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WO2025015059A1 - Procédé en aval pour séparer un mélange de produits de polyester dépolymérisés produits à partir de méthanolyse - Google Patents

Procédé en aval pour séparer un mélange de produits de polyester dépolymérisés produits à partir de méthanolyse Download PDF

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Publication number
WO2025015059A1
WO2025015059A1 PCT/US2024/037401 US2024037401W WO2025015059A1 WO 2025015059 A1 WO2025015059 A1 WO 2025015059A1 US 2024037401 W US2024037401 W US 2024037401W WO 2025015059 A1 WO2025015059 A1 WO 2025015059A1
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WO
WIPO (PCT)
Prior art keywords
monomer
isolated
mixture
products
methanolysis reaction
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/US2024/037401
Other languages
English (en)
Inventor
Yuanzhe LIANG
Jason Scott DESVEAUX
Hoon Choi
Katrina Marie Knauer
Gregg Tyler BECKHAM
Alan Jon Jacobsen
Ofei MANTE
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.)
Alliance for Sustainable Energy LLC
Amazon com Services LLC
Original Assignee
Alliance for Sustainable Energy LLC
Amazon com Services LLC
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 Alliance for Sustainable Energy LLC, Amazon com Services LLC filed Critical Alliance for Sustainable Energy LLC
Publication of WO2025015059A1 publication Critical patent/WO2025015059A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
    • C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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
    • 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

