WO2024257006A1 - Procédé de récupération de polyamides - Google Patents

Procédé de récupération de polyamides Download PDF

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Publication number
WO2024257006A1
WO2024257006A1 PCT/IB2024/055790 IB2024055790W WO2024257006A1 WO 2024257006 A1 WO2024257006 A1 WO 2024257006A1 IB 2024055790 W IB2024055790 W IB 2024055790W WO 2024257006 A1 WO2024257006 A1 WO 2024257006A1
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WO
WIPO (PCT)
Prior art keywords
polyamides
phase
mixture
salt
methanol
Prior art date
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Ceased
Application number
PCT/IB2024/055790
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English (en)
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WO2024257006A4 (fr
Inventor
Massimo Broccatelli
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Primpex Plastiche Riunite Italiane Import Export SPA
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Primpex Plastiche Riunite Italiane Import Export SPA
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Priority to EP24740979.0A priority Critical patent/EP4728001A1/fr
Publication of WO2024257006A1 publication Critical patent/WO2024257006A1/fr
Publication of WO2024257006A4 publication Critical patent/WO2024257006A4/fr
Anticipated expiration legal-status Critical
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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
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • 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

Definitions

  • the object of the present invention is a polyamide recovery process that finds application primarily, but not exclusively, in the chemical industry and, in particular, in materials recycling.
  • a chemical separation and purification process includes three main phases: in the first phase the material containing the polymer to be separated is dissolved in a solvent in which the polymer is soluble. In this phase it is required to select a solvent having specific affinity for the polymer to be separated and not for pollutants or other bound polymers. This produces a solution of the dissolved polymer in the affine solvent. In the second phase filtration of the polymer solution is implemented so as to separate undissolved pollutants.
  • Solvents such as propylene glycol, alkenic carbonates and Dimethyl sulfoxide (DMSO) are known to be used.
  • DMSO Dimethyl sulfoxide
  • the drawback of using these solvents for PA recovery is related to the need to use high process temperatures, both to solubilize the PA of interest and to reduce the viscosity of the solution so that the latter is more easily filtered.
  • CN 114800 943 A describes a method for recycling waste mats.
  • the technical task underlying the present invention is to devise a process for recovering polyamides that may substantially obviate at least some of the mentioned drawbacks.
  • Another important object of the invention is to obtain a process that requires low process temperatures. Another important task of the invention is to allow for a polyamide recovery process easier to implement.
  • Another important object of the invention is to allow for a polyamide recovery process having a reduced environmental impact.
  • Fig. 1 shows a diagram of the process according to the invention
  • Fig. 2 illustrates an alternative diagram of the process according to the invention.
  • measurements, values, shapes, and geometric references when associated with words such as “approximately” or other similar terms such as “nearly” or “substantially,” may be affected by production and/or manufacturing measurement errors or inaccuracies and, most importantly, may be affected by a slight deviation from the value, measurement, shape, or geometric reference with which it is associated. For example, when associated with a given value, such terms, preferably indicate a deviation of no more than 10 percent of that value.
  • polyamides subject to the recovery process according to the invention are collectively indicated by the reference number 1.
  • Polyamides 1 are a class of polymers in which the monomeric units constituting the polymer chain are linked together by amide bonds. They have the advantage of high tensile and frictional strength. Therefore, they are used, either as the only material or in combination with other polymers in the manufacturing of products for which high technical characteristics and resistance to environmental factors are required.
  • polyamides 1 may be used in the production of fibers, fabrics, nets, cordage, gaskets, etc.
  • they may be processed by the usual techniques used for thermoplastic polymers, such as extrusion, injection molding, blow molding, etc.
  • the invention comprises a novel process for recovering polyamides 1 starting from a material 10.
  • the material 10 is preferably a waste material, such as post-consumer fabric or cordage artifacts, or fishing nets, airbag balls, fabric floor coverings, packaging sheets or films, or a waste from industrial production of said artifacts.
  • material 10 includes polyamides 1 and pollutants 2.
  • Pollutants 2 include materials of various kinds depending on the original use for which material 10 was intended before use.
  • pollutants 2 may include fabrics containing fibers of various kinds, such as, for example, carbon fibers, polyolefin fibers, polyester fibers, elastomeric fibers, natural fibers, or fibers of other materials, woven with polyamide 1 fibers, for the production of clothing or work clothes such as gowns or overalls, etc., for example.
  • Material 10 may include pollutants 2 of another kind related to the use of material 10 itself.
  • cordage used for fishing nets may contain sand residues or shellfish shells clinging to the net.
  • Pollutants 2 may also be coating films or sealing agents.
  • pollutants 2 may consist in silicone resins used to waterproof the polyamide 1 fabric of airbag inflators in order to thereby prevent the escape of gases in the event of an accident.
  • the recovery process preferably includes a preliminary phase of material 10 size reduction.
  • Size reduction has the advantage of making material 10 more easily processable. For example, if material 10 is a fabric, size reduction may be implemented via cutting or fraying operations. Due to size reduction, the recovery process is therefore rendered more efficient and quicker.
