[go: up one dir, main page]

WO2025097116A1 - Procédés de recyclage chimique de déchets textiles mélangés - Google Patents

Procédés de recyclage chimique de déchets textiles mélangés Download PDF

Info

Publication number
WO2025097116A1
WO2025097116A1 PCT/US2024/054363 US2024054363W WO2025097116A1 WO 2025097116 A1 WO2025097116 A1 WO 2025097116A1 US 2024054363 W US2024054363 W US 2024054363W WO 2025097116 A1 WO2025097116 A1 WO 2025097116A1
Authority
WO
WIPO (PCT)
Prior art keywords
cotton
nylon
oxide
glycolysis
textile waste
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/US2024/054363
Other languages
English (en)
Inventor
Erha ANDINI
Sunitha SADULA
Dionisios VLACHOS
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of WO2025097116A1 publication Critical patent/WO2025097116A1/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
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • PET 2101715-001243 -2- chemical recycling techniques such as hydrolysis, methanolysis, glycolysis, and enzymatic depolymerization
  • these recycling techniques are met with challenges when used on mixed textile wastes since the polyesters in the waste products are often interlaced tightly with other fibers (e.g., synthetic or natural polymers) consisting of cotton, nylon, spandex, dyes, and finishes.
  • Fibers e.g., synthetic or natural polymers
  • SUMMARY Disclosed herein is a method for recycling a mixed textile waste, the method including (i.e., comprising) performing a microwave-assisted glycolysis on the mixed textile waste to produce a depolymerization solution, wherein the microwave- assisted glycolysis occurs at a temperature above 100°C, and wherein the mixed textile waste includes at least two materials selected from, but not limited to, polyesters, spandex, cotton or nylon.
  • Disclosed herein are also recycled fibers and/or products produced from any one of the recycling methods disclosed herein.
  • FIG.3 depicts the solid residues that form upon the glycolysis of the 50/50 PolyCotton blend at various temperatures and times.
  • FIG.4 depicts characterization data of the residual solid product formed from the glycolysis of the 50/50 PolyCotton blend.
  • FIG.5 depicts SEM photographs of the solid residue product of the glycolysis of the 50/50 PolyCotton, a 100% polyester material, a 100% cotton material, and the 50/50 PolyCotton blend before glycolysis.
  • FIG.6 depicts BHET yields from 100% polyester textiles containing dyes and finishes.
  • FIG.7 depicts solid residues of 100% polyester textiles that contained dyes and finishes.
  • the solid residues are products of a microwave-assisted glycolysis reaction performed on the 100% polyester textiles.
  • the conditions of the microwave-assisted glycolysis reaction are: 0.5 g of 100% polyester textile, 5 mg of ZnO, 5 ml of EG, 210°C, and 15 min. 2101715-001243 -4-
  • FIG.8 depicts the residual solid amounts of various textile blends after being subjected to a microwave-assisted glycolysis reaction.
  • FIG.9 depicts an exemplary recycling process for mixed textile wastes.
  • A Isolated components obtained from mixed textile waste with unknown compositions.
  • MDI methylene diphenyl diisocyanate.
  • FIG.10 depicts a techno-economic analysis of an exemplary recycling process for mixed textile wastes.
  • A The techno-economic analysis (TEA) process developed in ASPEN.
  • the present disclosure should not be construed as being limited to these embodiments; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the technology described herein to those skilled in the art.
  • the term “about” refers to a value that is ⁇ 5% of the stated value.
  • reference to a range of a first value to a second value includes the range of the stated values, e.g., a range of about 1 to about 5 also includes the more precise range of 1 to 5.
  • the ranges disclosed herein include any selected subrange within the stated range, e.g., a subrange of about 50 to about 60 is contemplated in a disclosed range of about 1 to about 100.
  • the present disclosure relates to a method for recycling a mixed textile waste, the method including one or more of the following: performing a microwave- assisted glycolysis on the mixed textile waste to produce a depolymerization solution, wherein the microwave-assisted glycolysis occurs at a temperature above 100°C and in a presence of a catalyst, wherein the mixed textile waste includes at least two materials selected from, but not limited to, polyesters, spandex, cotton or nylon. A representative illustration of this method is depicted in FIG.1.
