EP3172378B1 - Verfahren zur herstellung von nanofasern aus den stängeln von einjährigen pflanzen - Google Patents

Verfahren zur herstellung von nanofasern aus den stängeln von einjährigen pflanzen Download PDF

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Publication number
EP3172378B1
EP3172378B1 EP15730546.7A EP15730546A EP3172378B1 EP 3172378 B1 EP3172378 B1 EP 3172378B1 EP 15730546 A EP15730546 A EP 15730546A EP 3172378 B1 EP3172378 B1 EP 3172378B1
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Prior art keywords
minutes
cellulose
concentration
temperature
suspension
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English (en)
French (fr)
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EP3172378A1 (de
Inventor
Janusz KAZIMIERCZAK
Ewa KOPANIA
Arkadiusz BLODA
Grazyna KRZYZANOWSKA
Anna KLUSKA
Justyna WIETECHA
Danuta Ciechanska
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Instytut Biopolimerow I Wlokien Chemicznych
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Instytut Biopolimerow I Wlokien Chemicznych
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Priority to PL15730546T priority Critical patent/PL3172378T3/pl
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
    • 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
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • 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
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/123—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with Cl2O
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse

Definitions

  • This invention relates to the preparation of cellulose nano-fibres from stalks of annual crops.
  • a method is known of preparing cellulose nano-fibers from a fibrous pulp derived from natural fibers, root crops, fibre crops which contain hemicellulose, lignin, pectin and mineral substance.
  • the method comprises several consecutive steps of preparing the nano-fibres: hydrolysis of the fibrous pulp by means of a diluted acid at temperature of 70 - 90°C, extraction in alkaline medium, cryogenic disintegration, and defibrillation in a homogenizer at high pressure.
  • the obtained nano- fibers may be used as reinforcement in resin composites prepared by film casting, forming or extrusion for application in medical devices and packaging.
  • EP 2 415 821 known is a method of preparing a cellulose gel.
  • the method consists in that the cellulose material is first treated with an oxidizing agent generating carboxylic groups on the cellulose surface.
  • the suspension of the cellulose material is then homogenized and the obtained suspension of nano-fibers is treated with an organic-or inorganic acid to cause the cellulose nano-fibers aggregate into a gel.
  • the liquid gel is again mechanically processed.
  • the outcome is a gel which contains cellulose nano-fibres holding free carboxylic groups on its surface.
  • the prepared cellulose gel reveals low water absorption and swelling due to that the unreacted carboxylic groups are not as prone to dissociation as those reacted to salts.
  • Patent US 8546558 describes a method of preparing micro-fibril cellulose from a hemicellulose-containing sulfite pulp derived preferably from coniferous wood. The method involves mechanical grinding, action of hemicellulase or cellulase or mixture of the two and a further mechanical homogenization. Prospective uses of the micro-fibril cellulose are in food, cosmetics, pharmacy, paper, composites, coatings and thickeners.
  • a method to make cellulose nano-fibrils is described in the international patent application WO 2010092239 .
  • the method provides preparation of a suspension of cellulose fibers upon which adsorbed is a cellulose derivative (e.g. carboxymethylcellulose) or a polysaccharide or its derivative.
  • the fibers are then disintegrated to nano-fibrils.
  • Chemical-, mechanical-, thermo-mechanical or chemical-thermo-mechanical cellulose pulp was used as starting material. It was derived from wood, non-woody materials or recycled cellulose fibers.
  • the nano-fibrils sized below 1 micrometer find their uses in food, concrete, drilling fluids, coatings, cosmetics, drugs and paper.
  • WO 2013188657 is a method for the manufacture of nano-fibres from a cellulosic material by processing of an aqueous suspension with a cellulose depolymerizing agent such as ozone, cellulase or a combination of the two, and a parallel or subsequent mechanical disintegration which delivers nano-fibers from the cellulosic material.
  • a cellulose depolymerizing agent such as ozone, cellulase or a combination of the two
  • a parallel or subsequent mechanical disintegration which delivers nano-fibers from the cellulosic material.
  • Low energy consumption is an asset of the method in comparison to processes employing only mechanical disintegration.
  • Nano fibers from the method find their use in paper making.
  • the method of preparing cellulose nano-fibers from stalks of annual plants according to the invention consist in that the stalks cut into pieces 10-70 mm long are processed in following steps:
  • the digesting in step c) can, according to the invention, be run in a liquor with a content on dry mass of 5 - 15 wt.% of NaOH and 0,1 - 0,5 wt.% of anthraquinone or a liquor with 5 - 15 wt% of NaOH, 3 - 6 wt% of H 2 O 2 , 0.1 - 0,3 wt% of ethylenediaminetetraacetic acid (EDTA), 0,2 - 0,5 wt% of MgSO 4 and 2 - 5 wt% of water glass.
  • EDTA ethylenediaminetetraacetic acid
  • the cellulose pulp is, according to the invention, in addition to the bleaching in step e) preferably put to de-lignification by the action of 1 - 2 wt% of peracetic acid and 0,2 - 0,5 wt% of MgSO 4 , calculated on dry mass. Conditions: temperature of 80 - 90°C for 60-120 minutes.
