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WO2024220053A1 - Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques - Google Patents

Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques Download PDF

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Publication number
WO2024220053A1
WO2024220053A1 PCT/TR2023/051643 TR2023051643W WO2024220053A1 WO 2024220053 A1 WO2024220053 A1 WO 2024220053A1 TR 2023051643 W TR2023051643 W TR 2023051643W WO 2024220053 A1 WO2024220053 A1 WO 2024220053A1
Authority
WO
WIPO (PCT)
Prior art keywords
tank
waste
process step
mixture
feeding
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/TR2023/051643
Other languages
English (en)
Inventor
Gürcan KOMAN
Simge DİNÇER UZUNPINAR
Selçuk ERKOŞAN
Emrah EREN
Turgay Yilmaz
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.)
Aksa Akrilik Kimya Sanayii AS
Original Assignee
Aksa Akrilik Kimya Sanayii AS
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 Aksa Akrilik Kimya Sanayii AS filed Critical Aksa Akrilik Kimya Sanayii AS
Priority to PCT/TR2023/051643 priority Critical patent/WO2024220053A1/fr
Publication of WO2024220053A1 publication Critical patent/WO2024220053A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • 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
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • the invention relates to the production of acrylic fibre by using/adding recycled waste materials.
  • Acrylic fibres like other general-purpose synthetic fibres such as polyamide fibres and polyester fibres, are used in a wide variety of fields, such as clothing materials and interior product materials. On average, 15 billion pieces of clothing are thrown away unused annually worldwide. This type of thrown clothing has become a major problem in recent years and causes rapid depletion of natural resources. Although ready-made clothing and material manufacturers work to reuse and recycle these discarded clothes, the current situation causes delays in development due to the high labour cost required for separation work and the difficulty of high separation and collection technology, and prevents the recycling of waste products in sufficient quantities.
  • the Russian document with publication number RU2722499C1 comprises basic information about the recycling of acrylic products. It is not possible to use the methods mentioned in this document for recycling without damaging the chemical structure of acrylic fibres.
  • Japanese document with publication number JP20221121 14A describes postconsumer recycled acrylic fibre and the production method thereof.
  • the method involves grinding the textile products, separating, recovering and using the acrylic component.
  • the proposed recycled acrylic fibre comprises the acrylic component obtained by milling a textile and recovered from a mixture of milled fibres with an aspect ratio (fibre length/fibre diameter) of 10 or less.
  • the fibre product comprises a total of 5.0 to 99.0% by weight of the acrylic component.
  • the method of recovering the acrylic component from the milled fibre mixture and then spinning it into yarn is described.
  • the collected acrylic component is dissolved in a solvent to form an acrylic polymer solution (A), and this solution is turned into wet-yarn with a polymer mixture of 0.5% to 60.0% by weight, but the recovery rate is quite low compared to the energy spent. In addition, the strength and flexibility properties of the final product are low.
  • the Chinese document with publication number CN1 17164951 A describes the recovery method of waste acrylic fabrics in the technical field of environmental protection and recycling of waste acrylic fabrics.
  • the method comprises the process steps of: Dissolving (completely dissolving the acrylic fibres by adding the waste acrylic fibre textile to a solvent, heating and mixing), Soaking (keeping the polyacrylonitrile solution at low temperature and turning it from yellow transparent liquid into polyacrylonitrile white gel), Shaping (placing the polyacrylonitrile white gel to cure in a heat environment), Extraction (soaking the polyacrylonitrile solid in an extractant and performing solvent extraction with continuous release) and Drying (obtaining polyacrylonitrile porous material by drying the polyacrylonitrile solid subjected to solvent extraction).
  • the aim of this invention is not to obtain acrylic fibre, but to obtain material that can be used in making products made of polymer containing acrylonitrile monomer, which can be used in some technical fields.
  • Acrylic fibres can be reused, but materials with sufficient durability cannot be created for acrylic fibre production.
  • This invention is about converting wastes brought in solid and gel form into reusable materials.
  • Technical work is required to work at more ergonomic and optimal temperatures and to obtain more durable products.
  • the main aim of the invention is to produce acrylic fibre from recyclable acrylic fibre waste.
  • the aim of the invention is to prevent environmental pollution caused by waste materials and to prevent the consumption of natural and/or artificial resources.
  • Another aim of the invention is to ensure the recovery of waste products.
  • the aim of the invention is to use it in the recycling process of waste in both solid and liquid form.
  • the invention described in detail below, was put forth to produce acrylic fibre by recycling acrylic fibre waste without damaging their chemical structure to achieve recovery in the range of 15% to 100%
  • dope fibre is produced by wet and dry spinning method. Polymers, dopes and fibres, which occur as a result of process stoppages due to malfunctions during polymer and fibre production, during installation periods and during transitional production to reach the target machine condition, become waste. Threads and fabrics produced from acrylic fibres also constitute waste.
  • dry and wet fibre waste is mixed with the appropriate solvent and the tanks are heated to melt the fibre waste. In addition, these are melted with a continuous mixing process to obtain a homogeneous solution.
  • the invention comprises the processes of feeding to the slurry tank from 3 points and the subsequent recycling process.
  • One of said 3 feeding processes is the process of feeding the waste dope to the slurry tank.
  • This process comprises the process steps of a.1 . collecting waste dope-containing materials in the storage tank, a.2. performing at least one filtration process with the help of a pump to ensure the separation of unusable materials, a.3. conveying the waste dope-containing mixture obtained after the filtration process to the waste feeding tank, a.4. feeding of waste materials with a waste content ranging from 15% to 26% solid matter and a feeding rate of 150 kg/s to 400 kg/s to the slurry tank from the feeding tank.
  • the process of feeding waste to the slurry tank ensures that the waste comes to appropriate conditions before being recycled and that the final product obtained after the recycling process can be created in the desired qualities.
  • the materials added to the storage tank in process step a.1 . are subjected to mixing to ensure a homogeneous mixture and are heated to a temperature in the range of 70-100°C to accelerate the process.
