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WO2025162806A1 - Procédé de fabrication de fils de cellulose dérivés de matiéres premiéres cellulosique - Google Patents

Procédé de fabrication de fils de cellulose dérivés de matiéres premiéres cellulosique

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Publication number
WO2025162806A1
WO2025162806A1 PCT/EP2025/051628 EP2025051628W WO2025162806A1 WO 2025162806 A1 WO2025162806 A1 WO 2025162806A1 EP 2025051628 W EP2025051628 W EP 2025051628W WO 2025162806 A1 WO2025162806 A1 WO 2025162806A1
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WO
WIPO (PCT)
Prior art keywords
ionic liquid
cellulose
protic
range
liquid
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.)
Pending
Application number
PCT/EP2025/051628
Other languages
English (en)
Inventor
Enrique Herrero Acero
Murray J. Height
Martin GEBERT-GERM
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.)
Heiq Aeoniq Holding Ag
Original Assignee
Heiq Aeoniq Holding Ag
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 Heiq Aeoniq Holding Ag filed Critical Heiq Aeoniq Holding Ag
Publication of WO2025162806A1 publication Critical patent/WO2025162806A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts

Definitions

  • the present invention relates to a process for conditioning cellulose feedstock, including recycled materials containing cellulose, based on dissolution in ionic liquids and, if needed, addition of active substances to degrade and remove colors and/or if needed modify the molecular weight distribution of the cellulose polymers.
  • the process enables direct processing of recycled materials and subsequent spinning into high tenacity low fibrillation fibers.
  • the invention relates to high-tenacity, high-elongation, low-fibrillation fibres, in particular such fibres obtained using such a process.
  • the sustainability profile of regenerated cellulose yarns can be further improved when cellulose sources based on recycled cellulose raw materials are used.
  • cellulose sources based on recycled cellulose raw materials are used. Examples include post-industrial fabrics and post-consumer apparel such as articles that contain cotton, viscose, lyocell and other forms of cellulose.
  • Additional cellulose-containing streams e.g. agricultural waste, lignocellulose extracted pulp, bacteria-derived cellulose, algae-derived cellulose etc. may also be used as sources of cellulose.
  • WO-A-03029329 discloses how cellulose is dissolved in an ionic liquid without derivatization, and is regenerated in a range of structural forms without requiring the use of harmful or volatile organic solvents.
  • Cellulose solubility and the solution properties can be controlled by the selection of the ionic liquid constituents, with small cations and halide or pseudohalide anions favoring solution.
  • WO-A-2004084627 discloses a regenerated cellulose-encapsulated active substance and a method for encapsulating an active substance in a regenerated cellulose matrix.
  • the distribution of the active substance is preferably substantially homogeneous within the matrix of regenerated cellulose.
  • the regenerated cellulose (i) has about the same molecular weight as the original cellulose from which it is prepared (ii) is substantially free of added substituent groups relative to the starting cellulose and is also substantially free of entrapped ionic liquid degradation products.
  • WO-A-2009062723 relates to a method for producing regenerated biopolymers in the form of carbohydrates, using a solvent system that contains the biopolymers dissolved therein.
  • the solvent system is based on a melted ionic liquid and optionally a protic solvent or a mixture thereof.
  • the biopolymers dissolved in the solvent system are precipitated in a coagulation medium, said medium comprising a protic coagulant or a mixture of protic coagulants.
  • the method according to the invention is characterized in that the surface tension o of the coagulant or the mixture of coagulants is 99% to 30% of the surface tension o of water, the surface tension being measured according to ASTM D 1590-60 at a temperature of 50° C.
  • the method according to the invention is economical and flexible and leads to advantageous products, especially in the form of staple fibers which are especially not fibrillated and have an advantageous wet to dry strength ratio.
  • WO-A-2007076979 proposes a solvent system for biopolymers in the form of carbohydrates which is based on a molten ionic liquid, with additives being present in the solvent system if appropriate.
  • This solvent system comprises a protic solvent or a mixture of a plurality of protic solvents, and if the protic solvent is water alone, this is present in the solvent system in an amount of more than about 5% by weight.
  • Carbohydrates can be incorporated into the solvent system, in particular in the form of starch, cellulose and derivatives thereof, and the solvent system can then be employed for regenerating the carbohydrates dissolved therein.
  • CN-A-106146877 discloses a method for recovering waste textile by the aid of an ionic liquid.
  • the method comprises steps as follows: 1) pretreatment of the waste textile: the waste textile is crushed, and pretreated waste textile is obtained; 2) water swelling and dissolution in the ionic liquid: the pretreated waste textile, the ionic liquid and water are mixed and stirred under the vacuum condition, and a liquid containing cellulose is obtained.
  • the waste textile is pretreated and swollen in water, the dissolution process is uniform and mild, the dissolution efficiency is high, the effect is good, and the waste textile is thoroughly separated from insoluble matters.
  • a cellulose solution obtained through dissolution can be used for preparing a regenerated cellulose material with excellent performance, and polyester obtained through separation can serve as a polyester raw material to be recycled.
