WO2025032035A1 - Procédé d'obtention de pâte de cellulose à partir de textiles - Google Patents

Procédé d'obtention de pâte de cellulose à partir de textiles Download PDF

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Publication number
WO2025032035A1
WO2025032035A1 PCT/EP2024/072118 EP2024072118W WO2025032035A1 WO 2025032035 A1 WO2025032035 A1 WO 2025032035A1 EP 2024072118 W EP2024072118 W EP 2024072118W WO 2025032035 A1 WO2025032035 A1 WO 2025032035A1
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WO
WIPO (PCT)
Prior art keywords
fibers
process according
pulp
treatment
cellulose
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/EP2024/072118
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German (de)
English (en)
Inventor
Lennart MARX
Tobias BÖRNHORST
Mary Clare O'DONNELL
Daniel SLAK
Reiner MANTSCH
Arne Hüneke
Mathias LEIMBRINK
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Eeden GmbH
Original Assignee
Eeden GmbH
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 Eeden GmbH filed Critical Eeden GmbH
Priority to KR1020267002127A priority Critical patent/KR20260045787A/ko
Priority to CN202480048425.1A priority patent/CN121620624A/zh
Publication of WO2025032035A1 publication Critical patent/WO2025032035A1/fr
Priority to MX2026000823A priority patent/MX2026000823A/es
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment

