EP3882380B1 - Einstufiges verfahren zur sauren metallentfernung und bleichung - Google Patents

Einstufiges verfahren zur sauren metallentfernung und bleichung Download PDF

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Publication number
EP3882380B1
EP3882380B1 EP20163367.4A EP20163367A EP3882380B1 EP 3882380 B1 EP3882380 B1 EP 3882380B1 EP 20163367 A EP20163367 A EP 20163367A EP 3882380 B1 EP3882380 B1 EP 3882380B1
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Prior art keywords
stage
acid
cellulose
process according
during
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EP20163367.4A
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English (en)
French (fr)
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EP3882380A1 (de
Inventor
Mikael Lindström
Gunnar Henriksson
Amy TRAN CARLSTRÖM
Kajsa Fougner
Lennart BÖRJESON
Lennart KÄLLÉN
Zaheer Ahmad Mansoor
Tobias Sjögren
Tahani Kaldéus
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Re Newcell AB
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Re Newcell AB
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Priority to EP20163367.4A priority Critical patent/EP3882380B1/de
Priority to EP21710332.4A priority patent/EP4121584A1/de
Priority to CN202180018730.2A priority patent/CN115210417A/zh
Priority to PCT/EP2021/056406 priority patent/WO2021185704A1/en
Priority to US17/909,165 priority patent/US20230146394A1/en
Publication of EP3882380A1 publication Critical patent/EP3882380A1/de
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Classifications