  • WO-A-2021234226 provides a process for the production of a cellulose filaments or films, comprising the steps of dissolving a cellulose substrate in an ionic liquid consisting of the superbase cation 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-enium [mTBDH]+ and an anion to produce a solution forming a spinning dope, said anion being derived from an acid which is present at a stoichiometric excess to the superbase, extruding the spinning dope through a spinneret in a coagulation bath containing water to form filaments or films from the solution, withdrawing ionic liquid in an aqueous mixture with water from the coagulation bath, recovering the ionic liquid [mTBDH][OAc] from the aqueous mixture by removing water and optionally recycling the recovered ionic liquid to the dissolution step.
  • WO-A-2017019802 discloses methods and systems which use mixed textile feedstock, which may include post-consumer waste garments, scrap fabric and/or other textile materials as a raw feed material to produce isolated cellulose and other isolated molecules having desirable properties that can be used in the textile and apparel industries, and in other industries.
  • a multi-stage process is provided, in which mixed textile feed material is subjected to one or more pretreatment stages, followed by at least two pulping treatments for isolating cellulose molecules and other molecular constituents, such as polyester.
  • the isolated cellulose and polyester molecules may be used in a variety of downstream applications. In one application, isolated cellulose and polyester molecules are extruded to provide regenerated cellulose fibers and regenerated polyester fibers having desirable (and selectable) properties that are usable in various industrial applications, including textile production.
  • WO-A-2023104635 discloses a method for the production of cellulose yarns from recycling cellulose material, wherein the method comprises the following steps: (a) dissolution of the recycling cellulose material in a molten ionic liquid; (b) adapting the conditions such that active substances dissolved or dispersed in the molten ionic liquid or generated in situ in the molten ionic liquid act to degrade non-cellulose material initially contained in the recycling cellulose material and contained in the molten ionic liquid due to the dissolution of the recycling cellulose material, wherein the active substances can already be present during (a) or can be added after (a) and before or during (b).
  • Object of the present invention is correspondingly a method as claimed and fibers as claimed as well as uses of the fibers as claimed.
  • a method for the production of cellulose yarns from a feedstock cellulose material wherein the method comprises the following steps:
  • the solution containing at least one molten ionic liquid used for step (a) can be fresh ionic liquid or can be ionic liquid recycled from the process.
  • the initial molten ionic liquid for step (a) and/or the molten ionic liquid solution resulting from step (a) and/or step (b) preferably comprises a protic liquid in an amount of less than five weight percent.
  • step (b) i.e. to have a step of maintaining the heated solution with the dissolved cellulose material in a resting state, so essentially without stirring and preferably essentially without contact with air, leads to a stable process.
  • the corresponding resting time is usually implemented by a corresponding buffer tank for realizing step (b), so it is possible to have a first container for mixing and carrying out step (a), the output thereof is then transferred to a buffer container to implement step (b) and output of that buffer container is then used for step (c).
  • this can also be expressed as a minimum weight of extruded fiber of at least 12.5 g (e.g. for 25 dtex, and an extrusion speed expressed in weight of 0.12 g/min), or at least 25 g (e.g. for 50 dtex, and an extrusion speed expressed in weight of 0,25 g/min) or at least 37.5 g (e.g. for 75 dtex, and an extrusion speed expressed in weight of 0,375 g/min).
  • step (b) it is preferred to avoid contact with air during the resting step (b), and therefore contact with air in step (b), while the solution is in a resting tank, is preferably avoided.
  • This can be implemented by having an inert gas atmosphere above the liquid solution. This avoids oxidation of the material in the top layers of the liquid in the resting tank, which adds to reducing the stability problems of the extrusion process.
  • step (b) is carried out “essentially without stirring”
  • the corresponding energy input per unit volume (time average equivalent or continuously at this level) provided by corresponding stirring should however preferably not be above 1 W/m 3 , preferably not be above 0.5 W/m 3 , and most preferably not be above 0.1 W/m 3 .
  • the method includes a step before step (c), which reduces the protic liquid content in the molten ionic liquid cellulose solution to the desired level, e.g. by evaporation and degassing, in particular if the protic liquid is water.
  • step (b) the solution containing ionic liquid with dissolved cellulose material and a protic liquid is preferably maintained at a temperature in the range of 60-90°C, preferably in the range of 70-90°C or 80-90°C.
  • step (b) the solution containing ionic liquid with dissolved cellulose material and a protic liquid is preferably maintained for a time span in the range of 5-15 hours, preferably in the range of 7-10 hours.
  • step (b) the solution containing ionic liquid with dissolved cellulose material and a protic liquid is preferably heated to maintain, during step (b), a constant temperature around a fixed value, preferably a fixed value in the range of 75-90°C, with a deviation of less than 10°C, preferably of less than 5°C above and below that fixed value.
  • the zero shear viscosity of the solution containing ionic liquid with dissolved cellulose material and a protic liquid preferably is in the range of 1 ,000-50,000 Pa.s at 50°C, preferably in the range of 2,000-10,000 Pa.s at 50°C during step (b). These values were determined with a Rheometer MCR 302e from Anton Paar using a 25 mm plate. A force- controlled frequency sweep was used with frequency range from 100 rad/s to 0.1 rad/s.
