WO2024251760A1 - Procédé de dépolymérisation hydrolytique d'un polyamide - Google Patents

Procédé de dépolymérisation hydrolytique d'un polyamide Download PDF

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Publication number
WO2024251760A1
WO2024251760A1 PCT/EP2024/065383 EP2024065383W WO2024251760A1 WO 2024251760 A1 WO2024251760 A1 WO 2024251760A1 EP 2024065383 W EP2024065383 W EP 2024065383W WO 2024251760 A1 WO2024251760 A1 WO 2024251760A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
stream
range
chemical
feedstock
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Ceased
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PCT/EP2024/065383
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English (en)
Inventor
Stefan Blei
Faissal-Ali El-Toufaili
Vikram Raghavendhar RAVIKUMAR
Esther Matyka LARYEA
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BASF SE
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BASF SE
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Priority to AU2024285754A priority Critical patent/AU2024285754A1/en
Priority to CN202480037506.1A priority patent/CN121241089A/zh
Priority to EP24731886.8A priority patent/EP4724517A1/fr
Priority to KR1020267000441A priority patent/KR20260018163A/ko
Publication of WO2024251760A1 publication Critical patent/WO2024251760A1/fr
Priority to MX2025014676A priority patent/MX2025014676A/es
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J11/14—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 steam or water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/12—Preparation of lactams by depolymerising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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

  • the present invention relates to a process for hydrolytically depolymerizing polyamide 6 which is contained in a chemical feedstock which, in addition to polyamide 6, contains specific amounts of polyethylene terephthalate and polyamide 6.6. Further, the present invention relates to the use of a mixture comprising polyamide 6 and further contains specific amounts of polyethylene terephthalate and polyamide 6.6 for increasing the yield in e-caprolactam in a hydrolytic polyamide 6 depolymerisation reaction.
  • Polyamide and in particular polyamide 6 being characterized by the formula (-NH-(CH2)5-CO-) n , can be found in numerous materials, such as packaging, engineering plastics from automotive and textile filaments. The latter represents about 40 % of the polyamide 6 global market. At present, only a very small part of the textile filaments is recycled while it represents a significant percentage of the global CO2 emissions. There is thus a need to recycle polyamide 6 from such materials. Processes for alkaline depolymerizing a polyamide exists. Further, the processes in the art are energy-intensive processes. Said materials which are subjected to such recycling processes often contain other polymeric compounds such as polyethylene terephthalate and polyamide 6.6.
  • the process of the present invention wherein polyamide 6 is hydrolytically depolymerized and wherein the feedstock which is subjected to said hydrolytic depolymerization process contains the further polymeric compounds polyethylene terephthalate and polyamide 6.6 in specific amounts relative to polyamide 6 allow for increasing the yield in the valuable product, i.e. e-caprolactam, the monomeric compound resulting from depolymerizing polyamide 6. Yet further, the process of the present invention permits to reduce the overall energy consumption compared to known processes which permits to reduce the CO2 footprint and costs.
  • the present invention relates to a process for hydrolytically depolymerizing polyamide 6 comprised in a chemical feedstock F, the process comprising
  • the mass ratio r s is concerned, 0.02 ⁇ rs 2, more preferably 0.03 ⁇ r s ⁇ 1.9, more preferably 0.04 ⁇ r s ⁇ 1.8, more preferably 0.05 ⁇ r s ⁇ 1.75.
  • 0.05 ⁇ rs 1 preferably 0.05 ⁇ r s ⁇ 0.5, more preferably 0.05 ⁇ rs 0.15. It may be preferred that for the mass ratio rs, 0.04 ⁇ rs 1 , more preferably 0.04 ⁇ r s ⁇ 0.75, more preferably 0.04 ⁇ r s ⁇ 0.5.
  • r T RIPET I RIPA6.6, 0.005 ⁇ r T ⁇ 5. More preferably, 0.01 ⁇ r-r 5, more preferably 0.015 ⁇ r-r 4, more preferably 0.02 ⁇ TT 3.
  • the entire amount of polyamide 6 which is comprised in the mixture to be subjected to polyamide 6 depolymerisation conditions according to (iii) is comprised in the chemical feedstock F provided according to (i).