    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/50—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs by irradiation or ozonisation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the invention relates to a one-stage step in a process for regenerating reclaimed cellulose, where acid metal removal is combined together with acid oxidative bleach in one single stage.
  • WO 2012/057684 discloses a process for the derivatization of cellulose comprising the sequential steps: a) mixing cellulose with a viscosity below 900 ml/g with an aqueous solution to obtain a liquid, wherein particles comprising cellulose in said liquid have a diameter of maximum 200 nm, wherein the temperature of the aqueous solution is below 20°C, and wherein the pH of the aqueous solution is above 12, b) subjecting the liquid to at least one of the steps: i) decreasing the pH of the liquid with at least 1 pH unit, ii) increasing the temperature by at least 20°C, and c) derivatization of the cellulose.
  • WO 2010/124944 discloses a process for the hydrolysis of cellulose comprising the sequential steps (a) mixing cellulose with a viscosity below 900 ml/g with an aqueous solution to obtain a liquid, wherein particles comprising cellulose in said liquid have a diameter of maximum 200 nm, wherein the temperature of the aqueous solution is below 35°C, and wherein the pH of the aqueous solution is above 12, (b) subjecting the liquid to at least one of the steps: (i) decreasing the pH of the liquid with at least 1 pH unit and (ii) increasing the temperature by at least 20°C, and (c) hydrolysing the cellulose.
  • glucose manufactured according to the method and ethanol manufactured from the glucose.
  • WO 2013/124265 discloses a method for regeneration of a cellulose containing material, comprises the steps: a) exposing the cellulose containing material to oxygen with an alkali aqueous solution at a pH of at least 9, and a temperature of at least 20°C, b) dispersing the cellulose containing material in the alkali aqueous solution, wherein the temperature of the alkali aqueous solution is lowered below 15°C, and wherein the pH of the alkali aqueous solution is above 9, c) adding an organic solvent to the dispersion to precipitate cellulose, and d) separating the precipitated cellulose by at least one method selected from filtering and centrifugation.
  • the method makes it possible to maintain a high alkali pH value in the process, which saves costs since the pH value does not have to be lowered by additions of various additives.
  • WO 2018/104330 discloses a cellulose based fibre made of i) a cellulose dissolving pulp, and ii) a recycled cellulose textile, which is treated to swell the cellulose with a reducing additive and a) bleached with oxygen at alkaline conditions with a pH in the range 9-13.5 and/or b) bleached with ozone at acid conditions below pH 6, wherein the cellulose based fibre is manufactured with one selected from a Viscose process and a Lyocell process.
  • WO 2018/073177 discloses method for recycling textiles comprising cellulose with the following steps of: optionally disintegrating the textile, swelling the cellulose, under reducing conditions, wherein at least one reducing agent is present at least during a part of the swelling, and then performing at least one of the following two bleaching steps in any order: i) bleaching the material with oxygen at alkaline conditions with a pH in the range 9-13.5, and ii) bleaching the material with ozone at acid conditions below pH 6.
  • WO 2015/077807 discloses a process for pretreating reclaimed cellulose fibres to be used in the production of moulded bodies from regenerated cellulose by the Viscose or Lyocell process, wherein the treatment of the reclaimed cellulose fibres includes a chemical metal removing stage and an oxidative bleaching stage.
  • the process is described as a multistage process.
  • the metal removing stage can be acidic washing or treatment with a complexing agent, or a combination of both.
  • the oxidative bleaching stage can be treatment with peroxide, oxygen or ozone.
  • WO 2016/123643 A1 discloses a process for chemically pretreating reclaimed cellulose fibres to be used in the production of moulded bodies from regenerated cellulose.
  • problems in the state of the art include how to further reduce the metal content of regenerated cellulose. Another problem is how to further reduce the clogging properties of regenerated cellulose. In general, it is also desirable to provide a simpler and more efficient method to regenerate cellulose.
  • a process for chemically pretreating reclaimed cellulose fibres to be used in the production of moulded bodies from regenerated cellulose wherein the pretreatment includes one stage, in which stage acid metal removal and acid oxidative bleaching are carried out together, and wherein acetic acid is present during the stage.
  • a one-stage method is more efficient, faster and less costly compared to a multi-stage method according to the prior art.
  • the invention makes it possible to remove metals efficiently without using complex formers such as EDTA, which may be an environmental issue due to the longevity of EDTA and similar compounds.
  • a process for chemically pretreating reclaimed cellulose fibres to be used in the production of moulded bodies from regenerated cellulose wherein the pretreatment includes one stage, in which stage acid metal removal and acid oxidative bleaching are carried out together, and wherein acetic acid is present during the stage.
  • reclaimed cellulose can be regenerated and used for production of moulded bodies.
  • processes include but are not limited to: the Lyocell process, in particular using aqueous amine oxide, such as 4-methylmopholine N-oxide (EP 0356419 and EP 0584318 ), the viscose process (Kurt Götze, Chemiefasern nach dem Viskoseclar, 1967) and the Modal process (AT 287905).
  • Metal ions are present in recycled cellulose and it is desired to reduce the content of such metal ions.
  • the stage is one single stage and is intended to be used as a stage in the regeneration of reclaimed cellulose, including recycled clothing, for instance clothing comprising cotton.
  • the present stage according to the invention is to be carried out together with additional steps and stages in the regeneration of reclaimed cellulose. Additional stages are known in the art and can easily be combined with the stage according to the invention by a skilled person. A number of additional stages are suitably performed in the regeneration of reclaimed cellulose as described in the prior art. Buttons, zips and other objects of solid metal are in one embodiment removed before the stage.
  • a mechanical treatment is in one embodiment, carried out before the present stage, such as for instance shredding and milling.
  • a chemical treatment step is in one embodiment carried out before the stage according to the invention. Such a chemical treatment step may include a partial or entire dissolution of the reclaimed cellulose.
  • a step of removing non-cellulosic fibres is performed.
  • non-cellulosic include but are not limited to fibres comprising polyester, elastan, acryl.
  • the removal of non-cellulosic fibres is carried out by flotation. Any suitable acid can be used in order to obtain an acidic pH during the stage, i.e. a pH value below 7, provided that acetic acid is present. In order to obtain appropriate pH, mixtures of acids can be used. In one embodiment, a carboxylic acid is present during the stage.
  • an acid is present during the stage means that it may be present during at least a part of the stage, for instance an acid may be present at the beginning of the stage in order to create the desired pH value and during the stage one or more additional acids can be added. At least one or more acids are present during a part of the stage. In an embodiment where an acid is present during a part of the stage, it should be ensured that the pH value is acidic as desired during the entire stage, for instance by presence of acid(s) also in the beginning of the stage. Examples of acids which may be present together with acetic acid include but are not limited to hydrochloric acid, formic acid, citric acid. Mixtures including one or more of these acids are also encompassed. Mixture including these acids together with additional acids are also encompassed.