  • the cellulose content of the solution containing ionic liquid with dissolved cellulose material and a protic liquid during step (b) and/or step (c) is preferably in the range of 2-20% by weight, preferably in the range of 5-18% by weight.
  • the protic liquid of the solution containing ionic liquid with dissolved cellulose material and a protic liquid during step (b) and/or step (c) is preferably selected to be, preferably solely, water and the content thereof is in the range of 1.5-4.5% by weight, preferably in the range of 2-4% by weight.
  • the solution containing ionic liquid with dissolved cellulose material and a protic liquid is preferably maintained essentially without stirring in a storage vessel or a section of a storage tube or cavity, and wherein at least for transferring the solution containing ionic liquid with dissolved cellulose material and a protic liquid into said storage vessel or section of a storage tube, a pump is used, if need be assisted with negative headspace pressure, wherein preferably in the headspace above said solution a pressure in the range of 5-200 mbar, preferably in the range of 10-50 mbar is established.
  • a pump For transferring the solution containing ionic liquid with dissolved cellulose material and a protic liquid after step (b) for step (c) to the spinning beam a pump is used, if need be assisted by an inert gas, preferably nitrogen gas, preferably in the atmosphere above the solution containing ionic liquid with dissolved cellulose material and a protic liquid, preferably at an overpressure, in particular in the range of 1.5-4 bars, preferably in the range of 2-3.5 bars.
  • an inert gas preferably nitrogen gas
  • the temperature of the solution containing ionic liquid with dissolved cellulose material and a protic liquid can be reduced to a value in the range of 70-90°C, preferably in the range of 75-85°C.
  • Step (a) can incorporate or be followed by the following steps:
  • the dissolution firstly acts to separate out the non-soluble components e.g. synthetic fibers, mineral matter;
  • Active substances dispersed in the ionic liquid act to degrade the diverse dyestuffs associated with the cellulose, and also to degrade fatty and other organic impurities;
  • Absorbents inorganic may be homogeneously dispersed in the IL to specifically absorb impurities e.g. dyes and other unwanted ingredients.
  • the loaded absorbents are filtered off from the cellulose-IL solution and may be reused after a suitable regeneration process.
  • Active substances may also be chosen in such a way to reduce the molecular weight of the cellulose polymer chains to assist in subsequent fiber spinning. Reduction of molecular weight can be achieved through exposure to short wavelength radiation e.g. UV light or photocatalysis in the presence of a catalyst. Following dissolution of the cellulose materials in the ionic liquid and exposure to the oxidative atmosphere the active reagents (e.g. hydrogen peroxide and/or enzymes and/or catalyst salts) are added and the mixture is heated while stirring to a temperature between 40 and 120 °C and maintained at temperature for 0.5 to 24 hours duration to achieve the desired decolorization. The resulting solution may then be heated/cooled to achieve the desired target temperature and then may be used directly to the fiber spinning process.
  • active reagents e.g. hydrogen peroxide and/or enzymes and/or catalyst salts
  • Processing directly within the ionic liquid medium used for subsequent fiber spinning avoids intensive conventional pre-processing steps that would otherwise require intensive water and energy use, further improving the sustainability profile of the recycling path.
  • the resulting processing path requires less processing steps and enables a more direct utilization of recycled waste materials containing cellulosic components.
  • ionic liquids and fiber spinning process as described by W02007076979 and W02009062723 (the disclosure of which is included) provides a basis for achieving favorable regenerated cellulose fibers with ionic liquids that are tolerant to significant presence of protic components including water.
  • the process advantageously enables the pre-processing active substances that provide the in-situ decolorization and impurity degrading/absorbing actions without impacting the performance of the subsequent fiber spinning. This pre-processing would otherwise not be feasible with ionic liquid systems and fiber spinning processes that are less tolerant of water content.
  • Ionic liquids can be used for dissolving under oxidative atmosphere for the dissolution of the cellulose and also for the dissolution or dispersion of active substances, and can tolerate water or other protic solvents up to certain amount for the dissolution of cellulose and spinning while achieving excellent fiber properties, allowing at the same time for the introduction of catalytic components which do not increase the water or other protic solvents levels to a level that would adversely impact proper fiber spinning and consequently the fiber properties.
  • the hydrogen peroxide breaks down into residual water (ionic liquid process is tolerant to presence of remaining water), oxygen and non-colored residual degradation by-products.
  • the residual by-products may optionally be removed directly without degradation or through use of sorbent materials after its breakdown in contact with the ionic liquid processing medium.
  • the molecular weight of the cellulose polymer has a direct impact on the fiber spinning performance and also the mechanical properties of the resulting yarn;
  • Reduction of the molecular weight may occur through action of hydrogen peroxide alone and/or with addition of other components e.g. ozone or UV light or photocatalysis selected to cleave the cellulose polymer resulting in reduced average molecular weight;
  • Such additives may include enzymes and/or salts.