Definitions

  • Feedstock heterogeneity is the most significant challenge in recycling real-world plastic wastes.
  • Technologies for depolymerizing the most prominent polyester, PET are known and currently being scaled to handle currently unrecyclable forms of the polymer.
  • three key technical hurdles have limited widespread commercial success: (1) lack of technologies for handling increasingly heterogeneous polyester waste streams, (2) resilience to various contaminations in deconstruction and separation processes, (3) precise separation and recovery of high-purity individual products from mixed feedstocks. Therefore, developing robust and scalable technologies for high-purity product recovery from a mixture of deconstructed monomers is critical to the future of plastic recycling.
  • the methods disclosed herein are useful to overcome the existing technical hurdles by designing a downstream separation process that can remove contaminants and recover individual monomers from depolymerized mixed polyesters with high purity. Meanwhile, methods disclosed herein also fill the gap between deconstruction and redesign by enabling direct reuse of recovered monomers for making new polymers and/or other valuable products. With the developed downstream process, the processing cost, GHG emissions, and energy footprints for the plastic upcycling process can be much lower than the conventional manufacturing or separation approaches. As mentioned, the post depolymerization separation process can be challenging as the feedstock compositions are complex and varied. This invented process can be applicable to the wide range of the depolymerized product compositions and from various types of polyesters.
  • a method for isolating a monomer product from a mixture of polyester polymers comprising the steps of a methanolysis reaction of the mixture of polyester polymers, a solid-liquid separation of the resulting mixture of monomer products from the methanolysis reaction, purifying the mixture of monomer products, and isolating a monomer product from the mixture of monomer products.
  • the solid-liquid separation comprises microfdtration to remove large solid contaminants from the methanolysis reaction.
  • the microfdtration takes place at a temperature above room temperature.
  • the separated monomer products from the methanolysis reaction are further purified using activated carbon.
  • the separated monomer products from the methanolysis reaction are further purified using column chromatography comprising an ion exchange resin.
  • the monomer is isolated through meltcrystallization.
  • the isolated monomer is further purified using activated carbon.
  • the isolated monomer is further purified using column chromatography comprising an ion exchange resin.
  • the method further comprises distilling the methanolysis reaction solvent to isolate constituent solvents from one another.
  • the isolated solvents can be reused in the methanolysis reaction.
  • the monomers comprise MLA, DMT, dimethyl adipate (DMA), and dimethyl succinate (DMS).
  • the mixture of polyester polymers comprises polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polyethylene terephthalate (PET) and polybutylene succinate (PBS).
  • the methanolysis reaction comprises methanol, a catalyst, 1-4-butanediol (BDO), and ethylene glycol (EG).
  • BDO is isolated from EG.
  • the BDO is isolated from EG through a step comprising distillation, melt crystallization, liquid chromatography or solvent extraction methods.
  • the MLA is the isolated monomer product.
  • the DMT is the isolated monomer product.
  • the DMA is the isolated monomer product.
  • the DMS is the isolated monomer product.
  • the monomer product is isolated from the mixture of monomer products through distillation means.
  • FIG. 1 depicts a scheme for overview of the downstream process flow diagram
  • PVA Polylactic acid
  • PBAT Polybutylene adipate terephthalate
  • PET Polyethylene terephthalate
  • PBS Polybutylene succinate
  • MLA methyl lactate
  • DMT dimethyl terephthalate
  • DMA dimethyl adipate
  • DMS dimethyl succinate
  • BDO 1,4-butanediol
  • EG ethylene glycol
  • FIG. 2 depicts embodiments of chromatographic methods disclosed herein.
  • FIG. 2A depicts batch column separation of EG and BDO.
  • FIG. 2B depicts SMB zone configuration (2-2-
  • FIG. 2C depicts column profile reached at a steady state.
  • FIG. 2D depicts extract effluent histories.
  • FIG. 2E depicts raffinate effluent histories.
  • Column size i.d. 1.5 cm, Lc 60 cm
  • particle size 500 micron
  • diffusivity coefficient 0.005 cm2/min
  • port switching time 15.29 min
  • feed 50 mL/min
  • extract 73.0 mL/min extract 73.0 mL/min
  • FIG. 3 depicts downstream methods for contamination removal and monomer reclamation.
  • FIG. 3 A depicts simplified process flow diagram for ACM of PET, PLA, PBAT, and PBS delineated by process area.
  • FIG. 3B depicts normalized monomer yields through the downstream separation process for a 50:23:23:4 PET:PLA:PBAT:PBS feedstock.
  • FIG. 3C depicts dye and metals removal via activated carbon treatment of post-crystallization soluble monomer fractions. Metal concentrations in the liquid samples were determined via inductively couple plasma-mass spectrometry (ICP-MS).
  • FIG. 3D depicts separation efficiency of diesters from diols via single-solvent liquid liquid extraction (LLE) with heptane.
  • LLE liquid liquid liquid extraction
  • the monomer mixture contains BDO, EG, DMA, and DMS in a volume ratio of 1 : 1 : 1 : 1.
  • One-step LLE involved mixing the monomer mixture with the solvent once, followed by phase separation. The two-step LLE started with mixing half the total volume of solvent with the monomer mixture, separating the upper phase, then mixing the remaining solvent with the aqueous phase, and finally separating the phases again.
  • Methods, processes and systems disclosed herein are useful to separate and recover high-purity individual monomers from a mixture of deconstructed products from a catalyzed methanolysis depolymerization process of mixed polyester wastes.
  • a mixture of waste polyesters including PET, PBAT, PLA, PBS and others, can be depolymerized together via methanolysis to produce mixed products, e.g., DMT, MLA, DMA, DMS, BDO, EG.
  • the depolymerization can also be done sequentially in a way afforded by the thermophysical properties of the polymers (e g., a difference in melting points) or by way of difference in their thermodynamic behavior (e.g., difference in rates of reaction of polymers).
  • the deconstructed products first undergo a solid-liquid separation step (e.g., filtered with microfiltration to remove large solid contaminants) at elevated temperature, and are then purified with activated carbon and/or an ion exchange resin to remove residual colorants, metals, and other contaminants from the product stream.
  • a solid-liquid separation step e.g., filtered with microfiltration to remove large solid contaminants
  • an ion exchange resin to remove residual colorants, metals, and other contaminants from the product stream.
  • DMT is crystallized from the solution and recovered as a solid when the feedstock cools down. Further purification of DMT can be performed via melt-recrystallization and optional treatment with activated carbon and/or ion exchange resin.
  • the leftover solution i.e., the mother liquor
  • the resultant distillate is then further distilled to recover the methanol and purify the MLA.
  • the leftover products are collected from the bottom stream of the distillation and separated by a solvent extraction process.
  • DMA and DMS are effectively separated from BDO and EG via liquid-liquid phase separation by adding at least one organic solvent and/or water.
  • DMA and DMS form an organic phase and can be separated from each other via distillation.
  • the organic solvent can be recovered in the distillation process and then reused for liquid-liquid extraction.
  • BDO and EG form a separate phase and can be further separated via distillation, melt crystallization, liquid chromatography (any adsorption and SMB, and CCC approaches), or solvent extraction method (counter-current extraction). Recovery of water if being used in the liquid-liquid extraction step can be conducted via reverse osmosis, pervaporation or distillation.
  • FIG. 1A shows an HPLC column experimental result separating EG and BDO in the cation exchange column (Biorad 87H with 0.01M sulfuric acid mobile phase.
  • the retention time of EG and BDO peaks was at 15.9 and 21.1min, respectively, regardless of concentrations up to 500 g/L. This result indicates that the EG and BDO have a linear isotherm in this system.
  • FIGS 2C-2E depicts an example of SMB process at pilot scale operation.
  • 250 g/L of each EG and BDO in water was separated under 0.0 IM sulfuric acid continuously.
  • the process reached at a steady state after 1000 min.
  • EG and BDO were separately eluted out to raffinate and extract ports, respectively, with >99% yield and >99% purity.
  • Figure 3 shows the results for the downstream for contamination removal and monomer reclamation combining results from the process modeling and the experimental work.
  • Embodiments of methods disclosed herein contemplate a continuous process operating on real-life, complex substrates.
  • embodiments disclosed herein use a hot filtration to keep the DMT solubilized and remove solid contaminants.
  • processes disclosed herein also undergo further purification of monomers (e.g., activated carbon treatment).
  • Diols are notoriously difficult to separate from each other and from water mixtures due to prominent hydrogen bonding of the molecules.
  • processes disclosed herein are able to produce a mixture of diols in the absence of water which is an improvement over existing processes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des procédés et des compositions utilisés pour séparer et récupérer des monomères individuels de haute pureté à partir d'un mélange de produits décomposés à partir d'un procédé de dépolymérisation par méthanolyse catalysé de déchets de polyester mélangés.
PCT/US2024/037401 2023-07-10 2024-07-10 Procédé en aval pour séparer un mélange de produits de polyester dépolymérisés produits à partir de méthanolyse Pending WO2025015059A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363512804P 2023-07-10 2023-07-10
US63/512,804 2023-07-10

