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WO2024245773A1 - Procédé oxydant de fabrication de fils de cellulose régénérée provenant de matières premières de déchets recyclés - Google Patents

Procédé oxydant de fabrication de fils de cellulose régénérée provenant de matières premières de déchets recyclés Download PDF

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Publication number
WO2024245773A1
WO2024245773A1 PCT/EP2024/063592 EP2024063592W WO2024245773A1 WO 2024245773 A1 WO2024245773 A1 WO 2024245773A1 EP 2024063592 W EP2024063592 W EP 2024063592W WO 2024245773 A1 WO2024245773 A1 WO 2024245773A1
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Prior art keywords
cellulose
ionic liquid
protic
recycling
solution
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English (en)
Inventor
Enrique Herrero Acero
Uwe Pieles
Murray Height
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Heiq Aeoniq Holding Ag
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Heiq Aeoniq Holding Ag
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Publication of WO2024245773A1 publication Critical patent/WO2024245773A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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 recycled materials containing cellulose based on dissolution in ionic liquids and addition of active substances to degrade and remove colors and/or modify the molecular weight distribution of the cellulose polymers.
  • the process enables direct processing of recycled materials and subsequent spinning into fibers.
  • the process is advantageous for enabling processing of a wide range of postconsumer and post-industrial recycled articles for reuse in production of regenerated cellulose fibers.
  • 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.
  • the object of the present invention is the corresponding improved method as defined in claim 1.
  • the present invention relates to a method to produce cellulose yarns from recycling 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 (a1) and/or step (b) preferably comprises a protic liquid in an amount of less than five weight percent.
  • higher percentages are possible. This provided that it is made sure that during extrusion in step (c) the protic liquid content in the ionic liquid solution is less than five weight percent.
  • step (b) the active substances in step (b) will release water and will further increase the water content of the initial solution obtained in step (a) and/or (a1). It is possible to adjust the protic liquid content in the corresponding solution by degassing (e.g. by applying a underpressure or a vacuum), which will also carry protic liquid, in particular water, contained in the solution out of the solution.
  • degassing e.g. by applying a underpressure or a vacuum
  • This is possible for establishing a desired protic liquid content, so for establishing the desired protic liquid content for the initial molten ionic liquid as starting material for step (a), in particular in case of using molten ionic liquid recycled from the same process, or for controlling the protic liquid content further downstream in the process.
  • the active substances here act to degrade non-cellulose material initially contained in the recycling cellulose material. This is in contrast to the prior art solutions, e.g. in WO-A- 2021234226 only substances are used which react with the ionic liquid.
  • a ionic liquid bath is used for at the same time degrading non-cellulosic components and preparing for the spinning process.
  • the ionic liquid is only used for an intermediate step in the preparation of a cellulose base material for spinning, and there are distinct steps of pre-treatment and dissolving, but there is no use of active substances to degrade non-cellulose material in the ionic liquid.
  • no pulping agent is normally used, while this is key in the process of WO-A-2017019802.
  • 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 degassing, in particular if the protic liquid is water.
  • 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%. As mentioned, preferably 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.
  • Regenerated cellulose yarns produced with ionic liquids (IL) offer appealing fiber properties and a better sustainability profile (e.g. reduced global warming potential, energy use, biodegradability) compared to fibers from synthetic polymers such as polyester and polyamide.
  • 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.
  • short wavelength radiation e.g. UV light or photocatalysis in the presence of a catalyst.
  • the active reagents e.g. hydrogen peroxide and/or enzymes and/or catalyst salts
  • 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.
  • 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 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 (b) 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 (b) 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 preferably 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 or an enzyme such as a peroxidase, or a combination thereof is used.
  • the active substance is a substance with acts as an oxidizer and has a bleaching effect or is a degradation agent, preferably an enzymatic system such as peroxidase.
  • the ionic liquid from the beginning comprises or is supplemented after step (b) 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 peroxidases, 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 peroxidases, or cleaving agents activated by irradiation of electromagnetic irradiation, or strong bases, or a combination thereof.
  • step (b) 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 (b) 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 ]W[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).
  • 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 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1 -tetradecanol, 2-ethyl- 1-hexanol, 1 ,2-ethanediol, 1 ,2-
  • the produced cellulose yarn may be used directly in a variety of textile processes including texturizing; twisting; covered yards (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 the schematic process steps for conventional processing of recycled cellulose into regenerated cellulose fibers compared to the invention
  • Fig. 2 shows UV/Vis spectra of the measured dope solution before (empty circles) and after (5 min squares, 30 min diamonds, 60min solid circles) addition of hydrogen peroxide; in this case the 2-hour oxidation took place using N2 atmosphere;