  • the amount of polyethylene terephthalate which is comprised in the mixture to be subjected to polyamide 6 depolymerisation conditions according to (iii) is comprised in the chemical feedstock F provided according to (i). If only a part of polyethylene terephthalate is comprised in the mixture provided according to (i), it is preferred that after having provided said feedstock, further polyethylene terephthalate is added to said feedstock so that the above-described values and ranges for r s and preferably also for r T are achieved for the feedstock which is finally subjected to (iii).
  • the entire amount of polyethylene terephthalate which is comprised in the mixture to be subjected to polyamide 6 depolymerisation conditions according to (iii) is already comprised in the chemical feedstock F provided according to (i).
  • polyamide 6.6 which is comprised in the mixture to be subjected to polyamide 6 depolymerisation conditions according to (iii) is comprised in the chemical feedstock F provided according to (i). If only a part of polyamide 6.6 is comprised in the mixture provided according to (i), it is preferred that after having provided said feedstock, further polyamide 6.6 is added to said feedstock so that the above-described values and ranges for r s and preferably also for r T are achieved for the feedstock which is finally subjected to (iii). Preferably, the entire amount of polyamide 6.6 which is comprised in the mixture to be subjected to polyamide 6 depolymerisation conditions according to (iii) is already comprised in the chemical feedstock F provided according to (i).
  • the chemical feedstock provided according to (i) and preferably subjected to (iii) it is preferred that at least 50 weight-% of the chemical feedstock F provided according to (i) consist of the polyamide 6, the polyamide 6.6 and the polyethylene terephthalate. More preferably, from 60 to 100 weight-%, more preferably from 70 to 100 weight-%, more preferably from 75 to 100 weight-% of the chemical feedstock F provided according to (i) and preferably subjected to (iii) consist of the polyamide 6, the polyamide 6.6 and the polyethylene terephthalate.
  • At least 25 weight-% of the chemical feedstock F consist of polyamide 6, wherein it may be preferred that at least 30 weight-% or at least 40 weight-% or at least 50 weight-% or at least 60 weight-% or at least 70 weight-% or at least 80 weight-% or at least 90 weight-% of the chemical feedstock F consist of polyamide 6.
  • polyamide 6 depolymerisation conditions it is preferred that they comprise a polyamide 6 depolymerisation temperature T D in the range of from 230 to 330 °C, more preferably in the range of from 250 to 320 °C, more preferably in the range of from 270 to 310, such as in the range of from 270 to 280 °C or in the range of from 280 to 290 °C or in the range of from 290 to 300 °C or in the range of from 300 to 310 °C.
  • the depolymerisation temperature TD is the temperature of the liquid reaction mixture during (iii).
  • polyamide 6 depolymerisation conditions it is preferred that they comprise a polyamide 6 depolymerisation pressure PD in the range of from 40 to 140 bar, more preferably in the range of from 40 to 125 bar, more preferably in the range of from 40 to 110 bar, such as in the range of from 40 to 55 bar or in the range of from 55 to 70 bar or in the range of from 70 to 85 bar or in the range of from 85 to 100 bar or in the range of from 100 to 110 bar.
  • a polyamide 6 depolymerisation pressure PD in the range of from 40 to 140 bar, more preferably in the range of from 40 to 125 bar, more preferably in the range of from 40 to 110 bar, such as in the range of from 40 to 55 bar or in the range of from 55 to 70 bar or in the range of from 70 to 85 bar or in the range of from 85 to 100 bar or in the range of from 100 to 110 bar.
  • the chemical feedstock which is provided according to (i) and preferably subjected to (iii) may further comprise, in addition to polyamide 6, polyethylene terephthalate and polyamide 6.6, one or more other components such as at least one further organic polymeric compound, for example at least one semiaromatic polyamide including one or more of polyamide 6T and polyamide 6I; at least one polyurethane; at least one polyester; at least one polyether; at least one polyvinyl chloride; at least one natural fiber material such as wool and cotton; at least one cellulose material; at least one natural elastomer; at least one synthetic elastomer; at least one copolymer of two or more of said polymeric compounds including statistical copolymers, gradient copolymers, alternating copolymers, block copolymers, and graft copolymers; and at least one rubber material comprising one or more of at least one natural rubber material and at least one synthetic rubber material.
