EP4136282A1 - Procédé de récupération et de recyclage de produits chimiques dans un procédé de fibre de cellulose régénérée - Google Patents

Procédé de récupération et de recyclage de produits chimiques dans un procédé de fibre de cellulose régénérée

Info

Publication number
EP4136282A1
EP4136282A1 EP21789259.5A EP21789259A EP4136282A1 EP 4136282 A1 EP4136282 A1 EP 4136282A1 EP 21789259 A EP21789259 A EP 21789259A EP 4136282 A1 EP4136282 A1 EP 4136282A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
electrolysis
process according
spinning
sodium hydroxide
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
EP21789259.5A
Other languages
German (de)
English (en)
Inventor
Lars Stigsson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Treetotextile AB
Original Assignee
Treetotextile AB
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 Treetotextile AB filed Critical Treetotextile AB
Publication of EP4136282A1 publication Critical patent/EP4136282A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/006—Recovery of sodium sulfate from coagulation baths for the spinning of viscose
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
    • 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
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/02—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of cellulose, cellulose derivatives or proteins
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • process chemicals such as cellulose solvent and spin bath chemical should be recycled.
  • the reason for recycling is both economic and environmental.
  • derivatized cellulose is dissolved in sodium hydroxide forming a spin dope which is injected through a nozzle (spinneret) into an aqueous acidic spin bath (coagulation baths, stretching and washing baths) wherein regenerated cellulose fibers are formed.
  • the sodium hydroxide in the spin dope is neutralized by the acid (primarily sulfuric acid) forming a solution of sodium sulfate.
  • the spin bath coagulation bath, stretching baths
  • a side stream of spent acidic spin bath is taken for evaporation, the volume flow being set to achieve the desired water removal and required concentration of sodium sulfate.
  • Multistage evaporators and/or mechanical vapor compression units may be used for concentration of the spent spin bath solution.
  • Glauber salt can be converted to anhydrous sodium sulfate for sale.
  • the viscose process uses large quantities of sodium hydroxide which has to be purchased to make up for the losses by neutralization to sodium sulfate. It would therefore be of great advantage to establish a process wherein the sodium hydroxide could be recovered from spent spin bath and recycled to dissolve cellulose.
  • the viscose process is using toxic carbon disulfide for derivatization of the cellulose which needs to be contained and recycled for cost and environmental reasons.
  • New processes for the manufacturing of regenerated cellulosic fibers without using carbon disulfide have been proposed such as in US Pat. 8617354 incorporated herein in its entirety as reference. Also these new processes suffer from high cost of fresh spinning chemicals in configurations wherein an alkaline spin dope is neutralized in an acidic spin bath.
  • a key objective of the present invention is to recover and recycle fresh sodium hydroxide from spent acidic spin baths using a new and innovative recovery method.
  • the process of the present invention is built on the discovery that electrolysis can provide a solution to the problem of chemicals recovery in certain fiber spinning processes.
  • the main alternative configurations for electrolyzing sodium sulfate are two or three compartment electrolyzers or electrodialyzers.
  • electrochemical processes the separation of Na and S compounds is governed by an electrostatic field creating migration of ions over an ion exchange membrane.
  • the two compartment electrolyzer is very similar to the membrane based chlor-alkali electrolyzer concept and is thus technically proven for that application.
  • the acid and the base are electrochemically generated by splitting water.
  • On the anode side water is oxidized into oxygen and protons and on the cathode side water is reduced into hydrogen and hydroxide.
  • CEM cation exchange membrane
  • sodium may migrate from the the anode (+) to the cathode (-) side of the cell.
  • sodium hydroxide will be produced and in the anode compartment sulfuric acid mixed with sodium sulfate (about 50/50) will be produced.
  • a rather pure sulfuric acid can be produced.
  • the electrochemical reactions are the following;
  • Zn compounds may be used in alkaline spin dopes and it is preferable that Zn is recycled in a form suitable for addition to the spin dope or to the spin bath.
  • Zn can be recovered by ion exchange prior to electrolysis of the spent spin bath stream.
  • Another and preferable method to remove and recycle Zn is by alkalizing the acidic spin bath comprising Zn compounds to pHs above about 6, preferably above pH 8, forming separable Zn hydroxides that may be recycled and used for additives in cellulosic spin dopes or as additive to spin baths.
  • the electrolysis process and fiber spinning unit of the present invention is advantageously integrated in a kraft pulp mill or organosolv pulp mill for manufacturing of dissolving cellulose pulp.
  • Oxygen formed in the electrolysis process may be used in oxygen delignification units, in brown stock washing or as an oxidant in biomass gasification processes gasifying spent pulping liquors and/or biomass.
  • Hydrogen formed may be used as fuel in limekilns, for hydrotreatment of biomass and lignin or for addition to synthesis gas from gasifying biomass.
  • the present invention is directed to a process for the recovery and recycle of spinning chemicals for spinning regenerated cellulosic fibers using alkaline cellulose solvents for dissolution of cellulose, said process being characterized by that spinning and/or fiber washing chemicals are treated by electrolysis of sodium sulfate therein, forming one stream comprising sodium hydroxide and one stream comprising sulfuric acid, and wherein at least part of the formed sodium hydroxide is used for pre-treatment of cellulose for adjustment of intrinsic viscosity of the cellulose, and/or as an aid in removal of hemicellulose from cellulose, and/or for dissolving cellulose in a sodium hydroxide solvent, and/or wherein at least part of the formed sulfuric acid is used in one or more steps of the fiber washing, and/or in the cellulose spinning and/or for fiber regeneration.