  • the action of such additives in the ionic liquid medium is facilitated by the presence of water in the ionic liquid that is a feature of W02007076979 and W02009062723 (the disclosure of which is included).
  • enzymes e.g. Laccases
  • active substances like for example enzymes to achieve decolorization effect in ionic liquid processing medium
  • WO2016087186A1 and US8445704 describe use of ionic liquids as a processing medium for chemical modification and transformation of polysaccharides however there is no use of hydrogen peroxide/ozone, short wavelength radiation, photocatalysis and/or enzymes to address colors and impurities or to address the molecular weight of the cellulose.
  • US11168196 describes an approach to facilitate separation of blended cellulose/polyester waste however there is no provision for actively addressing colors, impurities, and/or molecular weight within the ionic liquid used to dissolve the cellulose component.
  • the adaptation of the conditions according to step (a2) can be carried out in different ways, for example by changing the solvent composition, by adding said active substances (alone or in a carrier solvent), by activating said active substances, by changing the temperature, the pH or by changing the pressure, or by introducing activation energy for example by irradiation, or a combination of such adaptations.
  • active substance in the context of (a2) includes substances which are suitable and adapted to fulfil the function to degrade non-cellulose material initially contained in the recycling cellulose material, and examples thereof are given further below.
  • the recycling cellulose material is preferably selected from at least one of cellulose containing streams such as waste, recycling yarns, recycling fabrics, recycling tissue, recycling clothing.
  • the non-cellulose material is typically selected from at least one of non-cellulosic material, including non-cellulosic fibres (e.g. PET, PA, elastane, PE, etc. or mixtures thereof), dyestuffs, fatty and other organic impurities, including oils, waxes and detergent residues, inorganic substances such as sand or clay, water soluble and water insoluble pigments.
  • non-cellulosic fibres e.g. PET, PA, elastane, PE, etc. or mixtures thereof
  • dyestuffs e.g. PET, PA, elastane, PE, etc. or mixtures thereof
  • fatty and other organic impurities including oils, waxes and detergent residues
  • inorganic substances such as sand or clay
  • this step includes at least one of filtration, decanting, centrifugation, sieving.
  • the ionic liquid solution comprises a protic liquid, preferably water.
  • the active substance is preferably selected from the group of absorbents, cleaving agents, including biological cleaving agents, physical cleaving agents and chemical cleaving agents, wherein preferably absorbents are selected from the group of substances adsorbing at least one of dyestuffs, fatty impurities and other organic impurities, and wherein preferably cleaving agents are selected from the group of direct cleaving agents or activatable cleaving agents, preferably activated by irradiation of electromagnetic irradiation, wherein the cleaving agents can be selected from the group of enzymatic systems including proteases, oxidoreductases, amylases, laccases and lipases, ozone, peroxides, photocatalysts, and a combination thereof.
  • cleaving agents including biological cleaving agents, physical cleaving agents and chemical cleaving agents, wherein preferably absorbents are selected from the group of substances adsorbing at least one
  • the active substance hydrogen peroxide is used.
  • the active substance is a substance with acts as an oxidizer and has a bleaching effect.
  • the ionic liquid from the beginning comprises or is supplemented after step (a2) or after (c), if present, with a system to reduce the molecular weight of the cellulose polymer, preferably selected from the group of enzymatic systems including cellulases or hemicellulases or cellulose oxidases, in particular endoglucanases, exoglucanases or cleaving agents activated by irradiation of electromagnetic irradiation, or strong bases, or a combination thereof.
  • a system to reduce the molecular weight of the cellulose polymer preferably selected from the group of enzymatic systems including cellulases or hemicellulases or cellulose oxidases, in particular endoglucanases, exoglucanases or cleaving agents activated by irradiation of electromagnetic irradiation, or strong bases, or a combination thereof.
  • step (a2) the temperature is preferably increased to a range of 40-120°C, and preferably maintained at this temperature for a timespan in the range of 0.5-24 hours.
  • step (a2) or after step (c) the cellulose yarn can directly be spun from the cellulose dissolved in the ionic liquid.
  • Said molten ionic liquid further comprises a protic solvent or a mixture of several protic solvents, wherein, in the case where the protic solvent is solely water, the cellulose dissolved in the molten ionic liquid, during or downstream of step (c), are precipitated in a coagulation medium, the coagulation medium comprising a solvent which does not dissolve the cellulose and is miscible with the molten ionic liquid, wherein preferably the molten ionic liquid is comprising a cation that is formed from compounds which contain at least one five- to six membered heterocyclic ring and a protic solvent, and the process involves precipitating dissolved cellulose in the form of carbohydrates in a coagulation medium, comprising a solvent which does not dissolve the cellulose and is miscible with the molten ionic liquid, wherein said protic solvent is selected from the group consisting of
  • protic solvent selected from the group consisting of alcohols, carboxylic acids or amines, such as methanol, ethanol, 1-propanol, 2-propanol and 1- butanol, amylalcohol and linear and branched alcohols and higher linear and branched alcohols.