  • at least one further organic polymeric compound for example at least one semiaromatic poly
  • the feedstock provided according to (i) and preferably subjected to (iii) further comprises such further organic polymeric compound
  • this further organic polymeric compound comprises at least one polytetrahydrofuran.
  • the further organic polymeric compound consists of at least one polytetrahydrofuran.
  • the chemical feedstock which is provided according to (i) and preferably subjected to (iii) may further comprise one or more of at least one pigment material and at least one glass fiber material.
  • no polyamide 6 depolymerization catalyst such as a mineral acid, such as one or more of hydrochloric acid, nitric acid, sulphuric acid and phosphoric acid, and/or a zinc salt such as zinc chloride, zinc acetate or zinc triflate is added for preparing the mixture to be subjected to hydrolytic polyamide 6 depolymerisation conditions.
  • a mineral acid such as one or more of hydrochloric acid, nitric acid, sulphuric acid and phosphoric acid
  • a zinc salt such as zinc chloride, zinc acetate or zinc triflate
  • at least one of the chemical materials Mj more preferably every chemical material Mj comprises, preferably consists of a waste material, said waste material preferably comprising, more preferably consisting of, one or more of at least one textile waste material and at least one engineering plastics waste material, more preferably comprising, more preferably consisting of at least one textile waste material.
  • the respective two or more materials may have different chemical compositions which are not subject to any specific restrictions with the proviso that the chemical feedstock exhibits the composition as discussed above.
  • the chemical feedstock F which is provided according to (i), it is preferred that it is provided in solid form, more preferably in the form of particles such as granules, wherein the particle size distribution of said particles is more preferably characterized by one or more of the following pairs of values, more preferably by two or more of the following pairs of values, more preferably by the following three pairs of values: a D10 value of the particle width in the range of from in the range of from 0.3 to 15 mm and a D10 value of the particle length in the range of from 0.3 to 15 mm; a D50 value of the particle width in the range of from in the range of from 0.5 to 20 mm and a D50 value of the particle length in the range of from 0.5 to 20 mm; a D90 value of the particle width in the range of from in the range of from 0.8 to 30 mm and a D90 value of the particle length in the range of from 0.8 to 30 mm.
  • More preferred pairs of values are, for example: a D10 value of the particle width in the range of from in the range of from 2 to 4 mm and a D10 value of the particle length in the range of from 3.5 to 5.5 mm; a D50 value of the particle width in the range of from in the range of from 2.5 to 4.5 mm and a D50 value of the particle length in the range of from 4 to 7 mm; a D90 value of the particle width in the range of from in the range of from 3 to 5 mm and a D90 value of the particle length in the range of from 4.5 to 8.5 mm.
  • particle as used in this context of the present invention comprises optionally pre- formed granules, and also comprises shredded pieces.
  • the chemical feedstock F is admixed according to (iii) in solid form with the liquid aqueous stream S w .
  • providing the chemical feedstock F according to (i) comprises bringing the chemical feedstock F from the solid form to a liquid form, and wherein according to (iii), the chemical feedstock F is admixed in liquid form with the liquid aqueous stream Sw.
  • the process of the present invention may preferably comprise
  • the pre-reaction unit U P R according to (d) comprises, preferably consists of, a mixing unit, preferably a static mixing unit.
  • static mixing unit refers to an arrangement of mixing elements which are installed in a pipe or duct, and which operate essentially without moving parts, preferably entirely without moving parts. According to the present invention, it may be preferred that said mixing unit is configured as a suitable pipe junction of the pipe for the stream SM and the pipe for the stream Sw, wherein no specific mixing elements are present.
  • the melting unit UM comprises a kneader or an extruder, more preferably an extruder, wherein more preferably, the melting unit U M consists of an extruder, wherein more preferably, the extruder is a single-screw extruder or a twin-screw extruder, more preferably a twin-screw extruder.
  • a filtration unit UF is arranged downstream of the melting unit UM and upstream of the reaction unit UR, preferably a filtration unit UF for separating particles having a particle size in the range of from 100 to 500 micrometer, preferably in the range of from 200 to 400 micrometer, from the liquid stream S M , wherein the process comprises passing the stream liquid stream S M through UF, prior to admixing according to (d).