  • polyamides 1 preferably include a polymer to be selected between nylon 6 and nylon 6,6. This type of polymer is the one most widely used in the applications previously described. It is also effectively recovered by the process according to the invention.
  • the process includes a phase of preparing a first solution 3.
  • the first solution 3 is advantageously a deep eutectic solvent.
  • the first solution 3 allows polyamides 1 to be solubilized at lower temperatures than solvents used in common purification processes.
  • polyamide 1 may advantageously be recovered by means of a process that is less energy-intensive than known purification processes.
  • components typically used in deep eutectic solvents are less toxic than components utilized in solvents used in purifications.
  • a deep eutectic solvent is formed when a solvent binds to a solute, such as a salt, by hydrogen bonds. Therefore, the function of the deep eutectic solvent solely consists in bringing the liquefied solute into contact with the solid material to be dissolved, which, in the case of the present invention, is solid polyamide. If the latter establishes hydrogen bonds with the solute in the deep eutectic solvent that are "stronger" than those between the solvent and the solute in the deep eutectic solvent, the solute will interact with the polyamide and modify it. In the case of polyamides, the modification produces a decrease in the attractive forces between the macromolecules of the polyamide resulting in the liquefaction of the same.
  • solution 3 includes at least methanol 4 and at least one salt 5.
  • Methanol 4 is a solvent in the liquid state at polar room temperature and protic with a low boiling temperature. Therefore, its use is advantageous, since it also makes the temperatures required to produce a deep eutectic solvent capable of solubilizing polyamides 1 very low.
  • Salt 5 is one of the salts that cause deep eutectic solvent formation with methanol 4.
  • it preferably includes at least one of Ca NO ⁇ AF O, NaSCN, CaDAF O, and calcium salicylate.
  • This list of salts is representative, but not exhaustive, of the salts that, when solubilized in methanol 4 to saturation, result in the formation of a deep eutectic solvent.
  • the process includes a solubilization phase.
  • the material 10 is added to the first solution 3.
  • the material 10 preferably already undergoes size reduction, as previously described.
  • each monomeric unit of polyamide binds to salt 5 thus decreasing the forces of attraction between the macromolecules of polyamide 1, so polyamide 1 liquefies thereby becoming separable from solid pollutants 2.
  • the first mixture 11 comprises material 10, methanol 4, salt 5 and liquefied polyamides 1. Since the amount of salt 5 bound to methanol 4 in the deep eutectic solvent obviously decreases at this stage, the amount of salt 5 is preferably kept constant in a 1 :1 molar ratio with the monomeric residue of polyamides 1. Therefore, during the process further additions are implemented so that the molar ratio of Sale 5/Residue monomer of polyamide 1 is consistently about 1 :1.
  • the next phase of the process includes an initial filtration phase in which the pollutants 2 are separated from the first mixture 11.
  • Filtration may be implemented using a Buchner filter to separate the solid pollutants 2 from the liquid components.
  • the first filtration phase may advantageously be implemented at a temperature lower than the boiling temperature of each of the components of the deep eutectic solvent, i.e. lower than the boiling temperature of methanol 4.
  • the energy consumption required to separate the polyamides 1 from the pollutants 2 is advantageously reduced with a consequent reduction in process costs.
  • a second mixture 12 is obtained. It includes the polyamides 1 linked to salt 5 and methanol 4.
  • the process includes a separation phase in which a separating agent 6 is added to the second mixture 12.
  • the separating agent 6 is a substance having the function of removing the salt 5 from both the methanol 4 and the polyamides 1.
  • a third mixture 13 is obtained. It deals with a mixture containing methanol 4, salt 5, polyamides 1 as well as the separating agent 6 bound to the salt 5.
  • the separating agent 6 performs the function of breaking the bond between salt 5 and polyamides 1.
  • the separating agent 6 includes a large number of salt 5 solvents, including aliphatic alcohols in a number of carbon atoms bigger than methanol.
  • the separating agent 6 preferably comprises at least one of the solvents selected from 1- butanol, acetamide and dimethyl sulfoxide. These liquid solvents have the advantage of being particularly effective in separating the salt 5 from the polyamides 1. In particular, they provide benefits where the polyamides 1 include nylon 6 or nylon 6,6. At this stage, polyamides may precipitate as a solid into powder.
  • a second filtration phase follows.
  • the third mixture 13 is subjected to filtration in order to obtain the polyamides 1 and a second solution 7.
  • the latter includes methanol 4, salt 5 and the separating agent 6.
  • the polyamides 1 are separated and purified.
  • the second filtration phase may also be implemented by using a Buchner filter to separate the solid polyamides 1 from the second solution 7. This second filtration phase provides benefits since it takes place at a temperature lower than the boiling temperature of methanol 4. As already mentioned, the filtration and purification process provides benefits in terms of energy and cost.
  • the process preferably includes a recovery phase following the second filtration phase.
  • methanol 4, salt 5 and the separating agent 6 are separated from the second solution 7.
  • These separation phases may be implemented by distillation from the most volatile to the least volatile component. For example, the distillation of methanol 4 may be implemented first, which has a lower boiling temperature than that of the other components present in the second solution 7. Next, distillation of the separating agent 6 is carried out occurs. At the end of the recovery phase, methanol 4, salt 5 and separating agent 6 are re-obtained separately.
  • This additional phase once the polyamides 1 are separated, has the advantage of recovering the substances used during the process with process costs being reduced. In addition, the process is more environmentally friendly, since the solvents and salts used may be recovered, which are not released into the environment.
