WO2024251759A1 - Procédé de dépolymérisation hydrolytique d'un polyamide - Google Patents

Procédé de dépolymérisation hydrolytique d'un polyamide Download PDF

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Publication number
WO2024251759A1
WO2024251759A1 PCT/EP2024/065382 EP2024065382W WO2024251759A1 WO 2024251759 A1 WO2024251759 A1 WO 2024251759A1 EP 2024065382 W EP2024065382 W EP 2024065382W WO 2024251759 A1 WO2024251759 A1 WO 2024251759A1
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WO
WIPO (PCT)
Prior art keywords
stream
polyamide
range
feedstock
aqueous
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Ceased
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PCT/EP2024/065382
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English (en)
Inventor
Stefan Blei
Faissal-Ali El-Toufaili
Vikram Raghavendhar RAVIKUMAR
Jochen Gauer
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BASF SE
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BASF SE
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Priority to CN202480037501.9A priority Critical patent/CN121285543A/zh
Priority to KR1020267000445A priority patent/KR20260018164A/ko
Priority to EP24731885.0A priority patent/EP4724422A1/fr
Priority to AU2024284238A priority patent/AU2024284238A1/en
Publication of WO2024251759A1 publication Critical patent/WO2024251759A1/fr
Priority to MX2025014673A priority patent/MX2025014673A/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—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