  • the mixing process is continued by keeping the mixture at a temperature of 70-100°C for 4-10 hours. While a temperature below 70°C cannot achieve the desired effect on the mixture in the desired time, a temperature above 100°C causes burning, flashing and/or deformations in the mixture.
  • Another of said 3 feeding processes is the waste acrylic fibre feeding process with dilute dope addition to the slurry tank.
  • This process comprises the process steps of b.1. adding dry waste containing waste acrylic fibre into the perforated tank and heating the tank to a temperature in the range of 70-110°C, b.2. cooling the acrylic fibre waste mixed with the dry waste separated from the perforated tank to a temperature between 50-90°C with the help of a pump and heat exchanger, and subjecting it to this process in a recirculating manner by re-entering it the perforated tank, b.3.
  • the mixture transferred to the slurry preparation tank as a result of the method step b.5. is dope.
  • the resulting dope is in diluted form.
  • the environment in the process step b.5., is kept in the temperature range of 60-120°C to ensure the appropriate temperature by the heat exchanger.
  • the filtration process is applied at least once after the process step b.5. and before the process step b.6.. Filtration processes ensure that the impurity content of many different qualities is kept at the desired level and the contents that can damage the final product are removed.
  • said solvent in process step b.6. contains one of the groups or combinations of individuals comprises dimethylacetamide, dimethyl sulfoxide, dimethylformamide and N-methyl-2-pyrrolidone.
  • said polymer in process step b.6. is polyacrylonitrile (PAN).
  • PAN polyacrylonitrile
  • the polyacrylonitrile ratio in acrylic fibres determines whether the acrylic fibre is acrylic or modacrylic.
  • Modacrylic fibres which stand out with their flame retardant properties, contain polyacrylonitrile in the range of 35-85% by weight, while acrylic fibres contain more than 85% polyacrylonitrile by weight.
  • the PAN polymer is one of the individuals or combinations selected from the group consisting of homopolymer, co-polymer, modified polymer and sulponated polymer.
  • PAN polymer is fed to the tank by measuring the feed amount with a scale using rotary valves. Rotary valve sets are adjusted and fed according to the recovery rate of polymer and waste polymer products.
  • nozzles in the tank where the polymer is fed.
  • Solvent solvent temperature 25-70°C
  • dilute dope prepared by melting dry fibre waste and heat stabilizer are given through these nozzles.
  • the mixture obtained after the process step b.6. comprises;
  • Wastes in dry form are dissolved with solvent on the perforated surfaces in the tanks. Meanwhile, the tanks are put into circulation.
  • dope in dilute form is circulated through heating exchangers.
  • Exchanger temperature is between 70-100°C. In the current process, it heats to 85°C.
  • heating is done in the tank shells and the tank internal temperature is kept between 70-100 °C. In the current process it is 80°C.
  • Circulation in the tank continues for 4-10 hours depending on the amount and type of waste. In the current process, it is done for 6 hours. After the melting process is fully completed, the diluted dope is taken into the storage tank.
  • the last of said 3 feeding processes is the feeding process of waste acrylic fibre melted in a vacuum environment.
  • This process proceeds in two directions when both solid and wet wastes are used. After the solid and wet wastes are processed separately, the processed wastes are combined, and the process continues.
  • Vacuum tanks are used to melt waste in wet form. By creating a vacuum in the tanks and removing the water in the waste, homogeneous melting is achieved and coagulation and agglomeration that may occur in the water-borne solution is prevented. Gradual ejector and heat exchanger systems are used in these tanks and the tanks are vacuumed in this way.
  • the feeding process of waste acrylic fibre melted in a vacuum environment comprises the process steps of: c.1 .
  • the internal pressure of the tank containing wet water mentioned in the process steps related to the feeding process of waste acrylic fibre melted in a vacuum environment is kept between 0.75 bar and full vacuum. After heating to 70-100°C depending on the amount of waste in the tank (85°C in the current process), the vacuum system is activated, and the vacuuming process is stopped when the temperature drops to 50-75°C (65°C in the current process).
  • Feeding is done to the slurry preparation tank according to the recovery rate from the storage tank mentioned in the process step c.9. Depending on the feed amount, recovery rates vary between 10% and 100%.
  • the recycling method is applied starting from the slurry tank.
  • This method comprises the process steps of: d.1. heating the slurry tank, d.2. separating the acrylic material that cannot be used in the resulting mixture by filtration process, d.3. heating the mixture resulting from the process step d.2. to 60-120°C using a slurry exchanger to ensure dope formation, d.4. cooling to 50-90 °C with the help of a heat exchanger to prevent the colour of the dope produced in the process step d.3. from changing, d.5. transferring it to the deaerator tank and heating it to remove air bubbles in the dope consisting of recycled materials obtained as a result of the filtration process. d.6.
  • the slurry in the slurry tank is heated to 60-120°C using a heat exchanger and dope is prepared.
  • the filtration process is carried out by one of the individuals or combinations selected from the group consisting of filter presses, pot filter, basket filter and blunder filter.
  • the above processes, which are applied after feeding the Slurry tank from 3 points, are sensitive processes and no step can be separated from the other.
  • the process steps that are desired to be covered by the protection of the invention are the 3 feedings to the slurry tank and the operations performed after the slurry tank. In other words, each of the 3 mentioned feeds is very important for the operation of the invention.
  • heating processes are carried out for 4-10 hours in order to obtain the desired mixture in all tanks.
  • the tanks are kept under nitrogen cover. In this way, the process is carried out above the flash temperature of the solvent.
  • the mixture created with blue and violet pigments is given to the mixer and the mixture is injected into the dope in order to provide the whiteness parameter for colourless products in fibre production machines.
  • different pigments can also be used for colouring.
  • the dyeing process can be carried out.
  • An alternative embodiment of the invention also comprises the dyeing process after the process step d.9, and dope dyeing and/or gel dyeing method is used in this dyeing process.
  • the final product number resulting from the process step d.9. varies between 1.10 and 45 dtex.
  • the strength of the product is 10-50 cN/T and the elongation is between 30- 60%.
  • the process steps for which the invention is intended to be protected are the 3 feedings to the slurry tank, the post-slurry tank operations and the recycled acrylic fibre obtained as the final product.

