EP2489780A1 - Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile - Google Patents

Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile Download PDF

Info

Publication number
EP2489780A1
EP2489780A1 EP20110154705 EP11154705A EP2489780A1 EP 2489780 A1 EP2489780 A1 EP 2489780A1 EP 20110154705 EP20110154705 EP 20110154705 EP 11154705 A EP11154705 A EP 11154705A EP 2489780 A1 EP2489780 A1 EP 2489780A1
Authority
EP
European Patent Office
Prior art keywords
aqueous phase
solvent
organic phase
carboxylic acid
phase
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
EP20110154705
Other languages
English (en)
French (fr)
Other versions
EP2489780B1 (de
Inventor
Pablo Dominguez De Maria
Thorsten vom Stein
Philipp Grande
Walter Leitner
Fabrizio Sibilla
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.)
Rheinisch-Westfaelische Technische Hochschule Aach
Original Assignee
Rheinisch Westlische Technische Hochschuke RWTH
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 Rheinisch Westlische Technische Hochschuke RWTH filed Critical Rheinisch Westlische Technische Hochschuke RWTH
Priority to EP11154705.5A priority Critical patent/EP2489780B1/de
Priority to PCT/EP2012/000656 priority patent/WO2012110231A1/en
Publication of EP2489780A1 publication Critical patent/EP2489780A1/de
Application granted granted Critical
Publication of EP2489780B1 publication Critical patent/EP2489780B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • 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
    • 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
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes

Definitions

  • the present invention relates to a method for processing lignocellulose, comprising the step of contacting a lignocellulosic substrate with a biphasic liquid system.
  • Lignocellulose in particular, but not restricted to, "wood" is mainly composed of three components: lignin, hemicellulose (composed of sugars: principally xylose, galactose, glucose), and cellulose (composed of glucose).
  • lignin hemicellulose
  • hemicellulose hemicellulose
  • glucose cellulose
  • a selective lignocellulose fractionation into these three components may lead to a number of useful chemicals and commodities. These compounds can be used as such, or conversely can be employed via further modifications, (bio)chemical derivatizations, etc.
  • lignin can be used in the fragrance or food industry, as a thermoplastic, as a source of phenolic derivatives, or directly as a biofuel.
  • xylose provides xylitol and furfural.
  • microorganisms able to metabolize C 5 sugars to produce fuels and other bio-based commodities.
  • cellulose pulps are used in pulp & paper industries, as well as a source of C 6 fermentable sugars (to produce fuels or chemical building blocks).
  • the cosolvents employed in the organosolv processes are miscible with water at least during the conditions under which the extraction is performed.
  • strong conditions of pressure and temperature must be applied, leading again to degradation problems.
  • alcoholic co-solvents have the disadvantage that etherification and by-product formation might happen under the acidic conditions of an organosolv process ( ChemSusChem, 2010, 3, 1349 ).
  • inert and bio-based, water-non-miscible solvents may represent an interesting approach for an efficient and in situ lignocellulose fractionation.
  • Tetrahydrofuran THF
  • Johansson et al., Biomass 1987, 13, 45-65 organosolv processes
  • problems of delignification may be expected under mild reaction conditions.
  • US 5,730,837 discloses a method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars.
  • Wood or herbaceous biomass is digested at elevated temperatures in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is a phase separation.
  • the lignin is present in the organic solvent
  • the cellulose is present in a solid pulp phase
  • the aqueous phase includes hemicellulose and any dissolved sugars.
  • WO 1995/18260 A1 is concerned with a method of delignifying wood or plant material, both virgin and post-consumer with a recyclable liquid composition
  • a recyclable liquid composition comprising sodium silicate up to 2.5%, sodium hydroxide up to 2.5%, alkyl or dialkyl glycol ether and/or diglycol ether and/or propylene glycol ether in an amount of 10 to 40%, hydrogen peroxide up to 10%, triethylamine and/or diethylmethylamine and/or dimethyl pyridine and/or methyl pyridine and/or methyl piperidine up to 10% and water to give 100%.
  • the liquid composition has a lower critical solution temperature between about 0 °C and about 100 °C and the method comprises heating said wood or plant material with an effective amount of said liquid composition to release lignin from said wood or plant material.
  • the above-mentioned international patent application also discloses a method of delignifying a lignin-containing plant-derived material with a recyclable liquid composition comprising water and an organic compound which can be azeotropically purified, said liquid composition having a lower critical solution temperature of between 0 °C and 100 °C above which lower critical solution temperature said liquid composition divides into a heavier aqueous phase and a lighter organic phase.
  • This method comprises treating said lignin-containing plant derived material with a lignin-removing amount of said liquid composition at a temperature between 100 °C and 210 °C for sufficient time to release lignin from said lignin containing plant-derived material.
  • the method according to the invention provides a novel approach for selective lignocellulose fractionation.
  • Carboxylic acid catalysts depolymerize hemicellulose selectively with the possibility of mild conditions being employed, whereas cellulose-pulp is not hydrolyzed.
  • the set-up of a two-phase system affords the selective hemicellulose hydrolysis, together with efficient in situ cellulose-pulp delignification and in situ lignin extraction into the organic phase. Water-soluble sugars remain in the aqueous phase and may be collected for further processing. Insoluble cellulose-pulp is then accessible for subsequent efficient enzymatic hydrolysis to afford glucose.
  • the reagents and solvents used can be derived from bio-based resources.
  • organic solvent for example bio-based 2-methyltetrahydrofuran (2-MTHF) may be used, showing excellent properties for lignin extraction, as well as for delignification of cellulose pulp fibers.
  • the lignocellulosic substrate (which may also be referred to as lignocellulosic feedstock) used may be any lignocellulose containing biomass such as wood or pre-processed lignocellulose.
  • lignocellulosic feedstock may be any lignocellulose containing biomass such as wood or pre-processed lignocellulose.
  • examples include, but are not limited to, non-woody plant biomass, cultivated crops such as, but not limited to grasses, for example, but not limited to, C4 grasses, such as switch grass, cord grass, rye grass, miscanthus, reed canary grass, or a combination thereof, sugar processing residues, for example, but not limited to, baggase, beet pulp, or a combination thereof, agricultural residues, for example, but not limited to, soybean stover, corn stover, rice straw, rice hulls, barley straw, corn cobs, wheat straw, canola straw, oat straw, oat
  • the lignocellulosic substrate may comprise cellulosic waste material or forestry waste materials such as, but not limited to, newsprint, cardboard and the like.
  • the lignocellulosic substrate may comprise one species of fiber or, alternatively, it may comprise a mixture of fibers that originate from different lignocellulosic feedstocks.
  • the lignocellulosic substrate may comprise fresh lignocellulosic feedstock, partially dried lignocellulosic feedstock, fully dried lignocellulosic feedstock, or a combination thereof.
  • the reaction vessel for step a) may be a batch reactor or a continuous reactor. Hence, the method according to the invention may be performed as a batch or a continuous process. If desired, the reaction vessel may be equipped with stirrers, solvent reflux or pressurizing installations.
  • the lignocellulosic substrate is contacted with a biphasic liquid system.