  • Fig. 3 shows UV/Vis spectra of the measured dope solution before (empty circles) and after (5 min squares, 30 min diamonds, 60min solid circles) addition of hydrogen peroxide; in this case the 2-hour oxidation took place using air;
  • Fig. 4 shows UV/Vis spectra of the measured dope solution before (empty circles) and after (5 min squares, 30 min diamonds, 60min solid circles) addition of hydrogen peroxide; in this case the 2-hour oxidation took place using N2 atmosphere;
  • Fig. 5 shows UV/Vis spectra of the measured dope solution before (empty circles) and after (5 min squares, 30 min diamonds, 60min solid circles) addition of hydrogen peroxide. In this case the 2-hour oxidation took place using air.
  • 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 involves direct dissolution of the recycled cellulose in ionic liquid under an oxidative atmosphere and 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 an 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.
  • Knitted fabric used in this work was made from cellulosic fibers (Viscose).
  • the knitted fabric was dyed with a reactive dye (Robana Blue Hispasol HEGN).
  • UV/Vis spectra U-2000, Hitachi, Japan
  • Quartz cuvettes Hellma GmbH, Germany
  • Dope preparation Dissolution of dyed cellulose in an ionic liquid (IL)
  • Oxidation step Conditioning of the dope solution under different headspace gases
  • Reaction step Addition of hydrogen peroxide solution to bleach the cellulose
  • a first step 1 % cellulose was added into 114.76 g of each IL.
  • the IL/cellulose mixture was heated and maintained at a temperature of 90°C in a sealable glass vial while stirring the solution for two hours, with the goal of oxidizing the cellulose, and therefore reducing the molecular weight via oxidation.
  • a second sample was performed replacing the air in the headspace with nitrogen. After 2 hours the absorbance was measured using UVA/is spectroscopy. After the UV/VIS measurement 3.47 g hydrogen peroxide solution (30% H2O2 in water) was added to the mixture at a temperature of 90°C while stirring. The concentrations following addition of the hydrogen peroxide solution are shown in Table 1.
  • the dope mixture preparation features a water content less than 5% w/w.
  • the addition of hydrogen peroxide defines the reaction start. UVA/IS measurements were taken 5 minutes, 30 minutes and 60 minutes after the reaction was started.
  • the spinning solution dope was prepared using the above procedure and using 1 -Ethyl-3- methylimidazolium acetate ([EMIM]OAc; CAS 143314-17-4) as the ionic liquid. UV/Vis spectra were measured directly before the addition of hydrogen peroxide and 5 minutes, 30 minutes and 60 minutes after the reaction was started.
  • [EMIM]OAc 1 -Ethyl-3- methylimidazolium acetate
  • the spinning solution dope was prepared using the above procedure and using 1 -Ethyl-3- methylimidazolium propionate ([EMIM]OPr; CAS 865627-64-1) as the ionic liquid. UV/Vis spectra were measured directly before the addition of hydrogen peroxide and 5 minutes, 30 minutes and 60 minutes after the reaction was started.
  • [EMIM]OPr 1 -Ethyl-3- methylimidazolium propionate
  • the degradation of the color proceeds rapidly in both air and nitrogen headspace conditions with contact time between 5 minutes and 30 minutes producing a distinct removal of color from the cellulose mixture.
  • Knitted fabric used in this work was made from cellulosic fibers (Viscose).
  • the knitted fabric was dyed with a reactive dye (Robana Blue Hispasol HEGN).
  • UV/Vis spectra U-2000, Hitachi, Japan
  • Quartz cuvettes Hellma GmbH, Germany
  • Hydrogen peroxide solution (5% in citrate buffer) was prepared from 30% starting solution (Carl Roth).
  • Dope preparation Dissolution of dyed cellulose in an ionic liquid (IL)
  • Reaction step Addition of hydrogen peroxide solution and/or peroxidase solution to the cellulose/IL mixture.
  • a first step 1 % of cellulosic fibers (0.15g) were added into 14.3g of 1-Ethyl-3- methylimidazolium propionate ([EMIM]OPr; CAS 865627-64-1) as the ionic liquid.
  • the I L/cellulose mixture was heated and maintained at a temperature of 45°C in a sealable glass vial while stirring the solution for minimum of 1 hour.
  • Two reference samples were prepared with the only addition of 600 pL hydrogen peroxide solution or 600 pL of peroxidase solution.
  • a test sample was prepared with addition of 600 pL hydrogen peroxide solution in combination with 600 pL of peroxidase solution. Samples were stirred for 16 hours and 65 hours followed by absorbance measurement by UV/Vis spectroscopy.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé de production de fils de cellulose à partir d'une matière cellulosique de recyclage, le procédé comprenant les étapes suivantes : (a) dissolution de la matière cellulosique de recyclage dans une solution contenant au moins un liquide ionique fondu, la solution contenant un liquide ionique comprenant de préférence un liquide protique à raison d'une quantité inférieure à 5% en poids ; (a1) ajout et dissolution et/ou dispersion d'au moins une substance active ou d'un précurseur de celle-ci dans ladite solution ; (b) adaptation des conditions afin que lesdites substances actives, dissoutes ou dispersées dans la solution contenant un liquide ionique fondu, ou générées in situ dans la solution contenant un liquide ionique fondu, agissent de manière à dégrader une matière non cellulosique initialement contenue dans la matière cellulosique de recyclage, et qui est contenue dans la solution contenant un liquide ionique fondu en raison de la dissolution de la matière cellulosique de recyclage, (c) extrusion de la solution de matière cellulosique contenant le liquide ionique fondu à travers au moins une buse de filage, ladite solution de matière cellulosique pendant l'extrusion à travers au moins une buse de filage comprenant un liquide protique à raison d'une quantité inférieure à 5% ; de préférence, l'étape (a) est réalisée au moins partiellement dans une atmosphère oxydante.
PCT/EP2024/063592 2023-05-26 2024-05-16 Procédé oxydant de fabrication de fils de cellulose régénérée provenant de matières premières de déchets recyclés Pending WO2024245773A1 (fr)

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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
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