 % yield of corresponding amount of cellulose rich fibre, 9 % of alkali soluble polysaccharides (mainly hemicellulose) and 6.4 % of nanoparticles of flax lignin. In total the conversion of flax into useful polymeric products was 60.4 %.
  • Example 15 Treatment of polymers of birch wood with acetic acid-phosphinic acid coking
  • Birch was fractionated with phosphinic acid cooking, into cellulose, hemicellulose, and lignin nanoparticles.
  • the starting situation (1.000 kg per moist wood, 57 % dry matter concentration) 1754 g of birch sticks (pin chips), 1000 g as calculated dry wood, was mixed into a solution, having a composition of 5000 g of acetic acid, 100 g of phosphinic acid and 246 g of water, at a cooking time at a temperature of 100 °C and at normal pressure was for 31 h 30 min, during which time the wood stick degraded into fibres.
  • the fibres were purified by a process according to example 1 and lignin nanoparticles were produced by a process according to example 12. Hemicellulose was isolated from fibres by extracting 2 % fibre slurry in 1 M NaOH solution for 24 h at room temperature.
  • the polysaccharide fraction that was dis- solved to alkali was purified by ultrafiltering trough a 5000 g/mol [cut off] membrane, after which it was freeze-dried.
  • the polymers of birch fibres could be fractionated by the process.
  • Hemicellulose 5.8 % Mw > 5000 g/mol
  • FIG 2 is illustrated the enzyme hydrolysis in cooking carried out according to example 10.
  • the experiment scores SR-5 pulp 1 and 2 of hydrolysis of canary grass pulp cooked according to example 11 mean the fibre sample before and after the alkali extraction.
  • Al- kali extraction clearly removes components that slow down hydrolysis from the pulp, such as hemicellulose, which appears well also on changes in the sugar composition of the pulp (table 4).
  • Alkali treatment after the hydrolysis of the pulp after 24 h is already 100 %, which corresponds in the analysis to DNS mg/ml of glucose.
  • Reactivity of fibres produces according to example 1 in an oxidation reaction catalyzed by laccase enzyme was measured as the consumption of dissolved oxygen.
  • the oxygen measurement was performed by determining the concentration of oxygen dissolved into the fibre suspension during the laccase treatment. Measuring was performed in a sealed sample vessel with SensorLink PCM800 apparatus using an oxygen electrode (Clark). It is evident from Figure 3 that the new organosolv fibres are very laccase reactive and that they can therefore be activated in the oxidation reaction catalyzed by laccase, for further utilizing, for example as suitable for functionalizating.
  • Example 18 Special properties of nanoparticles of lignin, laccase enzyme activity
  • Figure 4 is shown the oxygen consumption of birch lignin nanoparticles produced by process according to example 1 in an oxidation reaction catalyzed by laccase enzyme.
  • the oxygen measuring was performed by using the oxygen measuring process described in example 16. From Figure 4 is observed that the lignin nanoparticles produced by the organosolv cooking process described in the invention were very reactive in the oxidation reaction catalyzed by laccase.
  • Example 20 Physical and strength characteristics of fibres.
  • Figure 7 is shown the compensation on density difference of pulps of the experimental sequence (test sequence) compared with the industrial pulps.
  • Reference is the birch sulphate cellulose pulp used in the production of experimental sheets.
  • table 4 are shown extensively the physical characteristics of the birch pulp produced by cooking according to example 1 and a comparison to the industrial pulps.
  • test sequence is cooked birch according to example 1.
  • Reference point is a commercial birch pulp.
  • the permeability and smoothness of the sheet correlate to a certain degree with each others; some kind of on optimum, in accordance of these variables, would seem to correspond to 48 to 50 % fibre yield such as in example 4.
  • Example 23 The effect of laccase reactivity of the fibre on the strength of the sheet
  • Results are shown in the bar chart of Figure 10.
  • the laccase treatment of the fibres was performed in the sheet mould with laccase dosing or 500 nkat/g of dry fibre. According to the obtained results, the tensile strength of the paper produced from organosolv fibre made according to the invention could be increased clearly with the laccase treatment.
  • the fibre was washed with water according to example 5.
  • Cellulose ester plastics was commercial cellulose triacetate softened with 50 php of triethylcitrate (TEC).
  • CA-RM represents cellulose acetate plastics organosolv birch fibre (example 5) compound, CA-RM reed canary grass the fibre produced according to example 10.
  • Birch cellulose I, birch cellulose II and birch cellulose III represent birch sulphate cellulose fibre taken from different process steps. Birch cellulose 1 - after sulphate cooking, birch cellulose II - before the bleaching and birch cellulose III - bleached pulp.
  • Figure HB are presented yield strength comparisons.
  • the sample codes are the same as in Figure HA.
  • Figure HC depicts comparisons of breaking strength.
  • the sample codes are the same as in Figure 1 IA
  • the strength of cellulose acetate fibre compounds are generally better than with reference pulps.
  • the birch fibres produced by the process according to the invention gave a comparable result compared to the birch sulphate cellulose, when they are used as reinforcement for PLA.
  • a remarkable improvement was achieved very especially on the breaking strength with 20 % proportion of the inventive birch fibre compared to birch sulphate cellulose pulp taken any one of the process steps.
  • Blends have been compounded with a Brabender batch mixer intended for laboratory use, while using Nocke's tip mixing arms (volume of 80 cm3). Temperatures in the cellulose acetate mixtures were 220 °C and PLA in the mixtures were 190 0 C.
  • testing poles ("dog-bones") are produced with a Therino Haake MiniJet injection moulding apparatus. Injection pressure 600 to 700 bar, injection time 3 to 5 s, exit pressure 320 to 400 bar, exit time 15 to 30 s. Temperature of the mould with cellulose-acetates 40 to 50 0 C, with PLA 25 to 30 0 C.
  • testing poles were tested with a testing machine (Instron).
  • PLA + RM birch test poles have not been kept according to the standard for five days in condition cupboard but the samples have been tested immediately after making then. Due to the crystallinity of PLA the results of these testing poles may improve while PLA crystallises.
  • the poles have hydrophilic fibres that may waken the mechanical properties while absorbing moisture.
  • Example 25 Production of reed canary grass fibre at a low water concentration