  • a biphasic liquid system This is to be understood as the liquid system having two distinct liquid phases under the conditions of the method according to the invention.
  • the initial lignocellulosic substrate is present as a third, solid phase.
  • Other solid phases such as heterogenous catalysts, molecular sieves, ion exchangers, solid-state acids and the like are also possible.
  • a gas phase for example for pressurizing the reactor, may also be present.
  • aqueous phase As a first constituent of the biphasic liquid system an aqueous phase is present. In the aqueous phase the catalyst is preferably dissolved.
  • the second constituent of the biphasic system is an organic phase which is at least partially immiscible with the aqueous phase.
  • at least partially immiscible means that two distinct liquid phases are visible to the naked eye of an observer.
  • the second, organic phase comprises a solvent selected from the group comprising esters, lactones, ethers and/or cyclic ethers.
  • the solvent should be chosen to award a desired lignin extraction under the other boundary conditions of the method such as solvent recovery temperatures and the like.
  • esters include bio-based polypropanediol di-esters with fatty acids and diethyl succinate.
  • An example for a bio-based ether is an end-capped polypropylene glycol polyether.
  • An example for a bio-based cyclic ether is methyltetrahydrofuran.
  • a further proviso is that said solvent does not comprise a hydroxyl group or hydroxyl groups. This is based on the reasoning that OH groups might lead to undesired side reactions with other alcohols, the lignocellulose or with components extracted therefrom during the method according to the invention.
  • carboxylic acid catalyst examples include monocarboxylic acids, dicarboxylic acids and tricarboxylic acids such as formic acid, acetic acid, propanic acid, butyric acid, malonic acid, succinic acid, glutaric acid, adipinic acid, maleic acid, fumaric acid, lactic acid, malic acid, tartaric acid, citric acid and/or oxalic acid.
  • An advantage of using carboxylic acid catalysts is that they may be recovered from aqueous solutions by crystallization.
  • carboxylic acid catalyst monoesters of carboxylic acids and diesters of carboxylic acids, provided that there is at least one remaining COOH functional group present in the molecule.
  • step a) is performed at a temperature of ⁇ 85 °C to ⁇ 150 °C. Below this temperature range the reaction rate might be slower than desired and above this range cellulose depolymerization might occur to an undesired extent.
  • a preferred temperature range is ⁇ 125 °C to ⁇ 140 °C.
  • step a) is performed under a pressure of ⁇ 5 bar to ⁇ 25 bar.
  • Preferred ranges are ⁇ 10 bar to ⁇ 20 bar.
  • Pressurizing the reaction system can afford the biphasic liquid system even if the process temperature is above the boiling point of one of the constituents of the biphasic system.
  • the pressure may be raised to a level at which 2-MTHF is liquid at 140 °C.
  • the pressure may be applied via gases such as CO 2 or N 2 .
  • step a) is performed for a duration of ⁇ 2 hours to ⁇ 6 hours.
  • a preferred duration is ⁇ 2.5 hours to ⁇ 3.5 hours.
  • the carboxylic acid catalyst is selected from the group comprising dicarboxylic acids and/or monoesters of dicarboxylic acids. It is preferred that the carboxylic acid catalyst comprises oxalic acid and most preferred that that the carboxylic acid catalyst is oxalic acid.
  • the carboxylic acid catalyst is present in an amount of ⁇ 0.5 weight-% to ⁇ 2 weight-% in the first, aqueous phase.
  • the weight percentage is to be understood as the amount of the catalyst in the aqueous phase before contacting the aqueous phase with other phases such as the organic phase or the lignocellulosic substrate.
  • the catalyst amount is ⁇ 0.9 weight-% to ⁇ 1.8 weight-%.
  • the catalyst loading may be expressed as the molar concentration in the total liquid volume of the first, aqueous phase.
  • the catalyst loading may be ⁇ 0.05 M (in total liquid volume) to ⁇ 0.15 M (in total liquid volume).
  • the solvent in the second, organic phase comprises 2-methyltetrahydrofuran and/or 3-methyltetrahydrofuran. It is preferred that the solvent in the second, organic phase is 2-methyltetrahydrofuran and/or 3-methyltetrahydrofuran. Most preferred is 2-methyltetrahydrofuran (2-MTHF) as an extractive phase, as it can be derived from biomass, exhibits a miscibility gap with water, and has a boiling point (ca. 80 °C) that enables straightforward separation and recycling by distillation.
  • 2-MTHF 2-methyltetrahydrofuran
  • a combination of 2-MTHF as the solvent in the second, organic phase and oxalic acid as the carboxylic acid catalyst has proven to be particularly suited for carrying out the method according to the invention.
  • steps b1) to b3) a recycling of the carboxylic acid catalyst is effected.
  • the catalyst may be recovered by crystallization.
  • the sugar-containing mother liquor can then be further processed.
  • steps c1) to c3) With the additional procedure of steps c1) to c3) a recycling of the organic solvent is possible. At the same time the lignin dissolved therein is collected.
  • suitable solvent removal techniques include distillation and membrane separation.
  • step a) The aforementioned steps of group b1 to b3) and of group c1 to c3) may be performed sequentially. It is also possible to perform them independent of each other. Another example for a suitable procedure is to perform a batch run according to step a), remove the obtained cellulose-pulp by filtration and then to recover and recycle the catalyst and the organic solvent.
  • FIG. 1 The overall process concept is shown schematically in FIG. 1 in which lignocellulosic biomass is subjected to mild (T ⁇ 150 °C) carboxylic acid catalyzed hydrolysis in a biphasic reaction mixture comprising an aqueous phase and an immiscible organic phase.
  • a reaction vessel 10 is charged with a biphasic reaction mixture comprising a first, aqueous phase 12 and an immiscible, second organic phase 11 in the form of a cyclic ether such as 2-methyltetrahydrofuran (2-MTHF).
  • the aqueous phase 12 comprises a dicarboxylic acid such as oxalic acid as a catalyst.
  • the temperature within the reaction vessel 10 may be preferably chosen to be between 80 °C and 140 °C.
  • the reaction vessel 10 is charged with a lignocellulosic biomass by way of stream 13.