  • a mixture of acids is used.
  • hydrochloric acid can be mixed with acetic acid in order to achieve the desired pH.
  • the fact that at least acetic acid is present during the stage means that the acid can be added in the beginning of the stage, or before the stage or a combination thereof.
  • the acid is added in the beginning of the stage. Addition of an acid in the beginning of the stage or before the stage does not exclude the possibility of addition of further acid during the stage.
  • the pH is in the interval 1-3 during the stage. In another embodiment the pH is in the interval 2-3 during the stage. In an alternative embodiment, the pH is in the interval 0-4 during the stage. In yet another embodiment the pH is in the interval 1-5 during the stage. In a further embodiment, the pH is in the interval 1.5-5 during the stage. In a still further embodiment, the pH is in the interval 0-5 during the stage.
  • the temperature during the stage is in the interval 40-60 °C. In another embodiment, the temperature during the stage is in the interval 30-75 °C.
  • the temperature during the stage can vary. For instance, the temperature can be high and in the upper part of the interval in the beginning of the stage and lower towards the end. Also a lower initial temperature followed by a rise in the temperature is conceivable. It is not necessary that the temperature is within the ranges during the entire stage, temperatures below and above the ranges are also conceivable. In alternative embodiments, the temperature is outside the ranges during the entire stage.
  • At least one additional weak acid with a pKa above 3 and below 7 is present during the stage. 3 ⁇ pKa ⁇ 7.
  • a weak acid has the advantage that the cellulose is not hydrolysed by the acid, or at least not hydrolysed to any significant degree.
  • acetic acid is present during the stage. Without wishing to be bound by any particular scientific theory, the inventors believe that acetic acid is beneficial for removing dye. Although the mechanisms behind this are not fully understood, the inventors believe that addition of acetic acid gives an improvement in the removal of certain dyes.
  • the stage according to the present invention can suitably be combined with additional bleaching stages in order to fully remove any remaining dyes. Such additional bleaching stages are known and described in the prior art.
  • sulphuric acid is not present during the stage.
  • a common impurity in reclaimed cellulose such as reclaimed cotton is calcium.
  • Ca 2+ ions can react with the sulphuric acid and form CaSO 4 (gypsum), which makes the process less efficient. It is still possible to use sulphuric acid as evidenced by the examples, but longer treatment time and/or a higher concentration of sulphuric acid would be necessary. Further less efficient metal removal can be expected. Thus the use of sulphuric acid is often less preferred.
  • sulphuric acid is present during the stage. If used, sulphuric acid should be used at higher concentration and/or with longer treatment time.
  • an acidic oxidative bleach takes place simultaneously in the same stage in order to improve the efficiency.
  • hydrogen peroxide is present during the stage.
  • the dose of hydrogen peroxide is in one embodiment 2 to 40 kg hydrogen peroxide per odtp.
  • ozone is present during the stage.
  • the dose of ozone is 0.1 to 6 kg ozone per odtp. Since the acidic metal removal and the acidic oxidative bleach are carried out together in the same stage, the pH is acidic for all conceivable oxidative bleaching additives.
  • the oxidative bleaching agent is added before the step starts or at the start of the stage.
  • an oxidative bleaching agent is added in the beginning of the stage and at least one oxidative bleaching agent is added during the stage.
  • at least one oxidative bleaching agent is added in the beginning of the stage and at least one additional different oxidative bleaching agent is added during the stage.
  • ozone is added in the beginning of the stage and hydrogen peroxide is added during the stage at a later point in time.
  • hydrogen peroxide is added in the beginning of the stage and ozone is added during the stage. Also other combinations of additions of oxidative bleaching agents are encompassed.
  • the stage with both acid metal removal and acid oxidative bleaching is the only acidic chemical metal removal step in the process. Even if the detailed mechanisms are not fully investigated the inventors believe that the acidic metal removal and the acidic oxidative bleach should be carried out together in one stage. If acidic metal removal and the bleach are carried out separately the efficiency is lower as seen in the examples.
  • the combined acid metal removal and acid oxidative bleaching is in one embodiment the only chemical metal removal stage in the process, i.e. no additional acid chemical metal removal stages are carried out before or after the stage according to the invention.
  • the metal removal according to the invention is so efficient that it is more economical to use only one efficient stage and no additional acidic metal removal stages.
  • the acidic metal removal in the stage is the only acidic metal removal.
  • the stage is carried out during a time in the interval from 1 to 60 minutes. In yet another embodiment the stage is carried out during 2-60 minutes. In yet another embodiment the stage is carried out during 5-60 minutes. In yet another embodiment the stage is carried out during 10-60 minutes. Longer treatment times can also be used, but can also be less economical. Thus In one embodiment, the stage is carried out during a time of at least 1 minute, at least 2 minutes, at least 5 minutes, or at least 10 minutes.
  • the reclaimed cellulose fibres are in one embodiment, cotton fibres.
  • the cellulose fibres originate from pre-consumer cellulose containing waste such as cotton.
  • Pre-consumer cellulose containing waste includes but is not limited to combing waste and cuttings.
  • the cellulose fibres originate from post-consumer cellulose containing waste such as cotton.
  • Post-consumer cellulose containing waste includes but is not limited to laundry waste and used clothes.
  • the cellulose fibres comprise pulp prepared from cotton rags.
  • the reclaimed cellulose is mechanically shredded or milled prior to the use.
  • the production of moulded bodies is made with the Viscose process. In one embodiment, the production of moulded bodies is made with the Lyocell process. In one embodiment, the production of moulded bodies is made with the Modal process. These processes for production of moulded bodies are known in the art and can be performed by a skilled person.
  • the intrinsic viscosity of the regenerated cellulose is suitably adjusted as needed and as known depending on the intended production process for the moulded bodies. For instance, for a Viscose process the intrinsic viscosity can be adjusted to a value in the range 350-650 ml/g. For instance, for a Lyocell process the intrinsic viscosity can be adjusted to 350-500 ml/g.
  • Reactivity test based on wash, white jersey fabric.
  • the samples were treated mechanically by cutting in pieces 1 ⁇ 1 cm and thereafter treated in a mixer for 40 seconds. This shredding served to open the fiber structure.
  • the material was treated in a chemical step where the material was bleached at high pH, i.e. a pH above 7.
  • the second wash was a different metal removal step.
  • the samples were diluted to a concentration of 9 wt% and the pH was adjusted to 6 for all samples with NaOH and if needed with H 2 SO 4 .
  • the samples were wetted overnight and diluted to a concentration of 3.5 wt%. Thereafter the pH value of each pulp sample was adjusted and H 2 O 2 was added.
  • the samples had a dwell time of about 20 minutes before wash with deionized water. This gave a stage with combined acidic metal removal and acidic oxidative bleach. All samples were washed with 1.5 liters deionized water after filtering.
  • the samples were diluted to a concentration of 9 wt% and the pH was adjusted to 6 for all samples with NaOH. If needed the pH was also adjusted with H 2 SO 4 for the H 2 SO 4 -sample and with HCl for the HCl-sample and the acetic acid-sample.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)