  • the methanol 4 is preferably separated from the second mixture 12 before the filtration of the polyamides 1. Therefore, in some embodiments of the process implementation, the phase of achieving polyamides 1 purification may follow a different order.
  • the second mixture 12 preferably is subjected to a first partial separation phase in which methanol 4 is separated from the second mixture 12 via distillation.
  • a fourth mixture 14 is obtained. It includes salt 5 and polyamides 1.
  • This mixture is in a solid state and, in particular, may be in powder form.
  • the fourth mixture 14 is subjected to a second partial recovery phase in which the separating agent 6 is added to the former. In this way, a fifth mixture 15 is obtained.
  • the addition of liquid separating agent 6 may cause salt 5 to be solvated wherein only polyamides 1 remains in a solid state.
  • the second partial recovery phase is followed by the second filtration phase, in which the fifth mixture 15 is subjected to filtration in order to separate polyamides 1 and obtain a third solution 8.
  • the third solution 8 is a solution of salt 5 in the separating agent 6.
  • polyamides 1 are separated and recovered.
  • the separating agent 6 is separated from the third solution 8 so as to obtain salt 5 as well as the separating agent 6.
  • polyamides 1 comprises nylon 6 or nylon 6,6, salt 5 comprises NaSCN, and the separating agent 6 comprises 1 -butanol.
  • material 10 includes used airbags comprising nylon 6,6. In the preliminary size reduction phase, the airbags are frayed and shredded resulting in a frayed fabric.
  • NaSCN is placed in an amount of methanol 4 preferably between 50 cc and 350 cc, more preferably between 100 cc and 300 cc, even more preferably between 150 cc and 250 cc.
  • the NaSCN salt 5 is added until an initial solution 3 comprising methanol 4 saturated with NaSCN is obtained.
  • material 10 in the form of frayed tissue is added to the first solution 3 under stirring at a temperature preferably below 64 °C, more preferably between 50 °C and 64 °C, even more preferably between 55 °C and 60 °C. In this way, the first mixture 11 is obtained.
  • an amount of frayed fabric may be added preferably between 100 g and 300 g, more preferably between 150 g and 250 g.
  • Additions are preferably made under the same temperature conditions as previously indicated.
  • pollutants 2 comprise a silicone coating of nylon 6 fibers. After a certain time interval, the silicone coating separates from the nylon 6,6 fibers.
  • the first filtration phase is conducted, in which the first mixture 11 is filtered through a Buchner filter to separate the solid pollutants 2.
  • This phase is also preferably implemented while maintaining the temperature values of the previous phases. In this phase, the required temperature values have the advantage of avoiding solidification of the substances to be separated from the pollutants 2.
  • the first partial separation phase may be implemented in which the distillation of methanol 4 occurs.
  • This phase may be implemented in a vacuum and under mechanical agitation. In this way, the precipitate may be pulverized.
  • the second phase of partial recovery is carried out.
  • 1 -butanol is added to the fourth 14 mixture.
  • a volume of 1 -butanol may be added preferably between 200 cc and 400 cc, more preferably between 250 cc and 350 cc. The addition may be done under stirring. Dissolution of NaSCN in 1 -butanol is exothermic and causes heating of the fifth mixture 15 being formed.
  • the second filtration phase is implemented.
  • filtration of the nylon 6,6, in pure solid powder is carried out, which is separated from the third saline solution 8 of 1 -butanol.
  • the recovery phase may finally take place, in which the third solution 8 is subjected to vacuum distillation so as to separate the 1 -butanol from the salt 5 NaSCN.
  • material 10 comprises shredded sock production waste containing 97% nylon 6 fibers and 3% Lycra fibers.
  • polyamides 1 include nylon 6 fibers and pollutants 2 includes Lycra fibers.
  • methanol 4 and NaSCN are used as in the previous examples.
  • material 10 is gradually added to a volume of the first solution 3 of NaSCN in methanol 4 preferably between 200 cc and 400 cc, more preferably between 250 cc and 350 cc.
  • the amount of material 10 added is preferably between 100 g and 300 g, more preferably between 150 g and 250 g.
  • the material 10 separates within the first mixture 11 so that the Lycra fibers are almost totally separated from the nylon 6 fibers, which are dispersed in methanol 4.
  • nylon 6 unlike nylon 6,6, forms a dispersion of particles in methanol 4.
  • the first filtration phase is implemented in the manner previously described to remove Lycra fibers, and all the following phases are carried out based on temperature ranges and amounts, which were previously indicated in the individual phases. Also in this example, 1 -butanol is used as separating agent 6. At the end of the process, pure nylon 6 is obtained and the reagents used are recovered.
  • the invention includes a novel use of a deep eutectic solvent for the purification and recovery of polyamides.
  • a deep eutectic solvent for the purification and recovery of polyamides.
  • polyamides may be recovered from production waste or residues at lower temperatures than known processes.
  • the lower temperatures make it possible to reduce solution viscosity and mixtures during the process as well as to avoid thermal shock to the polymer to be recovered.
  • Another advantage of the process is related to the fact that the mixtures used allow for total recovery of the substances used, making the process more environmentally friendly.
  • the environmental advantage is also, and more importantly, related to the fact that through this process, waste containing this type of polymer is prevented from being dispersed into the environment.
  • wastes that constitute material 10 cannot be arranged in landfills, since the heat balance of their combustion is negative. Therefore, if not recovered through recovery processes, they are released into the environment.
  • the recovery process yields nylon powders that are particularly suitable for use in rotational molding processes.
  • this process corresponds to both the recovery of nylon from residues and the production of rotational molding powders in a single process.
  • the process has the advantage of allowing for recovery and purification of nylon by means of a process easier to implement due to use of purification techniques for which suitable equipment already exists.