Publications (1)

Publication Number Publication Date
WO2025015059A1 true WO2025015059A1 (fr) 2025-01-16

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010587A1 (fr) * 2014-07-18 2016-01-21 Sabic Global Technologies B.V. Purification de monomère à partir de polyesters recyclés
US20190256669A1 (en) * 2016-09-09 2019-08-22 Ester Industries Ltd. Modified polyester masterbatch for textile applications and manufacturing process thereof
US20210261748A1 (en) * 2017-02-20 2021-08-26 Ikea Supply Ag Polyester textile waste recycling
CN115436505A (zh) * 2022-08-09 2022-12-06 华测检测认证集团股份有限公司 一种聚酯类生物降解材料的定量测试方法
WO2023059579A1 (fr) * 2021-10-06 2023-04-13 Eastman Chemical Company Production de matières premières de pet et de copolyester de qualité vierge à partir de fibres de tapis de polyester

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010587A1 (fr) * 2014-07-18 2016-01-21 Sabic Global Technologies B.V. Purification de monomère à partir de polyesters recyclés
US20190256669A1 (en) * 2016-09-09 2019-08-22 Ester Industries Ltd. Modified polyester masterbatch for textile applications and manufacturing process thereof
US20210261748A1 (en) * 2017-02-20 2021-08-26 Ikea Supply Ag Polyester textile waste recycling
WO2023059579A1 (fr) * 2021-10-06 2023-04-13 Eastman Chemical Company Production de matières premières de pet et de copolyester de qualité vierge à partir de fibres de tapis de polyester
CN115436505A (zh) * 2022-08-09 2022-12-06 华测检测认证集团股份有限公司 一种聚酯类生物降解材料的定量测试方法

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