  • a “mixed textile waste” is a composition of textile waste materials that have been isolated from various textile waste and production sites (e.g., landfills, recycling bins, post-industrial waste sites, textile production companies, clothing brands, and textile sorting companies) and optionally have been mechanically processed (e.g., carded or shredded).
  • the mixed textile waste includes at least three materials selected from polyesters, spandex (or elastane), cotton and nylon.
  • the mixed textile waste includes polyesters, spandex (or elastane), cotton and nylon.
  • the mixed textile waste contains polyesters in a weight percentage, based on the total weight of the mixed textile waste, of about 0.1wt% to about 99wt%, about 5wt% to about 90wt%, about 10wt% to about 80wt%, about 20wt% to about 70wt%, about 30wt% to about 50wt%, or any weight percentage range or specific weight percent value falling within the range of about 2101715-001243 -6- 0.1wt% to about 99wt%.
  • Polyesters that the mixed textile waste can include are, but not limited to, polyethylene terephthalate (PET), poly-1,4-cyclohexylene- dimethylene terephthalate (PCDT), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), plant-based polyesters and combinations thereof.
  • PET polyethylene terephthalate
  • PCDT poly-1,4-cyclohexylene- dimethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • the mixed textile waste contains cotton in a weight percentage, based on the total weight of the mixed textile waste, of about 0.1wt% to about 99wt%, about 5wt% to about 90wt%, about 10wt% to about 80wt%, about 20wt% to about 70wt%, about 30wt% to about 50wt%, or any weight percentage range or specific weight percent value falling within the range of about 0.1wt% to about 99wt%.
  • Cottons that the mixed textile waste can include are, but not limited to, poplin, lawn, muslin, flannel, corduroy, canvas, jersey, Egyptian, brushed and combinations thereof.
  • the mixed textile waste contains nylons in a weight percentage, based on the total weight of the mixed textile waste, of about 0.1wt% to about 99wt%, about 5wt% to about 90wt%, about 10wt% to about 80wt%, about 20wt% to about 70wt%, about 30wt% to about 50wt%, or any weight percentage range or specific weight percent value falling within the range of about 0.1wt% to about 99wt%.
  • Nylons that the mixed textile waste can include are, but not limited to, nylon 6, nylon 66, nylon 6.10, nylon 4.6, nylon 12, ballistic nylon and combinations thereof.
  • the mixed textile waste contains spandex (or elastane) in a weight percentage, based on the total weight of the mixed textile waste, of about 0.1wt% to about 99wt%, about 5wt% to about 90wt%, about 10wt% to about 80wt%, about 20wt% to about 70wt%, about 30wt% to about 50wt%, or any weight percentage range or specific weight percent value falling within the range of about 0.1wt% to about 99wt%.
  • the mixed textile waste includes at least one textile material (e.g., a nylon, a polyester, a spandex or a cotton) containing one or more dyes and one or more finishes.
  • dyes include, but are not limited to, fiber reactive dyes, natural dyes, VAT dyes, direct dyes, acid dyes, disperse dyes (such as, but not limited to, Red 1, Red 13, Red 15, Red 54, Red 60, Red 86, 2101715-001243 -7- Red 179, Yellow 3, Yellow 64, Yellow 23, Yellow 219, Yellow 123, Blue 1, Blue 3, Blue 19, Blue 56, Blue 79, Blue 35, Blue 106, Green 6, Green 5, Green 2, and Green 9), all-purpose dyes, azoic dyes, basic/cationic dyes, mordant dyes and sulfur dyes.
  • fiber reactive dyes such as, but not limited to, Red 1, Red 13, Red 15, Red 54, Red 60, Red 86, 2101715-001243 -7- Red 179, Yellow 3, Yellow 64, Yellow 23, Yellow 219, Yellow 123, Blue 1, Blue 3, Blue 19, Blue 56, Blue 79, Blue 35, Blue 106, Green 6, Green 5, Green 2, and Green 9
  • all-purpose dyes such as, but not limited to, Red 1,
  • the microwave-assisted glycolysis is performed at a temperature ranging from 100°C to about 250 °C, from about 120°C to about 230°C, from about 150°C to about 210°C, from about 180°C to about 210°C, or above 250°C.
  • the temperature that the microwave-assisted glycolysis can be performed at depends on the composition of the mixed textile waste, the nature of the catalyst used in the glycolysis reaction, and the parameters of the microwave (e.g., the power of the microwave and the microwave’s ability to handle the vapor pressure produced from the reaction).
  • the microwave can perform the glycolysis reaction at any power or power range such as, but not limited to, those falling with a range of 0.1 W to 850 W. As long as the temperature of the glycolysis reaction allows the microwave to keep the vapor pressure produced from the reaction below 30 bar, then those temperatures can be used during the glycolysis reaction.
  • the microwave-assisted glycolysis is performed in the presence of a catalyst selected from, but not limited to, a metal oxide, a metal salt or a metal acetate.