  • the mild conditions together with the choice of, for example, oxalic acid as catalyst lead to the selective hydrolysis of amorphous hemicellulose yielding soluble sugars (mostly xylose) in the aqueous phase 12.
  • lignin is dissolved in the organic phase 11.
  • the product mixture is removed from the reaction vessel 10 via stream 14 and entered into a first separation unit 15.
  • the organic phase is entered as stream 16 into a second separation unit 19 which may be a distillation unit. Recovered organic phase is recycled into reaction vessel 10 via stream 21. Lignin obtained in the second separation unit 19 is carried out as stream 23.
  • the catalyst may be separated from the aqueous stream 18 leaving the first separation unit 15 by crystallization in a third separation unit 20 before further processing and is recycled into the process via stream 22.
  • Hemicellulose sugars may be extracted from the aqueous stream in the third separation unit 20 as stream 24.
  • the remaining biopolymers cellulose and lignin separate from each other owing to their very different structures and solubility properties.
  • the cellulose stays insoluble as solid pulp and can be filtered off as stream 17 from the fist separation unit 15 for subsequent enzymatic hydrolysis into glucose.
  • the pulp should be free of lignin, which is extracted in situ into the organic phase 11 of the biphasic reaction system as already described.
  • Oxalic acid, 2-methyltetrahydrofuran (2-MTHF), Avicel®, and reagents for PAHBAH colorimetric method were obtained from Sigma-Aldrich, and were used without further purification. Beech wood with a defined size (0.5-0.8 mm) was used. Accellerase-1500® was supplied by Genencor (the Netherlands).
  • Standard procedure for lignocellulose fractionation Wood loadings (50-100 gL -1 ) were suspended in water with oxalic acid (0.1 M) (5 mL). As organic phase, 2-MTHF (5 mL) was added, and the mixture transferred to a stainless steel high pressure reactor and pressurized with CO 2 (10-20 bar). The temperature was set between 125-150 °C for the indicated reaction time. After cooling and depressurization of the reactor, the organic phase was separated by decantation and 2-MTHF was evaporated to obtain the lignin fraction. The aqueous phase was filtered to isolate the cellulose pulp, and xylose and glucose concentrations were determined in the aqueous phase. The solid residue (mostly pulp) was washed with ethanol and dried until constant weight.
  • Enzymatic procedure Cellulose-pulp or Avicel® (20 gL -1 ) were suspended in citrate buffer pH 4.5 (20 mL), at 50 °C for several hours. Accellerase-1500® was then added (1 v%). Aliquots of the reactions were taken, heated to 100 °C for 5 minutes to denaturalize the enzymes and stop the process, and stored at -20 °C until colorimetric analysis was conducted. The amount of reducing ends was determined using the PABAH method ( M. Lever, Anal. Biochem.
  • Xylose and glucose determination HPLC: HPLC measurements were carried out on a Jasco HPLC equipped with a SUGARSH1011 column with 0.01 wt% aqueous acetic acid solution as eluent. Flow rate was set to 0.6 mL min -1 and samples of 30 ⁇ L were injected. Amounts of xylose and glucose present in the hemicellulose fraction were determined based on calibration curves built with commercially available real substrates.
  • Procedure for oxalic acid recycling The aqueous phases from a representative experiment for lignocellulose fractionation were concentrated 4-fold by evaporating water. The concentrated aqueous solution was stored at 10 °C for 15 h. Under these conditions up to 85% of oxalic acid crystallized in the form of needle-like crystals. The crystals were filtered off and subjected to HPLC and NMR analysis, and subsequently re-used directly in the process.
  • beech wood was taken as a prototypical lignocellulosic substrate with an approximate (variable) composition of 15-25% hemicellulose, 15-30% lignin, and 40-50% cellulose, together with some other minor components (salts, waxes, etc).
  • a first set of experiments was conducted with various variations of the multi-component reactive system and at different temperatures (85-150 °C). The reactions were carried out either under reflux conditions or in high-pressure reactors in the presence of additional CO 2 pressure to ensure a liquid reactive system at temperatures above the solvent's boiling point. Representative results are listed in Table 1.
  • Table 1 Oxalic acid-catalyzed fractionation of beech wood in an aqueous/organic biphasic reaction system. Typical reaction conditions: beech wood (0.5-0.8 mm, 100 g L -1 in aqueous phase), oxalic acid 0.1 M (in total liquid volume), biphasic system water-2-methyltetrahydrofuran (2-MTHF) (1:1 v/v, 10 mL total), 6 hours reaction time. Entry Organic phase T (°C) p CO 2 (bar) a Soluble Sugars b Lignin (wt%) c Solid residue (wt%) d Xylose (wt%) Glucose (wt%) 1 2-MTHF 85 Reflux 4.0 n.d.
  • beech wood 0.5-0.8 mm, 100 g L -1 in aqueous phase
  • oxalic acid 0.1 M in total liquid volume
  • biphasic system water-2-methyltetrahydrofuran (2-MTHF) (1:
  • glucose was also formed during the hydrolysis.
  • the amount of glucose was in the range of 2-3% at temperatures between 125-140 °C. This level is consistent with the glucose fraction in hemicellulose.
  • glucose formation increased rapidly when temperatures higher than 140 °C were set in the reactor. This additional glucose production is likely to have arisen from cellulose depolymerization, which is known to start at temperatures of 150 °C in the presence of organic acids.
  • higher temperatures lead to a decrease in selectivity for biomass fractionation, which adversely affects the potential as feedstock for the three main (pure) components of lignocellulose.
  • the aqueous phase in the experiments contained large amounts of the oxalic acid catalyst. Gratifyingly, this can be recovered and re-used in an efficient and clean manner. Under non-optimized conditions, it was observed that by reducing the volume of the aqueous phase to one fourth and cooling it down to 4 °C, approximately 85% of the originally charged oxalic acid crystallized within 15 hours and could be recovered by simple filtration. The oxalic acid showed high purity and could be used as catalyst again without further processing or activation.
  • the solid residue (mostly pulp) constituted the third feedstock stream from the separation method which was readily isolated by filtration from the reaction mixture after removal of the 2-MTHF, and washed with ethanol.
  • the mass of the crude material (50-58 wt%, Table 1) corresponds fairly well with the amount of cellulose in beech wood.