Definitions

  • the present invention relates to a process for obtaining pulp from textiles as well as to the pulp obtained by the process according to the invention and its further processing and use.
  • WO 2020/245053 proposes a method for producing a cellulosic paper stock in which used textiles are provided as starting material, wherein the used textiles comprise cellulose and non-cellulosic foreign substances, in particular synthetic plastic and/or metal oxides; the non-cellulosic foreign fibers are at least partially depleted from the cellulose in order to provide a depleted starting material and a cellulosic paper stock is formed from the depleted starting material.
  • WO 2020/245058 describes a method for continuously providing a processed cellulose-containing starting material, in particular a starting material for producing a cellulosic molded body, the method comprising: feeding a cellulose-containing starting material with a predefined composition to a reactor device; continuously processing the cellulose-containing starting material in the reactor device to obtain the processed cellulose-containing starting material; and discharging the processed cellulose-containing starting material from the reactor device.
  • WO 2019/140245 discloses a process for producing cellulose and/or terephthalic acid from a textile waste material containing cotton and/or a mixture of cotton and polyester material.
  • the textile waste material is treated with subcritical water at a temperature of 105 to 190 °C and a pressure of 40 to 300 psi for 0 to 90 minutes.
  • the cellulose thus produced has a degree of polymerization of 150-2500.
  • dissolved terephthalic acid and ethylene glycol are obtained.
  • WO 2010/104458 relates to a process for producing shaped cellulosic material from lignocellulose by a sequence of separation, dissolution and cellulose shaping steps.
  • US 2023/0124761 describes a process for treating a starting material comprising cellulosic and non-cellulosic material, the process comprising, inter alia, a pretreatment of the starting material intended to cause the viscosity and the average molecular weight of the cellulosic material to be changed.
  • the pretreatment may, for example, be a non-alkaline wash, an enzyme treatment, an amorphous phase water treatment, a treatment with a swelling agent, a supercritical CO2 treatment, a bleach treatment or a treatment with an organic solvent.
  • the cellulose from textiles is usually recovered in the form of pulp, which is then subjected to further processing, for example into longer fibers or yarns.
  • further processing for example into longer fibers or yarns.
  • efficient and sustainable recycling processes for textiles especially in "closed-loop recycling” so that the recovered pulp can be processed back into textiles.
  • a holistic approach that not only involves recovering the material, but also enables this to be done using a resource- and environmentally friendly process.
  • a first subject matter of the present invention is therefore a process for obtaining pulp from textiles, comprising the steps of: a) providing a starting textile fiber mixture comprising cellulose fibers and foreign fibers; b) separating the cellulose fibers and the foreign fibers by treatment with a methanolic solvent; and c) carrying out a hydrothermal treatment of the cellulose fibers to obtain the pulp.
  • pulp and “dissolving pulp” are used synonymously and refer to cellulose that is in the form of short fibers or particles.
  • the person skilled in the art generally understands these terms to mean cellulose that serves as a starting material for the production of cellulose regenerates from which fibers such as viscose or films can be produced.
  • cellulose is understood to mean a polysaccharide which is composed of ß-D-glucose units which are linked together in a ß-1,4-glycosidic manner.
  • both used and unused textiles are considered as sources for the starting textile fiber mixture, such as those obtained from used clothing collections or from leftovers from textile and clothing production. There are therefore no limits to the method according to the invention with regard to the starting textile fiber mixture.
  • the starting textile fiber mixture has a proportion of at least 10% by weight of natural fibers, in particular cotton fibers, based on the total weight of the starting textile fiber mixture.
  • these foreign fibers are selected from the group consisting of polyester fibers, in particular polyethylene terephthalate (PET) fibers, polyether fibers, polyurethane fibers, polyamide fibers and mixtures thereof.
  • PET polyethylene terephthalate
  • polyether fibers polyether fibers
  • polyurethane fibers polyamide fibers and mixtures thereof.
  • the method according to the invention provides for a separation of the starting textile fiber mixture to reduce the proportion of foreign fibers.
  • the starting textile fiber mixture is subjected to a treatment with a methanolic solvent.
  • a methanol-containing solvent is understood to mean a solvent or solvent mixture whose main component is methanol.
  • the proportion of methanol in the methanol-containing solvent is preferably at least 50% by volume, particularly preferably at least 60% by volume, and in particular at least 80% by volume, based on the total volume of the solvent.
  • This treatment is preferably carried out at a temperature of 160 to 240 °C and/or at a pressure of 1.8 to 8 MPa, particularly preferably 170 to 220 °C and/or at a pressure of 2.2 to 5.8 MPa, in particular 180 to 200 °C and/or a pressure of 2.7 to 4 MPa.
  • the preferred treatment duration has been found to be 1 to 120 minutes, preferably 1 to 60 minutes or 15 to 120 minutes, particularly preferably 10 to 90 minutes.
  • polyester fibers contained in the starting textile fiber mixture can be separated, with PET fibers being the most common type of fiber.
  • the PET can be gently converted back into its monomers, which can then be used to produce new PET.