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  • Paper (AREA)
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EP08851453.4A 2007-11-20 2008-11-20 Verfahren zur zerfaserung eines fasrigen rohmaterials Not-in-force EP2212469B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20075823A FI122535B (fi) 2007-11-20 2007-11-20 Menetelmä kuitumaisen raaka-aineen kuiduttamiseksi sekä massa ja sen käyttö
PCT/FI2008/050671 WO2009066007A2 (en) 2007-11-20 2008-11-20 Process for defibering a fibrous raw-material

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EP2212469A2 true EP2212469A2 (de) 2010-08-04
EP2212469B1 EP2212469B1 (de) 2013-11-20

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BR (1) BRPI0819738A2 (de)
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FI129824B (en) * 2020-03-31 2022-09-15 Chempolis Oy Separation of lignin
CN114763680B (zh) * 2021-01-15 2024-01-30 中国石油天然气股份有限公司 从木质纤维素原料中去除木质素的方法
WO2025182046A1 (ja) * 2024-02-29 2025-09-04 国立大学法人京都大学 樹皮溶液、樹皮成形品、及び積層材

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US3585104A (en) * 1968-07-29 1971-06-15 Theodor N Kleinert Organosolv pulping and recovery process
DE2737118A1 (de) * 1977-08-17 1979-03-01 Projektierung Chem Verfahrenst Verfahren zur gewinnung von zuckern, gegebenenfalls cellulose und gegebenenfalls lignin aus lignocellulosischen pflanzlichen rohstoffen
YU41117B (en) * 1977-08-31 1986-12-31 Paszner Laszlo Process for obtaining sugovar, lingnig and cellulose from lignocellulose

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WO2009066007A2 (en) 2009-05-28
FI122535B (fi) 2012-03-15
FI20075823L (fi) 2009-05-21
EP2212469B1 (de) 2013-11-20
FI20075823A0 (fi) 2007-11-20
WO2009066007A3 (en) 2009-10-22
BRPI0819738A2 (pt) 2015-06-16

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