Landscapes

  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP11154705.5A 2011-02-16 2011-02-16 Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile Not-in-force EP2489780B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11154705.5A EP2489780B1 (de) 2011-02-16 2011-02-16 Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile
PCT/EP2012/000656 WO2012110231A1 (en) 2011-02-16 2012-02-15 Integrated process for the selective fractionation and separation of lignocellulose in its main components

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11154705.5A EP2489780B1 (de) 2011-02-16 2011-02-16 Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile

Publications (2)

Publication Number Publication Date
EP2489780A1 true EP2489780A1 (de) 2012-08-22
EP2489780B1 EP2489780B1 (de) 2016-07-13

Family

ID=44515152

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11154705.5A Not-in-force EP2489780B1 (de) 2011-02-16 2011-02-16 Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile

Country Status (2)

Country Link
EP (1) EP2489780B1 (de)
WO (1) WO2012110231A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014132056A1 (en) * 2013-02-27 2014-09-04 Bio-Sep Limited Process operations for biomass fractionation
WO2014132055A1 (en) * 2013-02-27 2014-09-04 Bio-Sep Limited Biomass process optimisation
WO2014176531A2 (en) 2013-04-27 2014-10-30 The Regents Of The University Of California Co-solvent to produce reactive intermediates from biomass
US20150176090A1 (en) * 2013-12-20 2015-06-25 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration c5- and c6-carbohydrates and their derivatives
EP3689847A1 (de) * 2018-11-15 2020-08-05 CMP-Cimentos Maceira e Pataias S.A. Katalytisches und kontinuierliches thermochemisches verfahren zur herstellung von wertvollen derivative aus organischen materialien und abfällen
US11066525B2 (en) 2014-01-13 2021-07-20 Upm-Kymmene Corporation Method and apparatus for separating lignocellulose particle fraction and lignin particle fraction, lignin particle composition, lignocellulose particle composition and their use
WO2021245440A1 (en) * 2020-06-02 2021-12-09 Cmp-Cimentos Maceira E Pataias , S.A. Catalytic and continuous thermochemical process of production of valuable derivatives from organic materials and/or waste