  • by treating the PET with a methanolic solvent it is advantageously converted into dimethyl terephthalate as a monomer, which can then be polymerized again or used for other applications.
  • step b) of the process according to the invention can be carried out in the presence or absence of a catalyst.
  • Zn(OAc)2 or sodium methoxide for example, can be used as catalysts.
  • step b) of the process according to the invention can be carried out in a basic medium, for example by adding NaOH or KOH.
  • step b) of the process according to the invention is carried out in the absence of a catalyst, in particular no active addition of a catalyst is carried out.
  • the omission of the catalyst has the advantage that, on the one hand, contamination of the fibers by the catalyst is avoided and, on the other hand, no further salt load is generated, as would otherwise occur when the catalyst is separated off.
  • the starting textile fibre mixture When treating the starting textile fibre mixture with the methanolic solvent, this can be in liquid or vaporous form. Treatment with a vaporous methanolic solvent has the advantage that a larger amount of textile fibres can be brought into contact with the solvent and thus a better Mixing can also take place with long fiber material. Accordingly, an embodiment of the method according to the invention is preferred in which the treatment is carried out with a vaporous methanolic solvent. Alternatively, the starting textile fiber mixture can also be suspended in the solvent, whereby comprehensive wetting of the fibers is achieved. In a particularly preferred embodiment, the methanolic solvent is in equilibrium between vapor and liquid.
  • solvents can be mixed into the methanolic solvent.
  • This other solvent is preferably selected from the group consisting of water, dichloromethane and chloroform and mixtures thereof.
  • their proportion is preferably not more than 20% by volume, preferably not more than 10% by volume, based on the total volume of the solvent.
  • a methanol-water mixture is used, the water proportion preferably being a maximum of 10% by volume, based on the total volume.
  • the separation of the cellulose fibers from the starting textile fiber mixture in step b) of the method according to the invention can comprise further cleaning steps in addition to the separation of the foreign fibers.
  • oxidizing agents and/or metal complexing agents can also be added to the starting textile fiber mixture.
  • the oxidizing agent is preferably selected from the group consisting of oxygen, ozone and H2O2, while the metal complexing agents are preferably different from any catalysts used. Examples of suitable metal complexing agents would be EDTA, DTPA, MGDA, EDDS, NTA, IDS.
  • the treatment in step b) is carried out in the absence of oxygen. In this way, the risk of undesirable degradation of the cellulose fibers contained in the textile fibers can be minimized.
  • the process according to the invention comprises a step in which the starting textile fibre mixture is washed.
  • This The washing step preferably follows step b) of the process according to the invention.
  • the washing medium is preferably selected from the group consisting of methanol, ethanol, chloroform, dichloromethane, ethyl acetate, water and mixtures thereof.
  • the method according to the invention provides for carrying out a hydrothermal treatment.
  • this treatment is carried out at a temperature of 130 to 200 °C, preferably 160 to 190 °C, and/or a pressure of 0.3 to 1.6 MPa, preferably 0.6 to 1.3 MPa.
  • the preferred treatment duration is 1 to 120 minutes.
  • the water can be in the liquid phase or in vapor form or as a mixture thereof.
  • step c) can also be carried out in the absence or presence of a catalyst, with a hydrothermal treatment in the absence of a catalyst being preferred.
  • a catalyst such as NaOH or KOH
  • step c) can also be carried out in the absence or presence of a catalyst, with a hydrothermal treatment in the absence of a catalyst being preferred.
  • conventional processes generally use water and a catalyst such as NaOH or KOH, it has surprisingly been found in the context of the present invention that the process is economically efficient even without a catalyst and thus has the advantage that downstream neutralization and the associated disadvantages such as further salt loading or the use of further chemicals can be dispensed with.
  • a steam pressure digestion can be carried out before and/or after step c). In this way, the surface area of the fibers can be increased so that a more efficient treatment can take place.
  • the ratio of fibers to solvent in step b) of the process according to the invention is 1:1 to 1:20.
  • the ratio of fibers to water in step c) of the process according to the invention is 1:1 to 1:20.
  • Textiles are often dyed, which means that for recovery purposes, a decolorization step must be carried out during the recycling process in which the dyes that are bound to the cellulose fibers are removed or made colorless.
  • Two methods are available for decolorization: oxidative and reductive decolorization.
  • step c) of the process according to the invention is therefore preceded by a reductive and/or oxidative treatment of the cellulose fibers.
  • decolorization under basic conditions and the addition of oxidizing agents has proven to be the gentler and therefore preferred method.
  • Carrying out decolorization under basic conditions with an oxidizing agent offers the advantage that the cellulose fiber can be decolorized with less damage and at the same time a good decolorization result.
  • the decolorization step is preferably carried out at a temperature of 60 to 180 °C in a basic environment.
  • a suitable metal complexing agent such as EDTA, DTPA, MGDA, EDDS, NTA and/or IDS and/or a suitable stabilizing agent in the form of an antioxidant such as propyl gallate or MgSO4 may be added to further protect the cellulose and reduce the metal content.