Claims (11)

  1. Verfahren zur chemischen Vorbehandlung von rückgewonnenen Zellulosefasern, die zur Herstellung von Formkörpern aus regenerierter Zellulose verwendet werden sollen, wobei die Vorbehandlung eine Stufe umfasst, in der die saure Metallentfernung und die saure oxidative Bleiche zusammen durchgeführt werden, und wobei während der Stufe Essigsäure vorhanden ist.
  2. Verfahren nach Anspruch 1, wobei mindestens eine Säure, ausgewählt aus der Gruppe, bestehend aus Salzsäure, Ameisensäure, Zitronensäure und einer beliebigen Mischung davon, während der Stufe vorhanden ist.
  3. Verfahren nach einem der Ansprüche 1-2, wobei mindestens eine zusätzliche schwache Säure mit einem pKa über 3 und unter 7 während der Stufe vorhanden ist.
  4. Verfahren nach einem der Ansprüche 1-3, wobei Schwefelsäure während der Stufe nicht vorhanden ist.
  5. Verfahren nach einem der Ansprüche 1 bis 3, wobei Schwefelsäure während der Stufe vorhanden ist.
  6. Verfahren nach einem der Ansprüche 1-5, wobei während der Stufe Wasserstoffperoxid vorhanden ist.
  7. Verfahren nach einem der Ansprüche 1-6, wobei während der Stufe Ozon vorhanden ist.
  8. Verfahren nach einem der Ansprüche 1-7, wobei die Stufe mit der sauren Metallentfernung und der sauren oxidativen Bleiche die einzige Stufe der sauren chemischen Metallentfernung in dem Verfahren ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die Stufe über ein Zeitintervall von 1 bis 60 Minuten durchgeführt wird.
  10. Verfahren nach einem der Ansprüche 1-9, wobei die Temperatur während der Stufe im Bereich von 30-75 °C liegt.
  11. Verfahren nach einem der Ansprüche 1-10, wobei eine anschließende Herstellung von Formkörpern aus regenerierter Zellulose durchgeführt wird mit einem Verfahren ausgewählt aus der Gruppe bestehend aus dem Viscose-Verfahren, dem Lyocell-Verfahren und dem Modal-Verfahren.
EP20163367.4A 2020-03-16 2020-03-16 Einstufiges verfahren zur sauren metallentfernung und bleichung Active EP3882380B1 (de)