  • 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
  • the stream SE preferably further comprises one or more of e-caprolactam dimer and aminocaproic acid.
  • the at least one further organic polymeric compound which is comprised in the feedstock F according to (i) preferably comprises one or more of at least one polyamide 6.6; at least one semiaromatic polyamide including one or more of polyamide 6T and polyamide 61; at least one polyethylene terephthalate; 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.
  • the present invention relates to a process for hydrolytically depolymerizing polyamide 6, the process comprising
  • the at least one further organic polymeric compound according to (i) preferably comprises one or more of at least one polyamide 6.6; at least one semiaromatic polyamide including one or more of polyamide 6T and polyamide 61; at least one polyethylene terephthalate; 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.
  • the feedstock F according to (i) may further comprise other chemical compounds.
  • These compounds may comprise, for example, one or more of at least one pigment material and at least one glass fiber material.
  • pigment materials may comprise organic or inorganic pigments such as TiO 2 .
  • an aqueous stream SR comprising at least part of the water and at least part of at least one of the one or more decomposition products obtained according to (iii) is generated which stream S is then recycled according to (v).
  • the stream SR more preferably the at least one of the one or more decomposition products which are comprised in the stream SR, comprises one or more of at least one amine, at least one ketone, at least one ether, at least one amide, and at least one alcohol, wherein the at least one amine preferably comprises one or more of at least one aliphatic amine and at least one aromatic amine, the at least one ketone preferably comprises at least one aliphatic ketone, the at least one ether preferably comprises at least one aliphatic ether, the at least one amide preferably comprises at least one aliphatic amide, and the at least one alcohol preferably comprises at least one aliphatic alcohol.
  • the stream SR more preferably the at least one of the one or more decomposition products which are comprised in the stream SR, comprises one or more of aniline, 4-aminotoluene, 2,2-dimethoxy-3-methyl butane, 3,3-dimethoxypentane, dimethylacetamide, tripropylamine, 2-octanol, 2,2-dimethoxybutane, and cyclopentanone, wherein aniline is preferably comprised in the stream SR, preferably in the at least one of the one or more decomposition products which are comprised in the stream SR.
  • the stream SR comprises e-caprolactam and preferably one or more of N-ethylcaprolactam and 3-(2-oxazepan-1-yl)propanal.
  • the at least one further organic polymeric compound comprised in the feedstock F preferably comprises at least one polyurethane
  • the stream SE comprises one or more decomposition products of one or more of said at least one polyurethane
  • the stream SR comprises at least part of at least one of said one or more decomposition products.
  • one or more of the at least one polyurethane comprised in the feedstock F are prepared from at least one aniline-based isocyanate, wherein the one or more decomposition products comprised in SR comprise aniline.
  • 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 F exhibits the composition as discussed above.
  • Preferred ranges of the weight ratio of polyamide 6 relative to the at least one further organic polymeric compound are from 1 :1 to 10:1 or from 1.2:1 to 8:1 or from 1.4:1 to 6:1 or from 1.6:1 to 4:1 of from 1.8:1 to 3:1.
  • the chemical feedstock F which is provided according to (i)
  • the particle size distribution of said particles is 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 Sw. According to this alternative, it may be preferred that process wherein (i) further comprises
  • the polyamide 6 depolymerization conditions preferably further comprise a total residence time to of the aqueous depolymerization mixture in the unit U R, 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 to and wherein 0.90 ⁇ (toi / toi+i) 1.10, preferably 0.95 ⁇ (toi / toi+i) 1.05.
  • (C) recycling, as the stream SR, at least one stream Svw at least partially and at least one stream SRW at least partially to the reaction unit UR.
  • the recycling according to (C) may preferably comprise
  • the water treatment unit Uw according to (C.1) may preferably comprise a water recovery unit U R and a waste water unit Uww, wherein (x.1) further comprises
  • the purification unit UP 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 UD and a heat-consuming crystallization unit Uc, more preferably a heat-consuming water separation unit Uws, a heat-consuming distillation unit UD and a heatconsuming crystallization unit Uc, 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 UD and a heat-consuming crystallization unit Uc, the process comprising feeding the stream SL 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 UD, 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 Uwsi 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 Uwsi and Uws2 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 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.
  • 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.
  • the present invention also relates to the use of an aqueous stream SR or a part thereof, obtained by a process comprising
  • the present invention also relates to a method for increasing the £-caprolactam yield of a polyamide 6 depolymerization reaction, the method comprising
  • Providing the chemical feedstock, and the materials Mj, respectively, may comprise an upstream sorting stage.
  • the respectively spread waste material is subjected to sorting, either by composition and/or by color.
  • Sorting can be carried out either manually and/or optically. If carried out optically, 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.
  • 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.
  • the respectively obtained waste material can be subjected to a further treatment, such as cutting and/or milling.
  • stream SE further comprises one or more of E- caprolactam dimer and aminocaproic acid.
  • the at least one further organic polymeric compound comprised in the feedstock F comprises one or more of at least one polyamide 6.6; at least one semiaromatic polyamide including one or more of polyamide 6T and polyamide 6I; at least one polyethylene terephthalate; 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.
  • feedstock F comprises, in addition to the polyamide 6 and the at least one further organic polymeric compound, one or more of at least one pigment material and at least one glass fiber material.
  • the stream SR preferably the at least one of the one or more decomposition products which are comprised in the stream SR, comprises one or more of at least one amine, at least one ketone, at least one ether, at least one amide, and at least one alcohol
  • the at least one amine preferably comprises one or more of at least one aliphatic amine and at least one aromatic amine
  • the at least one ketone preferably comprises at least one aliphatic ketone
  • the at least one ether preferably comprises at least one aliphatic ether
  • the at least one amide preferably comprises at least one aliphatic amide
  • the at least one alcohol preferably comprises at least one aliphatic alcohol.
  • any one of embodiments 1 to 19, wherein the overall residence time in the chemical reaction unit U 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 process of any one of embodiments 1 to 20, being a continuous process, a semicontinuous process or a batch process. 22.
  • the process of any one of embodiments 1 to 21 , wherein generating the aqueous stream SR according to (iv) comprises subjecting to the stream SE obtained from the reaction unit U , optionally after subjecting SE to filtration, to thermal water separation, obtaining the stream SR.
  • thermo water separation comprises one or more of distilling and falling film evaporating.
  • 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.
  • the polymer, or the polymer product, or the polymer and the polymer product comprises or comprise polyamide 6 and optionally at least one further polymeric compound, said polyamide 6 being at least partially obtainable or obtained from SCPL, said SCPL being obtainable or obtained by a process according to embodiment 28, wherein the at least one further polymeric compound preferably comprises one or more of at least one polyamide 6.6; at least one semiaromatic polyamide including one or more of polyamide 6T and polyamide 6I; at least one polyethylene terephthalate; 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 cop
  • any one of embodiments 29 to 31 wherein the polymer, or the polymer product, or the polymer and the polymer product is or are one of the following or a part of one of the following: a part of a car, preferably a cylinder head cover, an engine cover, a housing for a charge air cooler, a charge air cooler flap, an intake pipe, an intake manifold, a connector, a gear wheel, a fan wheel, a cooling water box, a housing or a housing part for a heat exchanger, a coolant cooler, a charge air cooler, a thermostat, a water pump, a radiator, a fastening part or a part of a battery system for electromobility, a dashboard, a steering column switch, a seat, a headrest, a center console, a transmission component, a door module, a car exterior for an A, a B, a C or a D pillar cover, a spoiler, a door handle, an exterior mirror, a
  • a method for increasing the e-caprolactam yield of a polyamide 6 depolymerization 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. Preferred aspects of the present invention are further illustrated in the Figure 1 and the Examples as described hereinunder.
  • Fig. 1 shows the results of the experiments according to runs 1 to 10 as described in Table 2 above, in particular with regard to the total yield of the caprolactam species (i) c-caprolactam monomer, (ii) c-caprolactam dimer and (iii) aminocaproic acid.
  • the number of the respective run is shown on the x axis, the corresponding total yield (in %) is shown on the y axis.
  • a linear regression is included (dotted line) which further highlights the increase in yield over time.
  • a textile waste material M containing about 65 weight- % polyamide 6 and further containing at least one further organic polymeric material including a polyurethane which was prepared from an aniline-based isocyanate was subjected as feedstock F to polyamide 6 depolymerization as follows:
  • 1 .2 kg of the material M were provided in the form of solid granules having a diameter of in the range of from 1 to 4 mm.
  • This material was put in an autoclave UR having an inner volume of 20 dm 3 together with 10 kg of a liquid aqueous phase Sw having a composition as indicated in the table below.
  • the autoclave was then closed and the granule / aqueous phase mixture was heated within 2 to 4 hours from ambient temperature to a polyamide depolymerization temperature TD of 270 °C at a pressure of 55 - 60 bar(abs). This temperature was maintained for a residence time of 140 min.
  • the respectively obtained depolymerization reaction mixture SE was then cooled to ambient temperature. After having discharged the reaction mixture SE from the autoclave, SE was filtered through a 50 pm sieve.
  • the resulting filtered solution SE was then subjected to distillation in a distillation column at a bottoms temperature of 106 °C, a top temperature of 100 °C and a top pressure of 1013 mbar(abs).
  • the vapor top stream obtained from the distillation column was condensed, and the obtained liquid stream S was divided into 2 streams so that 25 volume- % of SR were fed back to the top of the column and 75 volume- % of SR were fed back as part of Sw in the next run, i.e. as feed to the autoclave UR (reflux ratio 1 :3).
  • the liquid stream SR obtained from condensation as described above contained to following compounds, as determined via GC analysis (mean area contents, based on values obtained from runs 1 to 10): Table 1
  • Decomposition products comprised in the stream SR According to the present invention and as described above, 75 volume-% of SR were fed back as part of Sw in the next run, i.e. as feed to the autoclave U .
  • 10 consecutive polyamide depolymerization reactions were carried out in the autoclave.
  • the aqueous stream Sw consisted of 10 kg fresh DI water, and the resulting product stream SE was subjected, after filtration, to a distillation as described above leading to a top vapor stream SR from 75 volume-% were fed back to UR as part of the aqueous stream Sw employed for the second run.
  • yield as used in this context of the present invention is defined - for each run - as the mass of the respective component contained in the stream SR obtained in this run, divided by the mass of polyamide 6 contained in the material M used as starting material for this run.
  • the 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 (about 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.