  • a catalyst selected from, but not limited to, a metal oxide, a metal salt or a metal acetate.
  • metal oxides include, but are not limited to, zinc oxide, cobalt oxide, chrome oxide, copper oxide, manganese dioxide, nickel oxide, sodium oxide, magnesium oxide, calcium oxide, lithium oxide, silver oxide, iron (II) oxide, iron (III) oxide, chromium (VI) oxide, and titanium (IV) oxide.
  • metal salts include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium sulfate and sodium sulfate.
  • metal acetates include, but are not limited to, zinc acetate, manganese acetate, cobalt acetate, copper acetate and lead acetate.
  • the microwave-assisted glycolysis is performed in a diol such as, but not limited to, ethylene glycol, propylene glycol, 1,4- butanediol, propylene-1,3-diol, ethylene glycol/butanediol adipate (EBA), neopentyl glycol/butanediol adipate (NBA) and hexanediol adipate (HA).
  • a diol such as, but not limited to, ethylene glycol, propylene glycol, 1,4- butanediol, propylene-1,3-diol, ethylene glycol/butanediol adipate (EBA), neopentyl glycol/butanediol adipate (NBA) and hexanediol adipate (HA).
  • the microwave-assisted glycolysis is performed for at least 1 minute, at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 30 minutes, at least 45 minutes, at least one hour, or any range of time of specific timepoint falling within the range of about 1 minute to about one hour.
  • the microwave- assisted glycolysis is performed for more than 45 minutes.
  • the duration of the microwave-assisted glycolysis reaction is dependent upon the composition of the mixed textile waste (e.g., if dyes and finishes are present), the nature of the catalyst used in the glycolysis reaction, and the parameters of the microwave (e.g., the power of the microwave).
  • High powered microwaves could complete the glycolysis reaction in a matter of seconds depending on the complexity of the mixed textile waste composition, catalyst, solvent and type of microwave reactor vessel material used. For complex mixed textile wastes (i.e., those containing different varieties of textile materials, dyes and finishes) longer reaction times (e.g., those greater than 45 minutes) may be preferred.
  • the mixed textile waste is mechanically processed before the microwave-assisted glycolysis is performed. Examples of mechanical processing include, but are not limited to, shredding and carding.
  • the microwave-assisted glycolysis reaction concurrently (i.e., simultaneously) depolymerizes at least a portion of the spandex material and polyester material present in the mixed textile waste.
  • the depolymerization solution includes at least one material selected from, but not limited to, bis(2-hydroxyethyl) terephthalate 2101715-001243 -9- (BHET), nylon, cotton, diphenyl-containing molecules (e.g., a diphenylmethane- containing molecule), spandex monomers, polyols (e.g., polytetrahydrofuran diols) and combinations thereof.
  • BHET bis(2-hydroxyethyl) terephthalate 2101715-001243 -9-
  • nylon e.g., a diphenylmethane- containing molecule
  • spandex monomers e.g., polyols (e.g., polytetrahydrofuran diols) and combinations thereof.
  • the method includes diluting the depolymerization solution with an aqueous solution to separate soluble materials (e.g., BHET, diphenyl-containing molecules, spandex monomers and/or polyols) in the depolymerization solution from insoluble materials (e.g., cotton and/or nylon).
  • the method includes distilling the depolymerization solution and subsequently cooling the distilled depolymerization solution.
  • the subsequent cooling occurs at a temperature of about 4°C for about 24 hours and forms BHET crystals in the distilled depolymerization solution.
  • the method includes removing the BHET crystals from the cooled depolymerization solution via a filtration method.
  • the depolymerization solution contains cotton, nylon, polyols, or combinations thereof, and the method includes removing the cotton, nylon, polyols or combinations thereof from the depolymerization solution by filtering the depolymerization solution through a filter.
  • the depolymerization solution also contains polyester depolymerization products (e.g., BHET) and diphenylmethane-containing molecules and the method includes removing the cotton, nylon, polyols or combinations thereof from the depolymerization solution before the polyester depolymerization products and diphenylmethane-containing molecules are recovered.
  • the method includes washing the filtered cotton, nylon, polyols, or combinations thereof with an aqueous solution; and/or drying the washed cotton, nylon, polyols, or combinations thereof at a temperature of at least 100°C for about 24 hours.