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EP20163367.4A EP3882380B1 (de) 2020-03-16 2020-03-16 Einstufiges verfahren zur sauren metallentfernung und bleichung
EP21710332.4A EP4121584A1 (de) 2020-03-16 2021-03-12 Einstufiges verfahren für säuremetall-reovale und bleichende produkte
CN202180018730.2A CN115210417A (zh) 2020-03-16 2021-03-12 用于酸性金属去除和漂白的一个阶段方法
PCT/EP2021/056406 WO2021185704A1 (en) 2020-03-16 2021-03-12 One stage method for acid metal rewoval and bleach
US17/909,165 US20230146394A1 (en) 2020-03-16 2021-03-21 One stage method for acid metal removal and bleach

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SE545655C2 (en) 2022-10-06 2023-11-28 Re Newcell Ab Method for manufacturing a product comrpising recycled fibers by filtration and acid treatment of a viscose dope
SE2230370A1 (en) * 2022-11-15 2024-05-16 Valmet Ab Method for bleaching cellulose pulp formed from recycled textile material

Family Cites Families (16)

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Publication number Priority date Publication date Assignee Title
AT287905B (de) 1968-09-20 1971-02-10 Chemiefaser Lenzing Ag Verfahren zur Herstellung von Faden aus regenerierter Cellulose
AT392972B (de) 1988-08-16 1991-07-25 Chemiefaser Lenzing Ag Verfahren zur herstellung von loesungen von cellulose sowie einrichtung zur durchfuehrung des verfahrens
ATA53792A (de) 1992-03-17 1995-02-15 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer formkörper, vorrichtung zur durchführung des verfahrens sowie verwendung einer spinnvorrichtung
SE501325E (sv) * 1993-01-29 1999-09-20 Kvaerner Pulping Tech Förfarande för klorfri blekning av massa, varvid massan surgöres med ättiksyra vid behandlingen med komplexbildare
JP2003253582A (ja) * 2002-03-06 2003-09-10 Nippon Paper Industries Co Ltd パルプの漂白処理方法
CN100557123C (zh) * 2004-03-09 2009-11-04 徐守才 碱性亚硫酸钠法草浆的少氯漂白及中段水全封闭回用技术
DK2425024T3 (da) 2009-04-28 2013-04-15 Heli Inovatio Handelsbolag Fremgangsmåde til hydrolyse af cellulose
ES2711754T3 (es) 2010-10-27 2019-05-07 Re Newcell Ab Proceso para la derivatización de celulosa
KR20140003559A (ko) * 2011-01-26 2014-01-09 군제 가부시키가이샤 친수성화 셀룰로오스 섬유의 제조 방법 및 산화 셀룰로오스 섬유의 환원 방법
WO2013124265A1 (en) 2012-02-20 2013-08-29 Renewcell Lux S.À.R.L Regeneration of cellulose
FI129086B (en) * 2012-09-14 2021-06-30 Teknologian Tutkimuskeskus Vtt Oy Method for producing soluble pulp
AT515152B1 (de) 2013-11-26 2015-12-15 Chemiefaser Lenzing Ag Verfahren zum Vorbehandeln von rückgewonnenen Baumwollfasern zur Verwendung bei der Herstellung von Formkörpern aus regenerierter Cellulose
AT517020B1 (de) * 2015-02-06 2020-02-15 Chemiefaser Lenzing Ag Recycling von cellulosischen Kunstfasern
SE541675C2 (en) 2016-10-19 2019-11-26 Re Newcell Ab Recycling of cellulosic textiles
US11414789B2 (en) * 2016-12-06 2022-08-16 Re:Newcell Ab Cellulose fibers
CN107724057A (zh) * 2017-09-30 2018-02-23 莆田学院 一种磁性氧漂稳定剂制备方法及其在漂白工艺中的应用

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EP4121584A1 (de) 2023-01-25

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