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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)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Polyamides (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

L'invention concerne un procédé de dépolymérisation hydrolytique de polyamide 6 préparé à partir de ε-caprolactame, le procédé comprenant (i) la fourniture d'une charge chimique F comprenant le polyamide 6 et comprenant en outre au moins un autre composé polymère organique ; (ii) la fourniture d'un flux aqueux liquide Sw ; (iii) le mélange de la charge F avec le flux Sw et la soumission du mélange obtenu à des conditions de dépolymérisation de polyamide 6 dans une unité de réaction UR, l'obtention d'un flux aqueux SE comprenant ε-caprolactame et un ou plusieurs produits de décomposition d'un ou de plusieurs desdits autres composés polymères organiques ; (iv) la production d'un flux aqueux SR comprenant au moins une partie de l'eau et au moins une partie du ou des produits de décomposition compris dans le flux S, ledit flux SR ; (v) l'introduction d'au moins une partie du flux aqueux SR dans l'unité de réaction chimique UR.
PCT/EP2024/065382 2023-06-06 2024-06-05 Procédé de dépolymérisation hydrolytique d'un polyamide Ceased WO2024251759A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202480037501.9A CN121285543A (zh) 2023-06-06 2024-06-05 用于水解解聚聚酰胺的方法
KR1020267000445A KR20260018164A (ko) 2023-06-06 2024-06-05 폴리아미드를 가수분해적으로 해중합하는 방법
EP24731885.0A EP4724422A1 (fr) 2023-06-06 2024-06-05 Procédé de dépolymérisation hydrolytique d'un polyamide
AU2024284238A AU2024284238A1 (en) 2023-06-06 2024-06-05 Process for hydrolytically depolymerizing a polyamide
MX2025014673A MX2025014673A (es) 2023-06-06 2025-12-05 Proceso para la despolimerizacion hidrolitica de una poliamida

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP23177610.5 2023-06-06
EP23177610 2023-06-06
EP23211697.0 2023-11-23
EP23211697 2023-11-23

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EP (1) EP4724422A1 (fr)
KR (1) KR20260018164A (fr)
CN (1) CN121285543A (fr)
AR (1) AR132875A1 (fr)
AU (1) AU2024284238A1 (fr)
MX (1) MX2025014673A (fr)
TW (1) TW202506856A (fr)
WO (1) WO2024251759A1 (fr)

Citations (4)

* 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
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
WO2023187045A1 (fr) * 2022-03-30 2023-10-05 Basf Se Procédé de dépolymérisation hydrolytique d'un polyamide

Patent Citations (4)

* 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
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
WO2023187045A1 (fr) * 2022-03-30 2023-10-05 Basf Se Procédé de dépolymérisation hydrolytique d'un polyamide

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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EP4724422A1 (fr) 2026-04-15
TW202506856A (zh) 2025-02-16
CN121285543A (zh) 2026-01-06
MX2025014673A (es) 2026-01-07
KR20260018164A (ko) 2026-02-06
AR132875A1 (es) 2025-08-06
AU2024284238A1 (en) 2025-12-18

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