  • the washed cotton, nylon, polyols, or combinations thereof are dried on a filter paper at a temperature of at least 100°C.
  • the polyols melt into the filter paper, thus allowing for a rapid, simple separation and removal of the polyols from the washed cotton and nylons.
  • the washed cotton, nylon, polyols, or combinations thereof are dried on a filter paper at room temperature (e.g., about 2101715-001243 -10- 20°C to 25°C) under vacuum. In these embodiments, the polyols do not melt into the filter paper, thus allowing for their recovery from the filter paper.
  • the method includes recovering BHET from the depolymerization solution; and/or polymerizing the recovered BHET into a recycled polyester product.
  • the method includes creating a yarn, filament and/or resin from the recycled polyester product.
  • the method includes at least one of the following: creating a garment or house furnishing from a yarn made from the recycled polyester product; creating a rope, cord or net from a filament made from the recycled polyester product; and/or creating a boat, pipe, tank, helmet, coating, adhesive, or sealant from a resin made from the recycled polyester product.
  • the method includes recovering a spandex monomer, for example ⁇ -methylenedianiline (MDA), from the depolymerization solution; transforming the recovered spandex monomer, for example MDA, into a polymerizable product, for example, methylene diphenyl diisocyanate (MDI); and/or polymerizing the polymerizable product, for example MDI, into a recycled spandex product.
  • MDA ⁇ -methylenedianiline
  • MDI methylene diphenyl diisocyanate
  • the method includes recovering a polyol from the depolymerization solution and/or polymerizing the recovered polyol with either recovered MDI or virgin MDI to produce a recycled spandex product.
  • the method includes recovering methylene diphenyl diisocyanate (MDI) and/or ethylene glycol derivatives of MDA from the depolymerization solution. 2101715-001243 -11-
  • the method includes creating a polyurethane foam, a resin, an adhesive, a plastic, or a high-performance polymer from at least a portion of the recovered spandex monomer, polymerizable product and/or recovered polyol.
  • the method includes recovering cotton from the depolymerization solution; and/or creating a yarn, a composite, a regenerated fiber, or a bioenergy material from the recovered cotton.
  • the method includes recovering nylon comprising the depolymerization solution; and/or creating a yarn, an automobile part, a food packing material, a strainer, a rope, a cord, a net, or a composite material from the recovered nylon.
  • the methods disclosed herein demonstrate efficacy in managing complex mixed textile waste, thus simulating real-world conditions of unsorted textile waste disposed in landfills. Because the sorting of unsorted textile waste disposed in landfills is recognized as a time-consuming and costly endeavor, some beneficial advantages of the methods disclosed herein are a reduction in processing costs and a rapid approach to recycling mixed textile waste. The methods disclosed herein allow for the rapid breakdown of polyester and spandex, and complete isolation of cotton and nylon from post-consumer mixed textile waste.
  • Example 1 Chemical Recycling of Finished and Mixed Textile Wastes Materials and Methods: Chemicals and materials Control fabrics used in this Example were purchased from JoAnn, including 100% polyester (white and colored with or without finishes) and 100% cotton (bleached and scoured).
  • the postconsumer textile waste was obtained from Goodwill provided by the University of Delaware Department of Fashion and Apparel Studies.
  • EG ethylene glycol
  • BHET BHET
  • zinc oxide ⁇ 50 nm
  • DMSO-d 6 deuterated dimethyl sulfoxide
  • Ultrapure type 1 water was used (Direct-Q3 UV-R). All textiles and chemicals were used as received. Reaction Procedures All experiments in this Example were performed on a Monowave 450 MW reactor (Anton Paar GmbH). This batch MW reactor controls the temperature, time, and maximum set power.
  • An in-built infrared sensor and an external Ruby thermometer allow for temperature control.500 mg of textiles, 5 ml of EG, and 5 mg of the catalyst were placed in a MW reaction vial. The vial was inserted into the MW reactor and the reactor was programmed to maintain a constant temperature. On completion of a reaction, the reaction vial was allowed to cool down rapidly to room temperature.100 mL of distilled water was added to separate BHET and oligomers. The unreacted polymers and larger oligomers were removed using a Whatman filter paper. The filtrate containing the products dissolved in water was analyzed using HPLC.