  • the feedstock F and the stream S w are admixed at a mixing ratio (mw/kg) I (mp/kg) in the range of from 1 :1 to 20:1 , preferably in the range of from 2:1 to 15:1 , more preferably in the range of from 5:1 to 10:1 , wherein mw is the amount of water comprised in Sw and m? is the amount of polyamide 6 comprised in the chemical feedstock F.
  • the overall residence time of the reaction mixture subjected to polyamide 6 depolymerization conditions in the chemical reaction unit U R is in the range of from 15 to 800 minutes, preferably in the range of from 30 to 600 minutes, more preferably in the range of from 45 to 360 minutes, more preferably in the range of from 60 to 240 minutes.
  • the term “overall residence time” as used in this context of the present invention refers to the sum of the residence times in all chemical reactors R mentioned above.
  • At least 1 , preferably z reactors R are stirred tank reactors, wherein every stirred tank reactor R may preferably have, independently from each other, from 2 to 6 compartments, preferably from 2 to 5 compartments, more preferably from 2 to 4 compartments, said compartments preferably being serially, more preferably being serially and vertically arranged, wherein 2 adjacent compartments are separated by a divider which comprises at least one flow-through opening.
  • Said at least one compartment comprised in a reactor R may preferably comprise at least one agitator, wherein preferably every compartment of every reactor R comprises at least one agitator, wherein more preferably, every compartment of every reactor R comprises one agitator, wherein the process comprises agitating the depolymerization mixture in a given compartment for at least part of the time during subjecting to depolymerization conditions in said compartment.
  • stirred tank reactor R preferably every stirred tank reactor R, has, independently from each other, preferably from 2 to 6 compartments, more preferably from 2 to 5 compartments, more preferably from 2 to 4 compartments, said compartments preferably being serially, more preferably being serially and vertically arranged, wherein said reactor R comprises at least one agitator and wherein 2 adjacent compartments are formed by, and separated by, one or more suitable components of said agitator such as blades comprised in the agitator, wherein the process comprises agitating the depolymerization mixture in a given compartment for at least part of the time during subjecting to depolymerization conditions in the reactor compartment.
  • the polyamide 6 depolymerization conditions preferably further comprise a total residence time t D of the aqueous depolymerization mixture in the unit UR, preferably in the z reactors R, more preferably in the z stirred tank reactors, wherein at least 85 weight-%, preferably at least 90 weight-%, more preferably at least 95 weight-% of the aqueous depolymerization mixture have a to in the range of from 30 to 90 min. More preferably, for z > 1 , the residence time of an aqueous depolymerization mixture in a reactor R is toi and wherein 0.90 ⁇ (toi I toi+i) 1.10, preferably 0.95 ⁇ (toi I ta+i) 1.05.
  • the water which is comprised in the stream S E leaving UR is suitably recycled as at least a part of Sw. According to this recycling, it is further preferred that the process further comprises
  • (iv) generating an aqueous stream SR comprises subjecting the stream S E obtained from the chemical reaction unit UR, optionally after subjecting S E to filtration, to thermal water separation, obtaining the stream SR;
  • thermo water separation according to (iv) preferably comprises one or more of distilling and falling film evaporating.
  • generating the aqueous stream S R according to (iv) comprises, preferably consists of, distilling the stream S E obtained from the reaction unit UR, optionally after subjecting S E to filtration, obtaining the stream SR.
  • Said distilling is preferably carried out in a distillation column at a bottoms temperature preferably in the range of from 70 to 140 °C, more preferably in the range of from 80 to 120 °C, more preferably in the range of from 90 to 110 °C, and a top pressure preferably in the range of from 0.5 to 1.5 bar, more preferably in the range of from 0.7 to 1.2 bar, more preferably in the range of from 0.8 to 1.1 bar, wherein the stream S R is obtained at the top of the distillation column.
  • said distilling preferably comprises subjecting the vapor top stream to condensation, obtaining a liquid stream S R , wherein at least a part of the liquid stream S R is fed back to the chemical reaction unit UR as part of the aqueous stream Sw according to (v).