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108883400B (zh) 2016-02-19 2021-09-17 洲际大品牌有限责任公司 由生物质源形成多值料流的方法
EP3810383A1 (de) 2018-06-25 2021-04-28 Katholieke Universiteit Leuven Fraktionierung und depolymerisierung von lignocellulosematerial
WO2023012094A1 (en) 2021-08-02 2023-02-09 Technische Universität Hamburg Process for continuous extraction of lignocellulosic material
LU102852B1 (en) 2021-08-02 2023-02-02 Technische Univ Hamburg Process for continuous extraction of lignocellulosic material
KR20240150445A (ko) 2022-02-24 2024-10-15 머쉬랩스 게엠베하 유색 진균 균사체의 생산

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3586537A (en) 1968-07-26 1971-06-22 Hoffmann La Roche Process for the production of xylose
US4087318A (en) * 1974-03-14 1978-05-02 Mo Och Domsjo Aktiebolag Oxygen-alkali delignification of lignocellulosic material in the presence of a manganese compound
EP0043342A1 (de) * 1980-06-20 1982-01-06 Battelle Memorial Institute Verfahren zur Delignifizierung von Holz und anderen Lignocellulosematerialien
US4409032A (en) 1977-08-31 1983-10-11 Thermoform Bau-Und Forschungsgesellschaft Organosolv delignification and saccharification process for lignocellulosic plant materials
US4594130A (en) * 1978-11-27 1986-06-10 Chang Pei Ching Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst
EP0211558A2 (de) * 1985-07-26 1987-02-25 Biodyne Chemicals, Inc. Verfahren zum Aufschluss von Lignocellulosematerial
WO1995018260A1 (en) 1993-12-28 1995-07-06 Mauvin Material And Chemical Processing Limited Process for delignifying virgin and post-consumer used ligno-cellulosic plant meterials for the purpose of preparing cellulosic fiber, free sugars and lignin by-products
US5730837A (en) 1994-12-02 1998-03-24 Midwest Research Institute Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
US20010018956A1 (en) * 1996-08-13 2001-09-06 Consortium Fur Elektrochemische Industrie Gmbh Multi-component system for modifying, degrading or bleaching lignin, lignin-containing materials or similar substances and processes for its use
WO2002075043A1 (en) 2001-03-20 2002-09-26 Wisconsin Alumni Research Foundation Method for producing pulp
WO2007008689A2 (en) 2005-07-08 2007-01-18 Wisconsin Alumni Research Foundation Method for treating lignocellulosic materials
CN101199944A (zh) 2007-11-23 2008-06-18 淮北中润生物能源技术开发有限公司 纤维素仿生催化水解系统及其在纤维素生物质生产液体燃料中的应用
WO2009145617A2 (en) 2008-05-29 2009-12-03 Coöperatie Cehave Landbouwbelang U.A. Method for treating vegetable material with acid as well as products obtained with this method
WO2010046051A2 (en) * 2008-10-21 2010-04-29 Eni S.P.A. Process for the production of lipids from biomass