  • Suitable systems acting as ionic liquids are for example those, which are described in US8163215 or in US8841441 or as in WO-A-03029329, the disclosure of which is included into this specification as concerns the ionic liquid systems.
  • Ionic liquids in the context of the present invention are preferably
  • [A 1 ] + [A 2 ] + [A 3 ] + [A 4 ] + [Y] n - (He), wherein n 4; and wherein [A 1 ] + , [A 2 ] + , [A 3 ] + and [A 4 ] + independently of one another are chosen from the groups mentioned for [A] + and [Y] n " has the meaning mentioned under (A). Possible is e.g. the use of 1-ethyl-3-methylimidazolium chloride.
  • Such compounds can thus contain oxygen, phosphorus, sulfur or, in particular, nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, particularly preferably 1 to 5, very particularly preferably 1 to 3 and in particular 1 to 2 nitrogen atoms. They can optionally also contain further hetero atoms, such as oxygen, sulfur or phosphorus atoms.
  • the nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid, from which a proton or an alkyl radical can then transfer to the anion in equilibrium in order to generate an electrically neutral molecule.
  • the system of the ionic liquid may also be one based systems containing a cationic 1 ,5,7- triazabicyclo[4.4.0]dec-5-enium [TBDH]+ moiety and an anion selected from the group according to Formula a), Formula b) and Formula c), as for example described in WO2018/138416, which is also included into this specification as concerns ionic liquid systems.
  • said molten ionic liquid comprises a protic solvent or a mixture thereof
  • the method involves, during or downstream of step (c), precipitating the cellulose in a coagulation medium, a protic coagulation agent or a mixture of protic coagulation agents being present in the coagulation medium, and wherein the surface tension o of the protic coagulation agent or the mixture of protic coagulation agents is 99% to 30% of the surface tension o of water, each surface tension being measured in accordance with ASTM D 1590-60 at a temperature of 50° C, wherein preferably the protic coagulation agent is selected from water, water in a mixture with the ionic liquid, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1- tetradecanol, 2-ethyl-1-hexanol, 1 ,
  • step (a) at least partly takes place under an oxidative atmosphere.
  • the oxidative atmosphere during step (a) is an oxygen containing atmosphere, more preferably air, preferably under atmospheric conditions.
  • the oxidative atmosphere at a humidity of less than 30 g/m 3 , more preferably at a humidity of less than 15 g/m 3 , most preferably at a humidity of zero or less than 10 or less than 5 g/m 3 .
  • the exposure to the oxidative atmosphere in step (a) takes place during a time span of at least 10 minutes, preferably at least 30 minutes, or in the range of 40-300 minutes, or in the range of 60-120 minutes.
  • the exposure takes place under ambient temperature conditions.
  • Oxidizing as chemical reaction is a function of temperature and time, kinetics is controlled also by temperature. So, the given conditions of temperature and time also equally extend to situations where an equivalent oxidizing effect is achieved for example at a lower temperature over a longer time span or at a higher temperature over a shorter time span.
  • an equivalent oxidizing effect is achieved for example at a lower temperature over a longer time span or at a higher temperature over a shorter time span.
  • neither the ionic liquid nor the cellulose nor the subsequent treatment with the active agent is negatively influenced by subjecting the ionic liquid with the cellulose to the oxidative atmosphere.
  • This exposure to oxidative atmosphere can be carried out as just exposing the corresponding container with the liquid on the surface to the oxidative atmosphere, however it can also be strengthened by active stirring of the solution under this atmosphere, and even more can be forced by bubbling oxidative atmosphere through the solution to speed up the process. It is also possible to circulate the ionic liquid cellulose solution through a specific gas/liquid mixing device to increase the efficiency of the process.
  • atmospheric pressure stands for pressures in the range of 0.8 to 1.1 bar (absolute pressure) and typically ambient temperature refers to temperatures in the range of 10 to 60° C, more typically 20 to 35°C.
  • the gas mixture used as input for the process is preferably ambient atmospheric air, i.e. air at ambient atmospheric pressure and at ambient atmospheric temperature, which normally implies a CO2 concentration in the range of 0.03-0.06% by volume.
  • air with lower or higher CO2 concentration can be used as input for the process, e.g.
  • An oxidative atmosphere is a gas which contains an oxidative species, preferably oxygen. Typically, that oxidative species is present in the oxidative atmosphere in a percentage of at least 10%, preferably at least 15% or in the range of 15-99%.
  • the oxidative atmosphere is air, i.e. a mixture of 20-25% oxygen, supplemented by nitrogen and less than 1% of other gases. This composition, when talking about air as oxidative atmosphere, is present at least at the beginning of the exposure of the ionic liquid solution to that oxidative atmosphere, during the process due to consumption of the oxygen the oxygen content in the oxidative atmosphere may decrease.
  • the feedstock cellulose can be recycling cellulose material in particular selected from at least one of cellulose waste, recycling yarns, recycling fabrics, recycling tissue, recycling clothing, other cellulose streams including cellulose containing waste streams.