  • Said liquid stream SR obtained from condensation may preferably be divided into 2 streams, wherein a first stream obtained from dividing is fed back to the chemical reaction unit U R as part of the aqueous stream Sw according to (v) and a second stream is fed back to the top of the distillation column, wherein the volume ratio of the first stream relative to the second stream is preferably in the range of from 10:1 to 0.5:1 , more preferably in the range of from 7:1 to 1 :1 , more preferably in the range of from 5:1 to 2:1.
  • the aqueous stream S R is generated in the course of subjecting the stream S E to one or more stages downstream of UR according to which a stream SCPL is prepared comprising purified e-caprolactam which may then be suitably recycled to the material value chain, such as a starting material for preparing polyamide 6.
  • Said one or more downstream purification stages which may further comprise one or more stages according to which heat contained in the stream S E is suitably recovered and, for example, used for at least partially meeting the heat demand of one or more of said downstream purification stages, may comprise, for example, the following sequence of stages:
  • the recycling according to (C) may preferably comprise (C.1) feeding the at least one stream Svw and the at least one stream SRW into a water treatment unit Uw, obtaining from Uw at least one aqueous recycle stream SR;
  • the water treatment unit U w according to (C.1) may preferably comprise a water recovery unit UWR and a waste water unit Uww, wherein (x.1) further comprises
  • the purification unit U P according to (B) may preferably comprise one or more of a heatconsuming water separation unit Uws, a heat-consuming distillation unit UD and a heat-consuming crystallization unit Uc, preferably two or more of a heat-consuming water separation unit Uws, a heat-consuming distillation unit U D and a heat-consuming crystallization unit Uc, more preferably a heat-consuming water separation unit Uws, a heat-consuming distillation unit U D and a heatconsuming crystallization unit U c , wherein at least part of the heat consumed in one or more of Uws, UD and Uc is provided by at least one of the one or more streams Sv.
  • the process may comprise one or more of the following; more preferably at least two or more of the following; more preferably all of the following: obtaining at least one at least partially condensed aqueous stream Svwi from Uws; obtaining at least one at least partially condensed aqueous stream Svw2 from UD; obtaining at least one at least partially condensed aqueous stream Svws from Uc; the process further comprising feeding one or more Svwi, Svw2 and Svws; preferably two or more
  • At least one of the streams SRW is obtained from Uws.
  • the purification unit UP may comprise a heat-consuming water separation unit Uws, a heat-consuming distillation unit U D and a heat-consuming crystallization unit Uc, the process comprising feeding the stream S L comprising e-caprolactam at a concentration CSL to Uws, obtaining from Uws a stream Uws comprising e-caprolactam at a concentration Cuws, feeding the stream Suws to the distillation unit U D, obtaining from UD a stream SUD comprising e-caprolactam at a concentration CUD, and feeding the stream SUD into the crystallization unit Uc, and obtaining from Uc a stream SCPL comprising e-caprolactam at a concentration CSCPL, wherein CSL ⁇ Cuws ⁇ CUD ⁇ CSCPL-
  • the water separation unit Uws may comprise at least two heat-consuming water separation sub-units U W si and Uws2, preferably two serially coupled heat-consuming water separation sub-units Uwsi and Uws2, wherein the stream SL is fed into Uwsi and wherein at least part of the heat consumed in one or more of U W si and Uws2 is provided by at least one of the one or more streams S v .
  • the process may comprise one or more of the following, more preferably all of the following: obtaining at least one at least partially condensed aqueous stream Svwn from Uwsi; obtaining at least one at least partially condensed aqueous stream Svwi2 from Uws2.
  • At least one aqueous stream S RWi is obtained from Uwsi and at least one aqueous stream S RW2 is obtained from Uws2, and wherein at least one of S R wi and S R w2, preferably S R wi and S R W2 are fed into Uw.
  • the evaporation unit UE may comprise two or more evaporation sub-units, the process comprising obtaining at least two vapor streams Svi and Sv2, passing the vapor stream Svi to at least one heat-consuming unit and passing the vapor stream Sv2 to at least one heat-consuming unit, wherein the vapor streams Svi and Sv2 differ from each other in either pressure and/or temperature.
  • stream SCPL i.e. the purified s-caprolactam stream
  • said stream S C PL is passed to a polyamide 6 production unit UPP where it is employed as starting material.