  • Used textiles are usually shredded so that their fibers are present in a variety of different fiber lengths.
  • the process according to the invention has a high tolerance for long fibers. Nevertheless, in some applications it may be preferable to limit the fibers to a certain length, for example to avoid spinning or knotting of the fibers during mechanical stirring. Therefore, an embodiment of the process according to the invention is preferred in which the starting textile fiber mixture is shredded before the treatment in step b).
  • the process according to the invention further comprises a step in which the pulp is mixed with further cellulose fibers such that the resulting mixture has a target value of the average intrinsic viscosity.
  • the pulp obtained by means of the process according to the invention can be mixed with cellulose fibers with a lower intrinsic viscosity in order to achieve a desired target value of the average intrinsic viscosity.
  • the process according to the invention produces high-quality pulp that can be further processed in a range of applications. Therefore, an embodiment is preferred in which the pulp obtained is subjected to further processing, for example further processing into textiles or paper, in particular further processing into textile fibers.
  • the regenerated pulp is further processed into spinning dope, which serves as the starting material for the production of cellulose fibers and thus textiles.
  • the pulp obtained is pressed into panels.
  • Another object of the present invention is pulp obtained according to the process according to the invention.
  • the pulp obtained by means of the process according to the invention is intended in particular for further processing into new textiles.
  • the cellulose has a certain chain length. Therefore, an embodiment is preferred in which the pulp has an intrinsic viscosity of at least 400 mL/g and/or a maximum of 700 mb g, preferably from 450 to 650 mL/g, more preferably from 450 to 580 mb/g, determined according to ISO 5351:2010.
  • the pulp obtained by the process according to the invention is characterized by a high degree of purity. Surprisingly, it has been shown that even without decolorizing the fibers, a significant increase in the degree of whiteness io can be achieved. Therefore, an embodiment is preferred in which the pulp has a brightness index according to ISO 11475 of at least 90%.
  • the pulp according to the invention is also characterized by a low content of foreign substances.
  • the pulp has an iron (Fe) content of 10 mg/kg or less.
  • the pulp according to the invention preferably contains less than 80 mg/kg SiO2 and/or less than 80 mg/kg calcium (Ca).
  • the ash content, determined at 650 °C +/- 10 °C, is preferably 0.2% or less.
  • the present invention further relates to the use of the pulp obtained by means of the process according to the invention, in particular for the production of textiles and/or paper.
  • the pulp can be further processed, for example, into fibers or pulp.
  • the pulp serves as a starting material for the production of cellulose acetate, which can be further processed, for example, into films.
  • Another object of the present invention are cellulose fibers obtained from the pulp according to the invention.
  • An undyed starting textile fiber mixture comprising cellulose and PET fibers in a ratio of 80:20 was suspended in methanol (2.5 g solid in 100 mL methanol). The suspension was heated to a temperature of 170 to 220 °C to depolymerize the PET. The cellulose fibers were then filtered off and dried. The cellulose fibers thus obtained were suspended in water and heated to a temperature of 160 to 190 °C. The pulp thus obtained was then filtered off, washed and dried. PET was subsequently no longer detectable using FTIR spectroscopy, which indicates a residual content of ⁇ 2%. This was confirmed by gravimetric analysis, which showed a complete degradation of the PET. The resulting pulp had an average intrinsic viscosity of 415 mg/L and was mixed in a subsequent step with further cellulose with a higher intrinsic viscosity to obtain a final product with an average intrinsic viscosity of 550 mb/g.
  • the workup was carried out without the active addition of a catalyst.
  • a dyed starting textile fiber mixture comprising cellulose fibers and PET fibers in a ratio of 50:50 was treated with vaporous methanol at a temperature of 170 to 220 °C to depolymerize the PET.
  • the dyed cellulose fibers were then separated and dried.
  • the cellulose fibers were decolorized by alkaline hydrolysis in an aqueous IM KOH solution at 90 to 140 °C and then washed and dried.
  • PET was no longer detectable using FTIR spectroscopy, indicating a residual content of ⁇ 2%. This was confirmed by gravimetric analysis, which showed complete degradation of the PET within the scope of the measurement accuracy.
  • the decolorized cellulose fibers were suspended in water at a concentration of 2% fiber content and heated to a temperature of 160 to 190 °C. The pulp thus obtained was then filtered off, washed and dried. The obtained pulp had an average intrinsic viscosity of 418 mg/L.
  • the workup was carried out without the active addition of a catalyst.
  • FIG. 1 shows an exemplary schematic sequence of the method according to the invention.
  • the textile waste to be processed can come from collected and sorted old textiles such as those that arise as part of the used clothing collection. This textile waste is shredded or otherwise reduced to a starting textile fiber mixture. To separate foreign fibers, the starting textile fiber mixture is treated with a methanolic solvent (S1). The separated cellulose fibers can optionally be decolorized. before they are subjected to hydrothermal treatment (S2). The pulp obtained in this way can then be further processed into cellulose fibers, for example.
  • S1 methanolic solvent
  • S2 hydrothermal treatment