  • said molten ionic liquid comprises a protic solvent or a mixture of several protic solvents, wherein the protic solvent is solely water and is present in the solution system in an amount of less than 5 wt. %, the cellulose dissolved in the molten ionic liquid are, during or downstream of step (c), precipitated in a coagulation medium, the coagulation medium comprising a solvent which does not dissolve the cellulose and is miscible with the molten ionic liquid, wherein preferably the molten ionic liquid is comprising a cation that is formed from compounds which contain at least one five-to six membered heterocyclic rings, preferably based on at least one of 1-ethyl-3-methylimidazolium, 1-butyl- 2,3-dimethylimidazolium, 1-butyl-3,5-dimethylpyridinium, 1-butyl-3-methylimidazolium with at least one counter ion selected from at least one of chloride, a
  • Said molten ionic liquid preferably comprises a protic solvent or a mixture thereof
  • the method during or downstream of step (c), involves precipitating the cellulose in a coagulation medium, a protic coagulation agent or a mixture of protic coagulation agents being present in the coagulation medium, and wherein the surface tension o of the protic coagulation agent or the mixture of protic coagulation agents is 99% to 30% of the surface tension o of water, each surface tension being measured in accordance with ASTM D 1590- 60 at a temperature of 50° C.
  • the degree of fibrillation is is evaluated by fixing single filaments (2.5 cm length) to a frame which is then placed into a cylinder with 20 ml of distilled water and 9 g of zirconia spheres (0.75 - 1 mm). The cylinder containing the filaments, water and zirconia spheres are agitated in a Labomat at 30°C for 3 hours and a rate of 50 rpm.
  • the produced cellulose yarn may be used directly in a variety of textile processes including texturizing; twisting; covered yarns (core spun yarns); knitting; weaving; seamless; circular knitting with other yarns (such as cotton, nylon, polyester, polypropylene, cellulosics, wool, silk, polyurethane); warp knitting; beaming process; staple fibers; nonwovens.
  • the produced cellulose yarn may be used directly in a variety of textile forms including Denim; Hosiery; Intimate; Sportswear; Fashion; Shoes; Sewing threads; Upholstery; Home textiles; Industrial textiles.
  • Fig. 1 shows schematic process steps for processing of recycled cellulose into regenerated cellulose fibers compared to a process possible with the invention
  • Fig. 2 shows the process scheme in particular including the step with a storage vessel for equilibration of the solution of cellulose material in ionic liquid with water.
  • Fig. 1 shows in the upper row a schematic process for conventional pre-processing of recycled cellulose materials to remove colors and impurities followed by dissolution in ionic liquid and subsequent fiber spinning.
  • the present invention as illustrated in the lower row allows direct dissolution of the recycled cellulose in ionic liquid if need be under an oxidative atmosphere and if need be subsequent active agent addition enabling colors and impurities to be processed directly in the ionic liquid dope with subsequent fiber spinning.
  • the present invention enables reduced process complexity and reductions in energy and water use compared to conventional processes.
  • Lyocell fibers are defined as a regenerated cellulose fibre obtained by dissolution, and an organic solvent (mixture of organic chemicals and water) spinning process without formation of derivatives, without limitation to NMMO.
  • the method for the production of a regenerated fiber using a Lyocell type of process are known for a person skilled in the art and can be found in numerous publications such as recently WO2022153170A1.
  • the fiber spinning process normally contains the steps: a) Cutting the cellulose pulp into pieces ⁇ 4 mm (may be carried out in a high-speed mixer, ball mill, shredder and the like) b) Preparation of a pre-mix: by putting in contact the cut cellulose pulp ( ⁇ 4 mm) with an organic solvent, potentially adding H2O. (Equipment selected from a group consisting of sigma mixer, reactor kneader, wiped film evaporator and the like) c) Homogenizing the pre-mix: The pre-mixing is homogenized through mechanical agitation mixing the dope for a time-period between 0 to 6 hours until a homogenous solution has been obtained.
  • Fig. 2 shows an overall view of the process which is proposed here. The key steps are defined in the claim, this figure illustrates all steps which can be carried out.
  • the process starts with a step of pulp preparation (A) followed by transferring the pulp into an ionic liquid in step (B). This is followed by the actual dissolution process, which is termed mash preparation (C) followed by dissolution in the dissolution unit (D).
  • mash preparation C
  • dissolution in the dissolution unit D
  • the resulting cellulose dissolved in ionic liquid with water is then transferred and filtered in step (E) and introduced into a storage vessel (F).
  • the resulting viscous material is introduced into the spinning block and airgap in unit (G) and ejected into the spin bath (H).
  • the fibers are subjected to washing and drying in unit (I), this can be followed by a spin finish application step (J) and texturizing (K).
  • the ionic liquid which is present in the spin bath and which results from the washing step can be recycled in the IL recovery unit (L) and can be transferred to the IL supply unit (M) for recycling and reusing it in unit (B).
  • the cellulose feedstock starting material is prepared.
  • This can be recycled cellulose material (for example recycled textiles), cellulose from waste streams (agricultural or food) or original cellulose material, it can be from bacterial origin or algal origin or from plant (wood) origin.
  • the material is cut and shredded to the appropriate size to form particles which are suitable for dissolution.