  • one or more further streams SNCPL can be additionally passed to U PP, said streams comprising non-recycled s-caprolactam, i.e. s-caprolactam from a conventional source.
  • the respectively prepared polyamide 6 material preferably may then be passed to a unit U T p where it is used as a starting material for preparing a material comprising polyamide 6, preferably a textile material comprising polyamide 6.
  • one or more further streams S N PA6 can be additionally passed to UTP, said streams comprising non-recycled polyamide 6, i.e. polyamide 6 from a conventional source.
  • further streams comprising one or more starting materials other than polyamide 6 can be passed to UTP.
  • the material, preferably the textile material MT obtained from UTP then preferably goes into the market and remains there for a given lifetime TMT.
  • the respective end-of-life material is suitably collected in a collecting unit U T c, preferably a textile material collecting unit, from which it is suitably passed as the feedstock F or part of the feedstock F to the process as described above, optionally after sorting as described herein.
  • the process of the present invention as described above may preferably be a continuous process. However, one or more process steps may be carried out in a batch-type mode, and one or more steps may be carried out in a semicontinuous mode.
  • the yield in e-caprolactam is in particular increased compared to
  • the present invention also relates to a method of increasing the yield in e-caprolactam in a hydrolytic polyamide 6 depolymerisation reaction, said reaction comprising
  • the yield in e-caprolactam is in particular increased compared to
  • Providing the chemical feedstock, and the materials Mj, respectively, may comprise an upstream sorting stage.
  • the sorting preferably comprises an infrared sorting, more preferably a near-infrared sorting and/or a mid-infrared sorting.
  • the waste material can be subjected to a suitable metal removing step. If a metal removing step is carried out, ferrous elements are preferably separated, for example by suitable magnetic means, and/or non-ferrous elements are preferably separated, for example by suitable eddy current separating means. After said sorting, the respectively obtained waste material can be subjected to a further treatment, such as cutting and/or milling.
  • polyamide 6 depolymerisation conditions according to (iii) comprise a polyamide 6 depolymerisation temperature T D in the range of from 230 to 330 °C, preferably in the range of from 250 to 320 °C, more preferably in the range of from 270 to 310.
  • polyamide 6 depolymerisation conditions according to (iii) comprise a polyamide 6 depolymerisation pressure PD in the range of from 40 to 140 bar, preferably in the range of from 40 to 125 bar, more preferably in the range of from 40 to 110 bar.
  • the chemical feedstock F provided according to (i) is in solid form, preferably in the form of particles, wherein the particle size distribution of said particles is preferably characterized by one or more of the following pairs of values, more preferably by two or more of the following pairs of values, more preferably by the following three pairs of values: a D10 value of the particle width in the range of from in the range of from 0.3 to 15 mm and a D10 value of the particle length in the range of from 0.3 to 15 mm; a D50 value of the particle width in the range of from in the range of from 0.5 to 20 mm and a D50 value of the particle length in the range of from 0.5 to 20 mm; a D90 value of the particle width in the range of from in the range of from 0.8 to 30 mm and a D90 value of the particle length in the range of from 0.8 to 30 mm.
  • z is in the range of from 1 to 10, preferably in the range of from 1 to 8, more preferably in the range of from 1 to 6, more preferably in the range of from 1 to 5, more preferably in the range of from 1 to 4, more preferably in the range of from 1 to 3.
  • every chemical material Mj comprises, preferably consists of a waste material, said waste material preferably comprising, more preferably consisting of, one or more of at least one textile waste material and at least one engineering plastics waste material, more preferably comprising, more preferably consisting of at least one textile waste material.
  • (iv) generating an aqueous stream S R comprises subjecting the stream SE obtained from the chemical reaction unit U R , optionally after subjecting SE to filtration, to thermal water separation, obtaining the stream S R ;
  • thermo water separation according to (iv) preferably comprises one or more of distilling and falling film evaporating.
  • distilling comprises subjecting the vapor top stream to condensation, obtaining a liquid stream S R , wherein at least a part of the liquid stream SR is fed back to the chemical reaction unit U R as part of the aqueous stream Sw according to (v).
  • polymer, or the polymer product, or the polymer and the polymer product is or are in the form of at least one of a granulate, a strand, a rod, a plate, a pipe, a foil, a layer, a film, a sheet, a fiber, a filament, a coating, an extruded article, a molded article, a soft foam, a half-rigid foam and a rigid foam.