Landscapes

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

Abstract

L'invention se rapporte à un procédé de production permettant de produire une fibre acrylique ayant des propriétés mécaniques améliorées en recyclant des déchets de fibres acryliques sans endommager leur structure chimique, et à la fibre acrylique recyclée obtenue par ce procédé.
PCT/TR2023/051643 2023-12-22 2023-12-22 Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques Pending WO2024220053A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/TR2023/051643 WO2024220053A1 (fr) 2023-12-22 2023-12-22 Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2023/051643 WO2024220053A1 (fr) 2023-12-22 2023-12-22 Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques

Publications (1)

Publication Number Publication Date
WO2024220053A1 true WO2024220053A1 (fr) 2024-10-24

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ID=93153198

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Application Number Title Priority Date Filing Date
PCT/TR2023/051643 Pending WO2024220053A1 (fr) 2023-12-22 2023-12-22 Procédé de revalorisation de déchets de fibres acryliques dans la fabrication de fibres acryliques

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013118132A1 (fr) * 2012-02-10 2013-08-15 Adab Omid Procédé de conversion de déchet gris de fibre acrylique en poudre acrylique
CN113122946A (zh) * 2019-12-30 2021-07-16 河北艾科瑞纤维有限公司 一种再生腈纶的制备方法及产品
JP2023121922A (ja) * 2022-02-22 2023-09-01 東レ株式会社 リサイクルアクリル系合成繊維の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013118132A1 (fr) * 2012-02-10 2013-08-15 Adab Omid Procédé de conversion de déchet gris de fibre acrylique en poudre acrylique
CN113122946A (zh) * 2019-12-30 2021-07-16 河北艾科瑞纤维有限公司 一种再生腈纶的制备方法及产品
JP2023121922A (ja) * 2022-02-22 2023-09-01 東レ株式会社 リサイクルアクリル系合成繊維の製造方法

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