  • the process according to the present invention is directed to incorporating electrolysis as a technology to enable to recirculate and reuse sodium hydroxide and/or sulfuric acid, as chemical recovery in fiber spinning processes.
  • either or both of these mentioned chemicals may be recovered.
  • either or both these chemicals may be recovered and reused in a process of spinning regenerated cellulosic fibers using alkaline cellulose solvents.
  • sodium hydroxide and/or sulfuric acid may also vary according to the present invention.
  • sodium hydroxide at least a part of this may be used for one or several of the following:
  • At least part of the formed sodium hydroxide is used for pre-treatment of cellulose for adjustment of intrinsic viscosity of the cellulose and/or for dissolving cellulose in a sodium hydroxide solvent.
  • sulfuric acid this is a suitable chemical to use in the fiber washing stage.
  • at least part of the formed sulfuric acid is used in one or more steps of the fiber washing.
  • the sulfuric acid may be used alone or together with other components to provide for an acidic treatment during the washing process after fiber spinning. Therefore, according to yet another embodiment of the present invention, the process involves washing produced fibers in a sulfuric acid containing liquid, wherein at least part of the sulfuric acid has been produced via electrolysis.
  • the intended acidic treatment in the washing process may be performed to ensure to wash out all sodium hydroxide from the produced fiber.
  • an electrolysis unit may be chosen based on its primary intended use. As an example, if sulfuric acid being recovered from the electrolysis unit is intended to be used in the fiber washing process, then the electrolysis unit is suitably placed in the proximity of the fiber washing line.
  • sodium hydroxide rich spinning or fiber washing chemicals are separated from a coagulation bath, a stretching bath or a fiber washing bath prior to an acidic fiber washing step thereby forming a sodium sulfate containing effluent, said sodium sulfate containing effluent thereafter being treated by electrolysis for at least partial recovery of sodium hydroxide and/or sulfuric acid.
  • the sodium sulfate containing effluent is concentrated with respect to sodium sulfate before treatment by electrolysis.
  • the process according to the present invention may be integrated in different types of fiber production processes.
  • the process is integrated in a kraft or organosolv pulp mill for manufacturing dissolving cellulose pulp.
  • the process is integrated in a viscose plant, preferably equipped with spin bath effluent evaporation.
  • the process according to the present invention may also include other steps in addition to the electrolysis.
  • the process includes purification of spin bath chemicals prior to electrolysis, preferably where at least Zn compounds are removed. To remove impurities or components providing disturbance or problems in the electrolysis is a suitable action to include according to the present invention. If such components are accumulated in the electrolysis it will be difficult to perform this process in an efficient way.
  • the process includes a complementary step of separating off impurities from the spinning effluent or the washing bath effluent or from sodium sulfate recovered from the spinning effluent or the washing bath effluent, prior to electrolysis of a substantially pure sodium sulfate solution.
  • the process includes separating off impurities from a stream of an alkaline spin bath liquid prior to electrolysis, and wherein the step of separating off impurities involves at least one of evaporation, precipitation, ion exchange, flocculation, flotation and/or filtration, or a combination thereof, preferably at least ion exchange.
  • at least Zn is recovered prior to electrolysis, preferably by ion exchange.
  • a sulfate rich effluent stream is separated from a fiber washing step, which stream is treated by at least one of evaporation or separation of impurities followed by electrolysis, preferably wherein at least part of the electrolysis treated stream is recovered and recycled.
  • the type of electrolysis unit may be of relevance according to the present invention.
  • the electrolysis is performed in a two or three compartment electrolyzer or electrodialyzer, preferably in a three compartment electrolyzer.
  • a three compartment electrolyzer is a very suitable alternative for the type of streams intended to treat according to the present invention, i.e. when implementing it in a fiber production process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé de récupération et de recyclage de produits chimiques de filage destinés au filage de fibres cellulosiques régénérées à l'aide de solvants de cellulose alcalins pour dissoudre la cellulose, ledit procédé étant caractérisé en ce que des produits chimiques de filage et/ou de lavage de fibre sont traités par électrolyse du sulfate de sodium en leur sein, formant un flux comprenant de l'hydroxyde de sodium et un flux comprenant de l'acide sulfurique, et au moins une partie de l'hydroxyde de sodium formé étant utilisée pour prétraiter la cellulose à des fins de réglage de la viscosité intrinsèque de la cellulose, et/ou en tant qu'aide à l'élimination de l'hémicellulose de la cellulose et/ou pour dissoudre la cellulose dans un solvant à base d'hydroxyde de sodium, et/ou au moins une partie de l'acide sulfurique formé étant utilisée dans une ou plusieurs étapes du lavage de fibres et/ou dans le filage de cellulose et/ou à des fins de régénération de fibres.
EP21789259.5A 2020-04-17 2021-04-16 Procédé de récupération et de recyclage de produits chimiques dans un procédé de fibre de cellulose régénérée Pending EP4136282A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE2050437 2020-04-17
PCT/SE2021/050349 WO2021211046A1 (fr) 2020-04-17 2021-04-16 Procédé de récupération et de recyclage de produits chimiques dans un procédé de fibre de cellulose régénérée