  • the particle size should be less than 3 mm (D50), preferably less than 1 mm.
  • the starting material has a degree of polymerization in the range of 500-1500, preferably in the range of 600-800.
  • step (B) in this step the material resulting from step (A) is transferred using pumps or pneumatic systems. If needed, in the same unit the ionic liquid can be warmed up with a heat exchanger to prepare for the dissolution.
  • the mixing typically takes a few minutes up to hours.
  • the incoming ionic liquid is tuned to have a water content in the range of less than 5 wt. %, the cellulose content is typically in the range of 5-25%, depending on the viscosity/degree of polymerization.
  • the device used can be an extruder, a kneader or another type of mixers and evaporator systems such as falling film and wiped blade configurations.
  • the temperature is in the range of less than 150°C, typically around 100°C, and the dissolution can be carried out while heating under negative pressure to remove evaporated water.
  • step E in this step the dissolved cellulose material in the ionic liquid and water is transferred to the storage vessel.
  • filtering can be important in this step, filters can be of the grid type.
  • filtration can alternatively or additionally be employed after step F and before step G.
  • the spin bath can be a static bath, but it can also be an accelerated bath.
  • (L) in this step the ionic liquid is recovered, i.e. excess water is removed and also any residuals, in particular in case of using recycled feedstock.
  • ionic liquid is recovered, i.e. excess water is removed and also any residuals, in particular in case of using recycled feedstock.
  • Possible is the use of evaporation, filtering, sedimentation, centrifugation, osmotic methods and combinations thereof.
  • the proposed process allows to maintain a high degree of polymerization throughout the whole process so there is no substantial decrease in the length of the cellulose chains. This allows to robustly reach the high tenacity and elongation values, and is in contrast to the environmentally unfriendly and unproductive viscose process, where during the production the degree of polymerization inherently undergoes significant reduction, leading to less beneficial fiber properties.
  • Tenacity, and elongation were measured according to the BISFA standard for testing methods for viscose, cupro, acetate, triacetate and lyocell filament yarns (2007 edition) Fibrillation is measured as described above.
  • a cellulose dope mixture was prepared by suspending cellulose powder (cut to ⁇ 4mm) in a mixture of ionic liquid (1-Ethyl-3-methylimidazolium acetate) and water as protic solvent. The mixture was subsequently heated and blended in a mechanical kneader at 90°C under vacuum to achieve an output homogeneous dope mixture batch of 20 kg composed of 10% w/w cellulose, >85% ionic liquid and ⁇ 5% water.
  • the as-prepared dope mixtures were directly pumped at a rate of 0.5 kg/h to a spinning nozzle consisting of 150 holes of 0.1mm diameter, with each hole exit maintained at 20mm air-gap height above a coagulating bath consisting of water.
  • the coagulated filaments were drawn from the bath and subsequently dried and wound onto bobbins for subsequent characterization.
  • the fiber spinning experiments were observed for spinning stability, that is the ability to achieve successful spinning of continuous filaments and collect on bobbins as a single length of contiguous multifilament yarn.
  • a stable production process is achieved when filaments can be produced stably (spinning without interruption or filament breakage) over a prolonged period of time of at least 10 minutes.
  • the period of stable production time can be expressed as a length of produced filament. For example, a 15km length of 150 dtex multifilament yarn produced in the 0.5kg/h spinning rate above would require >27 minutes of stable continuous production.
  • the spinning process is capable of maintaining stable continuous production conditions and product properties over long periods of time, i.e. over more than 3 hours or more than 8 hours at least.
  • stable production was assessed at achieving >15km continuous production.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé de production de fils de cellulose à partir d'une matière première cellulosique, et des fils obtenus au moyen dudit procédé, le procédé comprenant les étapes suivantes : (a) dissolution de la matière première cellulosique dans une solution contenant au moins un liquide ionique fondu, la solution contenant un liquide ionique avec un matériau cellulosique dissous comprenant un liquide protique en une quantité inférieure à 5% en poids et, à la fin de la dissolution, la solution contenant un liquide ionique avec un matériau cellulosique dissous et un liquide protique étant à une température dans la plage de 50 à 120 °C ; (b) maintien de la solution contenant un liquide ionique avec un matériau cellulosique dissous et un liquide protique à une température dans la plage de 40 à 95 °C pendant une durée comprise entre 3 et 18 heures sensiblement sans agitation ; (c) extrusion de la solution contenant un liquide ionique avec un matériau cellulosique dissous et un liquide protique à travers au moins une buse de filage, la solution contenant un liquide ionique avec un matériau cellulosique dissous et un liquide protique pendant l'extrusion à travers au moins une buse de filage comprenant un liquide protique en une proportion inférieure à 5 % en poids.