  • a method of increasing the yield in e-caprolactam in a hydrolytic polyamide 6 depolymerisation reaction comprising
  • the respective amounts are preferably determined based on identity preservation and/or segregation and/or mass balance and/or book and claim chain of custody models, more preferably based on mass balance, more preferably the International Sustainability and Carbon Certification (ISCC) standard.
  • ISCC International Sustainability and Carbon Certification
  • preparing the polymer, the polymer product, or the polymer and the polymer product may comprise one or more synthesis steps and can be performed by conventional synthesis and technics well known to the person skilled in the art. Examples of the synthesis steps are described in “Industrial Organic Chemistry”, 3 rd volume, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; complicatKunststoffhandbuch”, 11 volumes in 17 subvolumes, Carl Hanser Verlag, especially volume 6, degreePolyamide”, 1 st edition, 1966; “Injection Molding Reference Guide, 4 th edition, CreateSpace Independent Publishing Platform, 2011 , ISBN: 978-1466407824; WO 2008/155271 A1 and WO 2013/139827 A1 , each of which is incorporated herein by reference.
  • X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10 °C, 20 °C, and 30 °C.
  • X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D.
  • textile material covers textile raw materials and non-textile raw materials that are processed by various methods into linear, planar and spatial structures. It concerns the linear textile structures produced from them, such as yarns, twisted yarns and ropes, the sheet-like textile structures, such as woven fabrics, knitted fabrics, braids, stitch- bonded fabrics, nonwovens and felts, and the three-dimensional textile structures, i.e. body structures, such as textile hoses, stockings or textile semi-finished products; and it further concerns those finished products which, using the aforementioned products, are brought into a saleable condition by making up, opening up and/or other operations for onward transmission to the processor, the trade or the end consumer.
  • textile waste material covers a textile material as defined above, the inherent value of which has been consumed from the perspective of its current holder and, thus, is an end-of-life material for said holder.
  • engineering plastics refers to high-performance plastics grades which possess physical properties enabling them to perform for prolonged use in structural applications, over a wide temperature range, under mechanical stress, and in difficult chemical and physical environments used for example to fabricate plastic parts replacing traditional engineering materials like metals and ceramics.
  • Engineering plastics specifically apply in the fabrication of mechanical parts across several industries such as automotive, medical, electrical and electronics, aerospace, construction and consumer products.
  • engineering plastics waste material covers an engineering plastics material as defined above, the inherent value of which has been consumed from the perspective of its current holder and, thus, is an end-of-life material for said holder.
  • feedstocks F were prepared consisting of polyamide 6 (PA6), polyamide 6.6 (PA6.6), and polyethylene terephthalate (PET). These feedstocks were then subjected to hydrolytic depolymerization in an autoclave wherein the depolymerization mixture consisted of the respective feedstock and water, wherein the mass ratio of feedstock relative to water, mF : IT)H2O, was 1 :10. After the mixture was fed into the autoclave, the autoclave was sealed and heated to the respective temperature TD as indicated in Tables 1 , 2 and 3 below, which temperature T D was then maintained for Ato as indicated in said Tables.
  • PA6 polyamide 6
  • PA6.6 polyamide 6.6
  • PET polyethylene terephthalate
  • Heating to said temperature was carried out at a heating ramp of 30 to 70 K/h.
  • the obtained reaction mixture was cooled in the autoclave at a cooling ramp of 10 to 100 K/h.
  • the respectively obtained reaction mixtures were then removed from the autoclave, and probes were sampled and subjected to GC analysis which lead to the results (yields) shown in Tables 1 , 2, and 3.
  • Example 2 Inventive and comparative examples
  • the parameter T D was varied based on the advantageous feedstock F according to #2. Surprisingly, it was found that in terms of the yield in the valuable product E- caprolactam monomer, a temperature range exists for which said yield shows superior values.
  • samples were prepared in deionized water at concentration of approx. 200 mg/mL. Analysis was performed on a standard GC instrument equipped with a split/splitless injector and an FID. The injection volume was 1 pL (microL) at a split ratio of 15:1 . The injector temperature was 250 °C. The instrument was operated in constant pressure mode at 14.5 psi ( ⁇ 1 bar), and nitrogen was used as carrier gas. Separation was performed on a Wax 52 CB column, 50 m x 0.32 mm, 1 .2 pm from Agilent Technologies.