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  • Paper (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un procédé d'obtention de pâte de cellulose à partir de textiles, la pâte de cellulose obtenue par le procédé divulgué, et son traitement ultérieur et son utilisation.
PCT/EP2024/072118 2023-08-04 2024-08-05 Procédé d'obtention de pâte de cellulose à partir de textiles Pending WO2025032035A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020267002127A KR20260045787A (ko) 2023-08-04 2024-08-05 직물로부터 셀룰로오스 펄프를 수득하는 방법
CN202480048425.1A CN121620624A (zh) 2023-08-04 2024-08-05 从纺织品中获取纤维素浆料的方法
MX2026000823A MX2026000823A (es) 2023-08-04 2026-01-21 Proceso para obtener pulpa de celulosa a partir de textiles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23189810 2023-08-04
EP23189810.7 2023-08-04

Publications (1)

Publication Number Publication Date
WO2025032035A1 true WO2025032035A1 (fr) 2025-02-13

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PCT/EP2024/072118 Pending WO2025032035A1 (fr) 2023-08-04 2024-08-05 Procédé d'obtention de pâte de cellulose à partir de textiles

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KR (1) KR20260045787A (fr)
CN (1) CN121620624A (fr)
MX (1) MX2026000823A (fr)
WO (1) WO2025032035A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010104458A1 (fr) 2009-03-09 2010-09-16 Kiram Ab Procédé de fabrication de cellulose façonnée associé à un système de récupération d'usine de pâte à papier
WO2019140245A1 (fr) 2018-01-12 2019-07-18 Tyton Biosciences, Llc Procédés de recyclage de fibres de coton et de polyester à partir de déchets textiles
WO2020245058A1 (fr) 2019-06-04 2020-12-10 Lenzing Aktiengesellschaft Procédé de fourniture continue d'une matière de départ traitée contenant de la cellulose
WO2020245053A1 (fr) 2019-06-04 2020-12-10 Lenzing Aktiengesellschaft Procédé de fabrication d'une pâte à papier cellulosique à partir de vieux textiles
US20230124761A1 (en) 2013-04-17 2023-04-20 Evrnu, Spc Methods and systems for processing mixed textile feedstock, isolating constituent molecules, and regenerating cellulosic and polyester fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010104458A1 (fr) 2009-03-09 2010-09-16 Kiram Ab Procédé de fabrication de cellulose façonnée associé à un système de récupération d'usine de pâte à papier
US20230124761A1 (en) 2013-04-17 2023-04-20 Evrnu, Spc Methods and systems for processing mixed textile feedstock, isolating constituent molecules, and regenerating cellulosic and polyester fibers
WO2019140245A1 (fr) 2018-01-12 2019-07-18 Tyton Biosciences, Llc Procédés de recyclage de fibres de coton et de polyester à partir de déchets textiles
WO2020245058A1 (fr) 2019-06-04 2020-12-10 Lenzing Aktiengesellschaft Procédé de fourniture continue d'une matière de départ traitée contenant de la cellulose
WO2020245053A1 (fr) 2019-06-04 2020-12-10 Lenzing Aktiengesellschaft Procédé de fabrication d'une pâte à papier cellulosique à partir de vieux textiles

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Publication number Publication date
CN121620624A (zh) 2026-03-06
KR20260045787A (ko) 2026-04-03
MX2026000823A (es) 2026-03-02

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