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3586537A (en) 1968-07-26 1971-06-22 Hoffmann La Roche Process for the production of xylose
US4087318A (en) * 1974-03-14 1978-05-02 Mo Och Domsjo Aktiebolag Oxygen-alkali delignification of lignocellulosic material in the presence of a manganese compound
US4409032A (en) 1977-08-31 1983-10-11 Thermoform Bau-Und Forschungsgesellschaft Organosolv delignification and saccharification process for lignocellulosic plant materials
US4594130A (en) * 1978-11-27 1986-06-10 Chang Pei Ching Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst
EP0043342A1 (de) * 1980-06-20 1982-01-06 Battelle Memorial Institute Verfahren zur Delignifizierung von Holz und anderen Lignocellulosematerialien
EP0211558A2 (de) * 1985-07-26 1987-02-25 Biodyne Chemicals, Inc. Verfahren zum Aufschluss von Lignocellulosematerial
WO1995018260A1 (en) 1993-12-28 1995-07-06 Mauvin Material And Chemical Processing Limited Process for delignifying virgin and post-consumer used ligno-cellulosic plant meterials for the purpose of preparing cellulosic fiber, free sugars and lignin by-products
US5730837A (en) 1994-12-02 1998-03-24 Midwest Research Institute Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
US20010018956A1 (en) * 1996-08-13 2001-09-06 Consortium Fur Elektrochemische Industrie Gmbh Multi-component system for modifying, degrading or bleaching lignin, lignin-containing materials or similar substances and processes for its use
WO2002075043A1 (en) 2001-03-20 2002-09-26 Wisconsin Alumni Research Foundation Method for producing pulp
WO2007008689A2 (en) 2005-07-08 2007-01-18 Wisconsin Alumni Research Foundation Method for treating lignocellulosic materials
CN101199944A (zh) 2007-11-23 2008-06-18 淮北中润生物能源技术开发有限公司 纤维素仿生催化水解系统及其在纤维素生物质生产液体燃料中的应用
WO2009145617A2 (en) 2008-05-29 2009-12-03 Coöperatie Cehave Landbouwbelang U.A. Method for treating vegetable material with acid as well as products obtained with this method
WO2010046051A2 (en) * 2008-10-21 2010-04-29 Eni S.P.A. Process for the production of lipids from biomass

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
6 N. MOSIER; C. WYMAN; B. DALE; R. ELANDER; Y.Y. LEE; M. HOLTZAPPLE; M. LADISCH, BIORES. TECHNOL., vol. 96, 2005, pages 673 - 686
A. WISOGEL; S. TYSON; D. JOHNSON: "Handbook on bioethanol: Product and Utilization", 1996, TAYLOR & FRANCIS
A.M. KOOTSTRA ET AL., BIOTECH. BIOFUELS, 2009
BIOCHEM. ENG. J., vol. 43, 2009, pages 92
BIOCHEM. ENG. J., vol. 46, 2009, pages 126
BIOTECH. BIOENG., vol. 79, 2002, pages 610
BIOTECHNOL. PROG., vol. 17, 2001, pages 474
CHEMSUSCHEM, 13 March 2010 (2010-03-13), pages 49
CHEMSUSCHEM, vol. 3, 2010, pages 1349
J.W. LEE ET AL., BIORES. TECHNOL., vol. 100, 2010, pages 6307 - 6311
JOHANSSON ET AL., BIOMASS, vol. 13, 1987, pages 45 - 65
M. LEVER, ANAL. BIOCHEM., vol. 47, 1972, pages 273 - 279
N.S. MOSIER ET AL., BIOTECH. BIOENG., vol. 86, 2004, pages 756
R.P. CHANDRA; R. BURA; W.E. MABEE; A. BERLIN; X. PAN; J.N. SADDLER, ADV. BIOCHEM. ENGIN/BIOTECHNOL, vol. 108, 2007, pages 67 - 93
VOM STEIN, T.; GRANDE, P.; SIBILLA, F.; COMMANDEUR, U.; FISCHER, R; LEITNER, W.; DOMINGUEZ DE MARIA, P., GREEN CHEM., 18 December 2010 (2010-12-18), pages 44 - 1849
Y. LU ET AL., BIOTECHNOL. PROG., vol. 23, 2007, pages 116
Y. SUN; J. CHENG, BIORES. TECHNOL., vol. 83, 2002, pages 1 - 11
Y.H. ZHANG; M. E. HIMMEL; J.R. MIELENZ, BIOTECHNOL. ADV., vol. 24, 2006, pages 452 - 481