  • the temperature program started with a ramp from 80 °C to 185 °C at a heating rate of 7 °C/min, and a hold time at 185 °C for 30 min.
  • a second ramp was from 185 °C to 200 °C at a heating rate of 7 °C/min, and a hold time at 200 °C for 5 min.
  • the detector (Flame Ionization Detector, FID) temperature was 250 °C. Evaluation of purity values 0 G c was based on area-% distribution, corrected by the content of water determined by Carl Fisher Method.

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

Abstract

Un procédé de dépolymérisation hydrolytique de polyamide compris dans une charge chimique F, le procédé comprenant la fourniture de la charge chimique F, la fourniture d'un flux aqueux liquide Sw, la préparation d'un mélange comprenant la charge F et le flux aqueux liquide Sw et la soumission dudit mélange à des conditions de dépolymérisation de polyamide 6 dans une unité de réaction chimique UR, l'obtention d'un flux aqueux SE laissant UR, le flux SE comprenant ε-caprolactame, le mélange à soumettre à des conditions de dépolymérisation de polyamide 6 comprenant le polyamide 6 et comprenant en outre du polyéthylène téréphtalate et du polyamide 6,6 à un rapport massique rs = (mP A6,6 + mPET)/mPA6 avec 0,01 ≤ r s ≤ 2,5.
PCT/EP2024/065383 2023-06-06 2024-06-05 Procédé de dépolymérisation hydrolytique d'un polyamide Ceased WO2024251760A1 (fr)

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AU2024285754A AU2024285754A1 (en) 2023-06-06 2024-06-05 Process for hydrolytically depolymerizing a polyamide
CN202480037506.1A CN121241089A (zh) 2023-06-06 2024-06-05 用于水解解聚聚酰胺的方法
EP24731886.8A EP4724517A1 (fr) 2023-06-06 2024-06-05 Procédé de dépolymérisation hydrolytique d'un polyamide
KR1020267000441A KR20260018163A (ko) 2023-06-06 2024-06-05 폴리아미드를 가수분해적으로 해중합하는 방법
MX2025014676A MX2025014676A (es) 2023-06-06 2025-12-05 Proceso para la despolimerizacion hidrolitica de una poliamida

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330719A (ja) * 1994-06-01 1995-12-19 Toray Ind Inc ε−カプロラクタムの精製法
JPH07330720A (ja) * 1994-06-01 1995-12-19 Toray Ind Inc ε−カプロラクタムの精製法
JPH08217746A (ja) * 1995-02-09 1996-08-27 Toray Ind Inc ε−カプロラクタムの精製法
WO2008155271A1 (fr) 2007-06-20 2008-12-24 Basf Se Procédé de production de polyamides dans des extrudeuses
WO2013139827A1 (fr) 2012-03-21 2013-09-26 Basf Se Polyamides ignifuges de couleur claire

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330719A (ja) * 1994-06-01 1995-12-19 Toray Ind Inc ε−カプロラクタムの精製法
JPH07330720A (ja) * 1994-06-01 1995-12-19 Toray Ind Inc ε−カプロラクタムの精製法
JPH08217746A (ja) * 1995-02-09 1996-08-27 Toray Ind Inc ε−カプロラクタムの精製法
WO2008155271A1 (fr) 2007-06-20 2008-12-24 Basf Se Procédé de production de polyamides dans des extrudeuses
WO2013139827A1 (fr) 2012-03-21 2013-09-26 Basf Se Polyamides ignifuges de couleur claire

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Industrial Organic Chemistry", 1997, WILEY-VCH
"Injection Molding Reference Guide", 2011, CREATESPACE INDEPENDENT PUBLISHING PLATFORM
"Kunststoffhandbuch", vol. 6, 1966, CARL HANSER VERLAG, article "Polyamide"

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KR20260018163A (ko) 2026-02-06
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CN121241089A (zh) 2025-12-30
AU2024285754A1 (en) 2025-12-18
TW202506640A (zh) 2025-02-16

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