  • the cellulose pulp holding about 50 - 70 wt% of water is, after the bleaching in step e) and prior to the enzymatic treatment in step f), preferably put for 20 - 90 minutes to mechanical defibrillation followed by homogenizing in water suspension.
  • the sediment formed after homogenization and centrifugation in step g) can be recirculated to step f) and put to repeated enzymatic treatment with a solution of cellulase.
  • the multi-stage de-lignification combined with bleaching of the lingo-cellulose raw material, according to the invention, offers the chance of removing the non-cellulosic substance without a far-going degradation of cellulose thus providing a high output of cellulose pulp with excellent purity.
  • the multi-stage mechanical treatment of the pulp combined with enzymatic hydrolysis of cellulose makes it possible to prepare cellulose nano-fibres having a high proportion of length to thickness.
  • the method according to the invention enables the utilization of agriculture residues such as linen and hemp waste straw remaining after the separation of seeds for oil expression.
  • nano-fibres made according to the invention can be used as reinforcement in the production of composite materials, as thickener or constituent of a variety of coatings
  • Hemp stalks cut to pieces 40 - 60 long were loaded into a 15 dm 3 swing digester and put for 10 minutes to the action of 2 bar steam and then three times defibrillated in the disk mill of Sprout-Waldron type with a consecutive decrease of the distance between the defibrillating elements (0,5, 0,2 and 0,1 mm).
  • the slackened plant raw material was for 60 minutes digested at 110°C in a liquor containing: 5 wt.% of NaOH, 5,5 wt.% of H 2 O 2 , 0,3 wt. of EDTA, 0,5wt.% of MgSO 4 and 5% water glass calculated on dry mass at fluid module of 4:1.
  • the fibrous pulp was subjected to delignification with oxygen in a medium containing 2,5 wt% of NaOH and 0,5 wt% of MgSO 4 on dry mass with oxygen pressure at start of 0,2 MPa, pulp concentration 8wt%, for 60 minutes, at 120°C.
  • the cellulose pulp was bleached twice with sodium chlorite at NaClO 2 concentration of 1,4wt% and H 2 SO 4 concentration of 0,1wt% at 70°C, for 120 minutes. After every chemical treatment, the cellulose pulp was washed with demi water and centrifuged.
  • the prepared cellulose pulp was characterized by lignin content of 0,45% and alfa-cellulose content of 85,5 wt%, and average polymerization degree of 1266. Total output of the process was 65,9%.
  • An aqueous 2,5 wt% suspension of the cellulose in a conical flask was placed on the platform of incubator with a rotation shaker Labfors (Infors) and put to enzymatic treatment with cellulase (Ecostone L900, AB Enzymes) having endo-1,4-beta-glucanase activity of 500 J/g at pH of 4.8 at 50°C, for 180 minutes at agitation rate of 150 rpm.
  • the 1.5wt% aqueous suspension was for 10 minutes homogenized in the homogenizer Ultra Turrax T50 (IKA) at 10000 rpm.
  • IKA homogenizer Ultra Turrax T50
  • the suspension was quenched with refrigerating brine at -15°C.
  • the prepared fibers were characterized by thickness in the range of 30 to 120 nm and average molecular degree of 130.
  • the prepared cellulose pulp was characterized by lignin content of 9 wt% and alfa-cellulose content of 80,3 wt%, and average polymerization degree of 1306. Total output of the process was 69,5%.
  • the cellulose pulp was put to mechanical treatment for 60 minutes at 40 rpm in a laboratory shredder.
  • the 1,5wt% aqueous suspension of cellulose was put to enzymatic treatment like in Example 1 save amount of enzyme which was 300 J/g.
  • the residual enzyme in the cellulose pulp was deactivated like in Example 1.
  • the 1,5wt.% aqueous suspension of cellulose was homogenized by means of the homogenizer Ultra Turrax T50 in 3 cycles with the G45F tool and 3 cycles with W65SK tool at 10 000 rpm for 3 minutes in each of the cycles. During the homogenization, the suspension was quenched with refrigerating brine at about -15°C. The cellulose suspension was centrifuged as in Example 1 and the cellulose- -nano-fibers- containing supernatant was separated. The prepared fibers were characterized by thickness in the range of 40 to 160 nm and average molecular degree of 155.
  • Stalks of oil flax cut to 30 - 60 mm pieces were steam-treated, defibrillated, digested, put to delignification in oxygen medium, bleached with sodium chlorite and alkaline-extracted like in Example 1.
  • the prepared cellulose pulp was characterized by lignin content of 14 wt% and alfa-cellulose content of 72,4 wt%, and average polymerization degree of 1151. Total output of the process was 92,3%.
  • the cellulose pulp was enzyme-treated like in Example 1.
  • a 2,5 wt% suspension of the cellulose in water was next prepared and put to homogenization in the homogenizer Ultra Turrax T50 at 10 000 rpm for 3 minutes in each of the 5 homogenization cycles.
  • the suspension was quenched with refrigerating brine at about -15°C.
  • the cellulose suspension was thereafter for 20 minutes centrifuged at 4 500 rpm.
  • the deposit was again put to enzyme treatment like in Example 1, employing cellulase with endo-1,4-beta-glucanase activity of 200 J/g.
  • From the remaining sediment prepared was a 1,5 wt% cellulose suspension in demi water which was for 3 minutes mechanically processed in each of the 3 cycles by means of the homogenizer Ultra Turrax T50 at 10 000rpm.
  • the suspension was in the consecutive step for 20 minutes centrifuged at 4 500 rpm. Supernatants from both steps of the processing were combined thus improving the output of the process.
  • the prepared fibers were characterized by thickness in the range of 45 to 200 nm and average molecular degree of 190.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Claims (6)