  • the residual water from the product solution was then evaporated under vacuum (72 mbar) at 60°C using a rotary evaporator and the 2101715-001243 -13- resulting BHET was crystallized by cooling the residual solution overnight to 4°C in a refrigerator after the addition of a small amount of distilled water to the residue.
  • the resultant crystals were filtered using a glass filter and dried at 80°C.
  • HPLC was used to quantify BHET concentrations with an Agilent 1260 Infinity coupled with a UV detector and a Zorbax Eclipse Plus C8 column.
  • the mobile phase contained equal volumes of methanol and ultrapure water at a flow of ⁇ P/ ⁇ PLQ ⁇ ZLWK ⁇ DQ ⁇ LQMHFWLRQ ⁇ YROXPH ⁇ RI ⁇ / ⁇ $ ⁇ %+(7 ⁇ FDOLEUDWLRQ ⁇ FXUYH ⁇ ZDV ⁇ constructed using a commercial standard.
  • Conversions of textiles and yields of BHET were calculated using the following equations: , wherein m, i corresponds to the initial mass of textile samples, m ,f corresponds to the mass of the unreacted textile (obtained via filtration), mol BHET corresponds to the BHET moles produced, and molPET corresponds to the initial moles of PET.
  • Analysis of textile samples and products Textile samples and BHET crystals were characterized using a Bruker D8 ;5' ⁇ ZLWK ⁇ &X ⁇ . ⁇ UDGLDWLRQ ⁇ ⁇ c ⁇ DW ⁇ N9 ⁇ DQG ⁇ P$ ⁇ (OHPHQWDO ⁇ composition was measured using wavelength dispersive x-ray fluorescence (XRF) on a Rigaku Supermini 200 machine with a Pd anode. 1 H NMR and 13 C NMR spectra were recorded with Bruker AVIII400 and AVIII600 spectrometers in a DMSO-d6 solution.
  • XRF wavelength dispersive x-ray fluorescence
  • the NMR spectra were analyzed using the MestReNova software. Unknown peaks were identified with an Agilent gas chromatography– mass spectrometer with a DB5 column, LC-MS using Thermo Fisher Scientific Q- extractive Orbitrap, and electrospray ionization mass spectrometry.
  • the attenuated 2101715-001243 -14- total reflectance-Fourier transform infrared (ATR-FTIR) data were collected using a Nicolet Nexus 640 spectrometer with a Smart Orbit Diamond ATR Accessory by scanning the sample from 400 to 4000 nm.
  • DSC was conducted using a TA instruments Discovery 250 at a heating rate of 10°C/min and cooling rate of 5°C/min using 5 to 10 mg of sample.
  • TGA was carried out using a TA instruments Discovery 5500 at a heating rate of 10°C/min under a N 2 atmosphere.
  • SEM images of the textile samples were recorded on an Auriga 60 microscope (Carl Zeiss NTS GmbH) equipped with a Schottky field emission gun. Before imaging, the samples were deposited on an adhesive carbon tape and sputtered by a DESK IV sputter unit (Denton Vacuum Inc.) equipped with Au/Pd target.
  • GPC was performed using an Agilent Technologies 1260 equipped with a PL–hexafluoroisopropanol (HFIP) gel column and refractive index detector.
  • the mobile phase was HFIP + 10 to 20 mM trifluoroacetic acid, the flow rate was 0.3 mL/min, and the column was held at 40°C.
  • Column calibration was performed with narrow dispersity poly(methyl methacrylate) standards.
  • Technoeconomic assessment The process was developed for a textile feed throughput of 500 kg/hour.
  • Experiment 1 Microwave-Assisted Glycolysis of Polyester:Cotton Blends Feedstock Characterization
  • the feedstocks used in this Experiment are well-defined feedstocks of white 100% polyester textile, white 100% cotton textile, and a white 50/50 blend of polyester and cotton T-shirt, referred to hereafter as 50/50 PolyCotton. These feedstocks were chosen due to the polyester and cotton dominance in the fiber market, holding 54 and 22% share, respectively.
  • the known compositions set benchmark standards for complex mixtures whose composition vary.
  • time-dependent microwave- assisted glycolysis experiments were performed at various temperatures to understand the effect of cotton on polyester glycolysis when the two are interlaced tightly. Only the polyester reacted while the cotton remained intact. Higher temperatures accelerated the complete depolymerization of the polyester (FIG.2) . The cotton did not participate in the glycolysis chemistry.
  • the color of the solution upon glycolysis changed from a light yellow hue at 150°C after 15 min to a 2101715-001243 -16- dark orange hue at 210°C after 45 min (FIG.2). This coloration occurred due to the gradual decomposition of cotton upon prolonged heating at elevated temperatures.
  • the conversion increased at short times and then evolved slowly due to the slow depolymerization of the polyester and the cotton swelling by the solvent, which hindered mixing.
  • the conversion kept increasing up to 30 min, whereas at 210°C, complete polyester conversion was achieved in less than 15 min.
  • nylon The dissolution of nylon occurred instantly upon contact with formic acid due to protonation of the carbonyl bonds by formic acid.