Publications (1)

Publication Number Publication Date
EP4136282A1 true EP4136282A1 (fr) 2023-02-22

Family

ID=78084826

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21789259.5A Pending EP4136282A1 (fr) 2020-04-17 2021-04-16 Procédé de récupération et de recyclage de produits chimiques dans un procédé de fibre de cellulose régénérée

Country Status (2)

Country Link
EP (1) EP4136282A1 (fr)
WO (1) WO2021211046A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4368753A1 (fr) 2022-11-08 2024-05-15 TreeToTextile AB Tissu avec de la cellulose régénérée
WO2024102053A1 (fr) 2022-11-08 2024-05-16 Treetotextile Ab Tissu contenant de la cellulose régénérée

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS535974B2 (fr) * 1974-10-21 1978-03-03
US4504373A (en) * 1982-06-01 1985-03-12 Allied Corporation Electrodialytic water splitting process and apparatus for conversion of alkali metal sulfate values derived from spent rayon spin baths
DE3315626A1 (de) * 1983-04-29 1984-10-31 Hoechst Ag, 6230 Frankfurt Verfahren zur anreicherung von schwefelsaeure
PT2406291T (pt) * 2009-03-09 2018-12-28 Treetotextile Ab Processo de fabrico de celulose moldada combinado com um sistema de recuperação de fábrica de pasta de papel
US10138578B2 (en) * 2013-07-01 2018-11-27 Treetotextile Ab Alkali recycle in cellulose spinning process
EP3231899A1 (fr) * 2016-04-14 2017-10-18 TreeToTextile AB Procédé et système pour la production d'une composition de solution à filer
EP3231901A1 (fr) * 2016-04-14 2017-10-18 TreeToTextile AB Procédé pour le filage de cellulose dissoute comprenant recuperer du liqueur de coagulation epuisee d'une solution de hydroxide de sodium comme solvant aqueux pour cellulose
EP3983583A4 (fr) * 2019-06-13 2023-07-12 TreeToTextile AB Fibres produites à partir de déchets cellulosiques recyclés

Also Published As

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WO2021211046A1 (fr) 2021-10-21

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