  1. Art und Weise der Herstellung von Zellulose-Nanofasern aus den Stängeln der einjährigen Pflanzen charakterisiert sich dadurch, dass die 10-70 mm langen Fragmente der Stängel der einjährigen Pflanzen in folgenden Etappen bearbeitet werden:
    a) Behandlung mittels des Wasserdampfs unter dem Druck von 1 ,5-3 bar innerhalb von 5-60 Min.;
    b) mechanische Zerfaserung in einer Scheibenmühle innerhalb von 3-10 Min.;
    c) Beuchen in der Flüssigkeit, die 5-15% NaOH im Verhältnis zur trockenen Stängelmasse enthält, Flüssigkeitsmodul 3:1-8:1, innerhalb von 60-120 Min., Temperatur 110-160°C;
    d) Delignifizierung im Sauerstoffumfeld mittels wässriger Lösung, die 2-4% NaOH und 0,2-0,5% MgSO4 enthält, im Verhältnis zur trockenen Masse, Anfangsdruck des Sauerstoffs von 0,2 -0,5 MPa, Konzentration der Masse 8-15%, innerhalb von 60 - 120 Min., Temperatur 110 - 120°C;
    e) mindestens zweimaliges Bleichen mittels des Natriumchlorits bei NaClO2-Konzentration von 1 - 1,5% und H2SO4-Konzentration von 0,05 - 0,1%, Temperatur 60 - 70°C, innerhalb von 60 - 120 Min. und die darauf nachfolgende alkalische Extraktion in der NaOH-Lösung von der Konzentration 0,5 - 1%, Temperatur 70 - 80°C, innerhalb von 60-120 Min.;
    f) enzymatische Behandlung erhaltener Zellulosemasse mittels der Zellulase von der Aktivität Endo-1,4-beta-Glukanase von 10-1000 J/g, im Verhältnis zur trockenen Masse, bei pH-Wert von 4 - 7, Temperatur 40 - 60°C, innerhalb von 30-480 Min., bei Mischgeschwindigkeit 50 - 500 U/min., danach Waschen der Zellulosemasse mittels des enthärteten Wassers und Abfiltrieren unter vermindertem Druck, danach Desaktivierung des in der Zellulosemasse übrig gebliebenen Enzyms bei der Temperatur 90 - 125°C, innerhalb von 10 - 30 Min.;
    g) Homogenisierung der wässrigen Zellulose-Suspension von der 0,5-3%-Konzentration mit der Drehgeschwindigkeit von 5000 - 20000 U/min., innerhalb von 1 - 10 Min., abgekühlt während der Homogenisierung mittels der Sole von der Temperatur ca. - 15°C, danach Zentrifugieren der Suspension bei der Drehgeschwindigkeit von 4000 - 15000 U/min. innerhalb von 5 - 30 Min., um den die Zellulose-Nanofasern enthaltenden Supernatant zu erzielen
  2. Art und Weise gemäß Vorbehalt 1 charakterisiert sich dadurch, dass die Beuchen-Flüssigkeit 0,1% Antrachinon enthält.
  3. Art und Weise gemäß Vorbehalt 1 charakterisiert sich dadurch, dass die Beuchen-Flüssigkeit 3 - 6% H2O2, 0,1 - 0,3% Versensäure, 0,2 - 0,5% MgSO4 und 2 -5% Wasserglas enthält.
  4. Art und Weise gemäß Vorbehalt 1 charakterisiert sich dadurch, dass die Zellulosemasse nach dem Beuchen in der Etappe e) mit der zusätzlichen Delignifizierung mittels der Überessigsäure von der Konzentration 1 - 2% der Überessigsäure und 0,2 - 0,5% MgSO4, im Verhältnis zur trockenen Masse, Temperatur 80 - 90°C, innerhalb von 60-120 Min. behandelt wird.
  5. Art und Weise gemäß Vorbehalt 1 charakterisiert sich dadurch, dass die Zellulosemasse von der Feuchtigkeit 50 - 70% nach dem Beuchen in der Etappe e) vor der enzymatischen Behandlung in der Etappe f) mit der mechanischen Zerfaserung innerhalb von 20 - 90 Min. und danach der Homogenisierung in der wässrigen Suspension behandelt wird.
  6. Art und Weise gemäß Vorbehalt 1 oder 2 oder 3 charakterisiert sich dadurch, dass der nach der Homogenisierung und Zentrifugierung in der Etappe g) entstandene Schlamm zurück in die Etappe e) zugeführt wird.
EP15730546.7A 2014-07-23 2015-05-05 Verfahren zur herstellung von nanofasern aus den stängeln von einjährigen pflanzen Active EP3172378B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15730546T PL3172378T3 (pl) 2014-07-23 2015-05-05 Sposób wytwarzania nanowłókien celulozowych z łodyg roślin jednorocznych