  • Formic acid was strong enough to disrupt the hydrogen bonding between the amide groups within nylon chains but weak enough to avoid cotton degradation.
  • the dissolved nylon was simply filtered off from cotton. The cotton was further washed with water and air-dried overnight at 70°C. Nylon was recovered by distilling out the formic acid.
  • the isolated cotton and nylon were characterized by TGA, FTIR, DSC, and XRD. Some formic acid and dyes remained in the isolated cotton. Complete removal of formic acid can be achieved through subsequent washing with methanol and water. The remaining dyes, likely covalently bonded to cotton fibers, proved more challenging to remove.
  • Solvent dissolution and distillation for nylon recovery substantially reduced its crystallinity.
  • the decrease in recovered nylon’s number average molecular weight compared to 100% nylon textile without treatment was likely due to the reaction treatment at elevated temperatures.
  • the mixed textile waste offers the potential for making multiple products (see Table 1).
  • the polyester obtained from the recycling process presents a clear entry point for the yarn making of textiles through melt spinning.
  • MDA a high-value monomer used in various industries, has a market value ranging from $2.5 to $100/kg. MDA can be reintroduced into textile production by chemically transforming it into methylene diphenyl diisocyanate (MDI), followed by polymerization with polyols to create recycled spandex.
  • MDI methylene diphenyl diisocyanate
  • Successful fiber-to-fiber cotton recycling relies on preserving a high DP in cellulose (9000 to 15,000). However, multiple home laundering cycles lead to the aging of cotton fibers. Cutting and shredding the textile waste before chemical degradation results in fiber damage and breakage. All these result in a lower DP value of postconsumer cotton textile waste than virgin cotton.
  • the short cotton fibers produced can be blended with virgin cotton to improve the quality of recycled yarn and reduce the cost of virgin yarn raw materials. They can also be used in composites to make regenerated fibers (e.g., viscose and lyocell) and cellulose nanocrystals or as fermentation feedstock for energy applications.
  • the market values range from $2.2 to $5.0/kg and $0.1/kWh for bioenergy.
  • 2101715-001243 -23- The recovered nylon can be melted and turned back into yarns or used in automotive, food, industrial, and composite applications. Its market value ranges from $2.5 to $50/kg.
  • FIG.9 directly illustrates the potential for transforming mixed textile waste, regardless of its composition, back into textiles or for open-loop recycling.
  • dyes and changes in properties might hinder the use of recovered BHET, MDA, cotton, and nylon in various applications.
  • additional steps may be needed.
  • recycled BHET that is colorized can be decolorized using activated carbon after redissolving in fresh EG at 100°C for 3 hours through subsequent recrystallization in EG, yielding white BHET at ⁇ 99% purity.
  • Adjusting processing conditions during manufacturing can also enhance nylon’s crystallinity by influencing its mechanical properties.
  • Colorized nylon like BHET, can be decolorized using activated carbon after dissolution in formic acid at 100°C for typically longer times due to the potentially higher concentration of dyes.
  • the high solubility and low purity of MDA in EG can complicate its recovery, thus highlighting the possibility of needing to perform additional methods, such as distillation and extraction.
  • Removing EG through vacuum distillation and using solvent-solvent extraction to separate MDA and other diphenyl-containing molecules from dyes is an efficient strategy for improving purity of isolated MDA. Because textile wastes tend to have an unknown material composition, determining the precise conversion and yield of the waste can be challenging.
  • Example 2 Techno-economic Assessment of an Exemplary Chemical Recycling Process for Mixed Textile Wastes 2101715-001243 -24-
  • TAA techno-economic analysis
  • Table 3 Overall Cost Distribution for Low Product Sales Case and High Product Sales Case Total Costs (USD/year) Low Product Sales High Product Sales Capital Cost $6,489,103.22 $6,489,103.22 Operating Cost $92,002,865.47 $92,335,443.10 Raw Material Cost $83,597,167.67 $83,905,109.92 Product Sales $85,339,601.32 $148,663,134.84 2101715-001243 -25-
  • the techno-economic analysis used the profitability index (PI) as a key metric. For cases 1 and 2, PIs of 0.95 and 1.29 were obtained, respectively, with a value of 1 indicating breakeven.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