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9863090B2 (en) 2013-02-27 2018-01-09 Bio-Sep Limited Process operations for biomass fractionation
WO2014132055A1 (en) * 2013-02-27 2014-09-04 Bio-Sep Limited Biomass process optimisation
CN105358581B (zh) * 2013-02-27 2019-03-15 保赛有限公司 生物质分级分离的工艺操作
CN105408544B (zh) * 2013-02-27 2018-10-19 保赛有限公司 生物质工艺优化
CN105408544A (zh) * 2013-02-27 2016-03-16 保赛有限公司 生物质工艺优化
US10000891B2 (en) 2013-02-27 2018-06-19 Bio-Sep Limited Biomass process optimisation
WO2014132056A1 (en) * 2013-02-27 2014-09-04 Bio-Sep Limited Process operations for biomass fractionation
EP2989207A4 (de) * 2013-04-27 2016-11-23 Univ California Ko-lösungsmittel zur produktion reaktiver zwischenprodukte aus biomasse
WO2014176531A2 (en) 2013-04-27 2014-10-30 The Regents Of The University Of California Co-solvent to produce reactive intermediates from biomass
US10774394B2 (en) 2013-04-27 2020-09-15 The Regents Of The University Of California Co-solvent to produce reactive intermediates from biomass
US9359650B2 (en) * 2013-12-20 2016-06-07 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration C5- and C6-carbohydrates and their derivatives
US20150176090A1 (en) * 2013-12-20 2015-06-25 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration c5- and c6-carbohydrates and their derivatives
US11066525B2 (en) 2014-01-13 2021-07-20 Upm-Kymmene Corporation Method and apparatus for separating lignocellulose particle fraction and lignin particle fraction, lignin particle composition, lignocellulose particle composition and their use
EP3689847A1 (de) * 2018-11-15 2020-08-05 CMP-Cimentos Maceira e Pataias S.A. Katalytisches und kontinuierliches thermochemisches verfahren zur herstellung von wertvollen derivative aus organischen materialien und abfällen
WO2021245440A1 (en) * 2020-06-02 2021-12-09 Cmp-Cimentos Maceira E Pataias , S.A. Catalytic and continuous thermochemical process of production of valuable derivatives from organic materials and/or waste

Also Published As

Publication number Publication date
WO2012110231A8 (en) 2012-11-01
EP2489780B1 (de) 2016-07-13
WO2012110231A1 (en) 2012-08-23

Similar Documents

Publication Publication Date Title
EP2489780B1 (de) Integriertes Verfahren zur selektiven Spaltung und Trennung von Lignozellulose in die Hauptbestandteile
US8901325B2 (en) Method for producing furfural from lignocellulosic biomass material
US11492753B2 (en) Process for the treatment of lignocellulosic biomass
US9765478B2 (en) Treatment of biomass to dissolve lignin with ionic liquid composition
US10072099B2 (en) Process for the organosolv treatment of lignocellulosic biomass
EP2235254B1 (de) Verfahren zur vorbehandlung von lignocellulosematerial im hinblick auf die herstellung von bioethanol und herstellungsverfahren für bioethanol
US20180223383A1 (en) Sugar compositions
CA2933847A1 (en) Processes and apparatus for producing furfural, levulinic acid, and other sugar-derived products from biomass
US10174131B2 (en) Biomass processing method
AU2015252695B2 (en) Liquid co-extraction process for production of sucrose, xylo-oligosaccharides and xylose from feedstock
WO2014106220A1 (en) Processes for fractionating whole plants to produce fermentable sugars and co-products
US20150184259A1 (en) Processes and apparatus for producing fermentable sugars from biomass by hot-water extraction and enzymatic hydrolysis
WO2016029069A1 (en) Processes for producing cellulosic fructose from lignocellulosic biomass
EP3822407A1 (de) Verfahren zur herstellung von bioprodukten aus lignocellulosischem material
US20150361474A1 (en) Processes for producing cellulosic fructose from lignocellulosic biomass
US20200207925A1 (en) Lignocellulosic biomass treatment method and system
WO2015116411A1 (en) Methods and apparatus for removing dissolved gases from fermentation streams

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20130220

17Q First examination report despatched

Effective date: 20130912

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011028041

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: D21C0003200000

Ipc: D21C0011000000

RIC1 Information provided on ipc code assigned before grant

Ipc: D21C 11/00 20060101AFI20151118BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHEINISCH-WESTFAELISCHE TECHNISCHE HOCHSCHULE AACH

INTG Intention to grant announced

Effective date: 20160208

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 812435

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160715

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011028041

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 812435

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161013

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161114

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161014

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011028041

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161013

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

26N No opposition filed

Effective date: 20170418

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170228

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20171031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160713

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20210218

Year of fee payment: 11

Ref country code: NL

Payment date: 20210217

Year of fee payment: 11

Ref country code: IT

Payment date: 20210222

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210225

Year of fee payment: 11

Ref country code: GB

Payment date: 20210219

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011028041

Country of ref document: DE

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20220301

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220216

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220216