Applications Claiming Priority (2)

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PL408962A PL230426B1 (pl) 2014-07-23 2014-07-23 Sposób wytwarzania nanowłókien celulozowych z łodyg roślin jednorocznych
PCT/PL2015/000075 WO2016013946A1 (en) 2014-07-23 2015-05-05 Method of preparing cellulose nano-fibres from stalks of annual plants

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EP3172378B1 true EP3172378B1 (de) 2018-04-25

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US12195919B2 (en) 2021-11-18 2025-01-14 Kanbol, Inc. Multi-step low temperature and low pressure process for agricultural feedstock stock preparation with hemicellulose and lignin recovery
US12338578B2 (en) 2021-05-28 2025-06-24 Kanbol, Inc. System and method for refining agricultural fibers to a pulp specification

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US10287366B2 (en) 2017-02-15 2019-05-14 Cp Kelco Aps Methods of producing activated pectin-containing biomass compositions
US10196778B2 (en) 2017-03-20 2019-02-05 R.J. Reynolds Tobacco Company Tobacco-derived nanocellulose material
CN108193539A (zh) * 2017-12-28 2018-06-22 云南云景林纸股份有限公司 一种获取均匀分离桉木纸浆纤维的制备方法
CN108589365B (zh) * 2018-05-22 2019-10-11 南京林业大学 一次研磨法制备木质纤维素ⅱ晶型纳米纤维的方法
JP7520873B2 (ja) * 2019-01-22 2024-07-23 イーナ トレーディング アンパーツゼルスカブ セルロース繊維の調製
CN110273312A (zh) * 2019-07-23 2019-09-24 呼伦贝尔学院 一种天然牧草基纳米纤维素的提取和制备方法
CN110744668B (zh) * 2019-10-30 2021-09-28 凉山德农生物能源股份有限公司 一种小桐子基纳米纸浆的制备方法
CN111763992B (zh) * 2020-06-23 2021-12-21 徐州璞素室内装饰材料有限公司 一种书画用麻布生产用苎麻原料揉搓装置
CN112878085A (zh) * 2021-02-09 2021-06-01 齐齐哈尔大学 一种用大麻皮制备纳米纤维素的方法
CN113718541B (zh) * 2021-07-13 2022-10-21 大连工业大学 一种本征疏水亲油纳米纤维素的制备方法
WO2024079809A1 (ja) 2022-10-12 2024-04-18 日本たばこ産業株式会社 たばこ製剤、たばこシート、たばこ充填物、喫煙物品、たばこ製剤の製造方法、及びたばこシートの製造方法
JPWO2024079810A1 (de) 2022-10-12 2024-04-18
EP4635310A1 (de) 2022-12-12 2025-10-22 Japan Tobacco Inc. Tabakfolie, verfahren zur herstellung einer tabakfolie, tabakfüllstoff und rauchartikel

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Publication number Priority date Publication date Assignee Title
US12338578B2 (en) 2021-05-28 2025-06-24 Kanbol, Inc. System and method for refining agricultural fibers to a pulp specification
US12195919B2 (en) 2021-11-18 2025-01-14 Kanbol, Inc. Multi-step low temperature and low pressure process for agricultural feedstock stock preparation with hemicellulose and lignin recovery

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PL3172378T3 (pl) 2018-08-31
WO2016013946A1 (en) 2016-01-28
PL408962A1 (pl) 2016-02-01
PL230426B1 (pl) 2018-10-31
EP3172378A1 (de) 2017-05-31

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