L'invention concerne des procédés de recyclage de déchets textiles mélangés, ces procédés comprenant la mise en oeuvre d'une glycolyse assistée par micro-ondes sur les déchets textiles mélangés pour produire une solution de dépolymérisation, la glycolyse assistée par micro-ondes se produisant à une température supérieure à 100 °C en présence d'un catalyseur, les déchets textiles mélangés comprenant au moins deux matériaux textiles choisis parmi les polyesters, l'élasthanne, le coton ou le nylon. Des produits créés à partir des déchets textiles mélangés recyclés sont également divulgués.
PCT/US2024/054363 2023-11-02 2024-11-04 Procédés de recyclage chimique de déchets textiles mélangés Pending WO2025097116A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363595513P 2023-11-02 2023-11-02
US63/595,513 2023-11-02

Publications (1)

Publication Number Publication Date
WO2025097116A1 true WO2025097116A1 (fr) 2025-05-08

Family

ID=95581561

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/054363 Pending WO2025097116A1 (fr) 2023-11-02 2024-11-04 Procédés de recyclage chimique de déchets textiles mélangés

Country Status (1)

Country Link
WO (1) WO2025097116A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190218362A1 (en) * 2018-01-12 2019-07-18 Tyton Biosciences, Llc Methods for recycling cotton and polyester fibers from waste textiles
WO2021021031A1 (fr) * 2019-07-30 2021-02-04 Lai Trillion Procédé de séparation et de récupération de polymères et/ou de fibres à partir de matériaux composites solides ou de mélanges liquides
US20210060821A1 (en) * 2018-03-12 2021-03-04 Regeneration Bvba Textile article and method for the production and disassembly of a textile article
WO2023105077A1 (fr) * 2021-12-09 2023-06-15 University College Cork - National University Of Ireland, Cork Procédé de recyclage de déchets plastiques comprenant du pet
WO2023105977A1 (fr) * 2021-12-08 2023-06-15 パナソニックＩｐマネジメント株式会社 Dispositif d'enseignement hors ligne et procédé d'enseignement hors ligne
WO2024256661A1 (fr) * 2023-06-14 2024-12-19 University College Cork - National University Of Ireland, Cork Recyclage des textiles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190218362A1 (en) * 2018-01-12 2019-07-18 Tyton Biosciences, Llc Methods for recycling cotton and polyester fibers from waste textiles
US20210060821A1 (en) * 2018-03-12 2021-03-04 Regeneration Bvba Textile article and method for the production and disassembly of a textile article
WO2021021031A1 (fr) * 2019-07-30 2021-02-04 Lai Trillion Procédé de séparation et de récupération de polymères et/ou de fibres à partir de matériaux composites solides ou de mélanges liquides
WO2023105977A1 (fr) * 2021-12-08 2023-06-15 パナソニックＩｐマネジメント株式会社 Dispositif d'enseignement hors ligne et procédé d'enseignement hors ligne