PCT/EP2025/051628 2024-01-31 2025-01-23 Procédé de fabrication de fils de cellulose dérivés de matiéres premiéres cellulosique Pending WO2025162806A1 (fr)

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003029329A2 (fr) 2001-10-03 2003-04-10 The University Of Alabama Dissolution et traitement de cellulose au moyen de liquides ioniques
DE10202838A1 (de) 2002-01-24 2003-08-07 Basf Ag Verfahren zur Abtrennung von Säuren aus chemischen Reaktionsgemischen mit Hilfe von ionischen Flüssigkeiten
WO2004084627A2 (fr) 2003-03-21 2004-10-07 The University Of Alabama Encapsulation dans une matrice de cellulose et procede associe
WO2007076979A1 (fr) 2005-12-23 2007-07-12 Basf Se Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
WO2009062723A1 (fr) 2007-11-14 2009-05-22 Basf Se Procédé de fabrication de biopolymères régénérés, et produits régénérés pouvant être ainsi obtenus
US8445704B2 (en) 2008-03-13 2013-05-21 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
WO2016087186A1 (fr) 2014-12-01 2016-06-09 Bioecon International Holding N.V. Procédé pour la conversion de cellulose
CN106146877A (zh) 2015-04-17 2016-11-23 中国科学院化学研究所 一种利用离子液体回收废旧纺织品的方法
WO2017019802A1 (fr) 2015-07-28 2017-02-02 Evrnu, Spc Procédés et systèmes de traitement de matière première textiles mixtes, isolement des molécules constituantes, et régénération de fibres polyester et cellulosique
WO2018138416A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procédé de fabrication d'une fibre ou d'un film de cellulose
US10724060B2 (en) 2014-02-17 2020-07-28 The University Of Toledo Enhancement of lignocellulose saccharification via a low temperature ionic liquid pre-treatment scheme
US11168196B2 (en) 2016-12-20 2021-11-09 Aalto University Foundation Sr Separation and upcycling of cellulose-containing blended waste
WO2021234226A1 (fr) 2020-05-19 2021-11-25 Aalto University Foundation Sr Recyclage de liquides ioniques conjugués acide-superbase par élimination de l'eau dans le procédé de filature de lyocell
WO2022153170A1 (fr) 2021-01-12 2022-07-21 Grasim Industries Limited Fibre cellulosique régénérée à haute ténacité
WO2023104635A1 (fr) 2021-12-06 2023-06-15 Heiq Materials Ag Procédé de fabrication de fils de cellulose régénérée dérivés de charges de déchets recyclés

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003029329A2 (fr) 2001-10-03 2003-04-10 The University Of Alabama Dissolution et traitement de cellulose au moyen de liquides ioniques
DE10202838A1 (de) 2002-01-24 2003-08-07 Basf Ag Verfahren zur Abtrennung von Säuren aus chemischen Reaktionsgemischen mit Hilfe von ionischen Flüssigkeiten
WO2004084627A2 (fr) 2003-03-21 2004-10-07 The University Of Alabama Encapsulation dans une matrice de cellulose et procede associe
WO2007076979A1 (fr) 2005-12-23 2007-07-12 Basf Se Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
US8163215B2 (en) 2005-12-23 2012-04-24 Basf Aktiengesellschaft Method of forming regenerated carbohydrates with solvent systems based on molten ionic liquids
WO2009062723A1 (fr) 2007-11-14 2009-05-22 Basf Se Procédé de fabrication de biopolymères régénérés, et produits régénérés pouvant être ainsi obtenus
US8841441B2 (en) 2007-11-14 2014-09-23 Basf Se Method for producing regenerated biopolymers and regenerated products obtained by said method
US8445704B2 (en) 2008-03-13 2013-05-21 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
US10724060B2 (en) 2014-02-17 2020-07-28 The University Of Toledo Enhancement of lignocellulose saccharification via a low temperature ionic liquid pre-treatment scheme
WO2016087186A1 (fr) 2014-12-01 2016-06-09 Bioecon International Holding N.V. Procédé pour la conversion de cellulose
CN106146877A (zh) 2015-04-17 2016-11-23 中国科学院化学研究所 一种利用离子液体回收废旧纺织品的方法
WO2017019802A1 (fr) 2015-07-28 2017-02-02 Evrnu, Spc Procédés et systèmes de traitement de matière première textiles mixtes, isolement des molécules constituantes, et régénération de fibres polyester et cellulosique
US11168196B2 (en) 2016-12-20 2021-11-09 Aalto University Foundation Sr Separation and upcycling of cellulose-containing blended waste
WO2018138416A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procédé de fabrication d'une fibre ou d'un film de cellulose
WO2021234226A1 (fr) 2020-05-19 2021-11-25 Aalto University Foundation Sr Recyclage de liquides ioniques conjugués acide-superbase par élimination de l'eau dans le procédé de filature de lyocell
WO2022153170A1 (fr) 2021-01-12 2022-07-21 Grasim Industries Limited Fibre cellulosique régénérée à haute ténacité
WO2023104635A1 (fr) 2021-12-06 2023-06-15 Heiq Materials Ag Procédé de fabrication de fils de cellulose régénérée dérivés de charges de déchets recyclés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Testing methods for viscose, cupro, acetate, triacetate and lyocell filament yarns", 2007, THE INTERNATIONAL BUREAU FOR THE STANDARDISATION OF MAN-MADE FIBRES

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