WO2023105077A1 (fr) * 2021-12-09 2023-06-15 University College Cork - National University Of Ireland, Cork Procédé de recyclage de déchets plastiques comprenant du pet
WO2024256661A1 (fr) * 2023-06-14 2024-12-19 University College Cork - National University Of Ireland, Cork Recyclage des textiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANDINI ERHA, BHALODE POOJA, GANTERT EVAN, SADULA SUNITHA, VLACHOS DIONISIOS G.: "Chemical recycling of mixed textile waste", SCIENCE ADVANCES, vol. 10, no. 27, 5 July 2024 (2024-07-05), US , pages 1 - 12, XP093311947, ISSN: 2375-2548, DOI: 10.1126/sciadv.ado6827 *

Similar Documents

Publication Publication Date Title
US12173123B2 (en) Polyester textile waste recycling
Baloyi et al. Recent advances in recycling technologies for waste textile fabrics: a review
JP7615113B2 (ja) 廃棄物織物から綿およびポリエステル繊維をリサイクルするための方法
TWI841885B (zh) 由聚酯棉織物及/或纖維回收棉的回收方法
US12365780B2 (en) Polyester textile waste recycling
Choudhury et al. Recycling of Blended Fabrics for a Circular Economy of Textiles: Separation of Cotton, Polyester, and Elastane Fibers.
US20210246581A1 (en) Retrieving and repolymerizing textile fibers
US12371546B2 (en) Feedstock purification of polyester waste for recycling processes
KR20240174107A (ko) 실온에서 테레프탈릭 폴리에스테르를 테레프탈레이트 에스테르로 탈중합하는 방법
Nahar et al. A Modified Hydrolysis Method of Decolorizing Reactive‐Dyed Polycotton Waste Fabric and Extraction of Terephthalic Acid: A Perspective to Reduce Textile Solid Waste
Björquist Separation for regeneration-Chemical recycling of cotton and polyester textiles
WO2025097116A1 (fr) Procédés de recyclage chimique de déchets textiles mélangés
WO2024121765A1 (fr) Procédé de traitement d'un fil ou d'un textile comprenant des fibres élastomères en combinaison avec des fibres synthétiques de polyamide et/ou de polyester
WO2024256661A1 (fr) Recyclage des textiles
WO2024026510A1 (fr) Procédés de purification de monomères recyclés, monomères recyclés et utilisations associées
Doifode Chemical Recycling of Elastane and Elastane Blends
CN116829323A (zh) 使纤维素废弃纺织品增值的通用方法
JP2025183512A (ja) ポリエステルの回収方法
JP7708983B2 (ja) ポリエステルの回収方法およびリサイクルポリエステルの製造方法
JP2025183511A (ja) ポリエステル成分の回収方法及びリサイクルポリエステルの製造方法
WO2025253987A1 (fr) Procédé de récupération d'un composant polyester et procédé de production de polyester recyclé à l'aide d'un composant récupéré
WO2025164373A1 (fr) Procédé de récupération de polyester et procédé de fabrication de polymère de polyester recyclé
JP2025184333A (ja) ポリエステルの回収方法
JP2025183508A (ja) ポリエステル成分の回収方法及びリサイクルポリエステルの製造方法
JP2025183509A (ja) ポリエステル成分の回収方法及びリサイクルポリエステルの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24887100

Country of ref document: EP

Kind code of ref document: A1