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

Abstract

L'invention concerne un procédé de récupération de polyamides (1) à partir d'un matériau (10) comprenant des polyamides (1) et des polluants (2), ledit procédé comprenant : une phase de préparation d'une première solution (3) étant un solvant eutectique profond et comprenant au moins du méthanol (4) et au moins un sel (5) ; une phase de solubilisation dans laquelle le matériau (10) est ajouté à la première solution (3) pour obtenir un premier mélange (11) dans lequel les polyamides (1) se lient au sel (5) ; une première phase de filtration dans laquelle des polluants (2) sont séparés du premier mélange (11) pour obtenir un second mélange (12) comprenant des polyamides (1) liés au sel (5) et au méthanol (4) ; une phase de séparation dans laquelle un agent de séparation (6) est ajouté au deuxième mélange (12) pour soustraire le sel (5) à la fois du méthanol (4) et des polyamides (1) et obtenir un troisième mélange (13) dans lequel le sel (5) et les polyamides (1) sont à nouveau séparés ; une deuxième phase de filtration dans laquelle le troisième mélange (13) est soumis à une filtration de façon à obtenir les polyamides (1) et une deuxième solution (7).
PCT/IB2024/055790 2023-06-13 2024-06-13 Procédé de récupération de polyamides Ceased WO2024257006A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP24740979.0A EP4728001A1 (fr) 2023-06-13 2024-06-13 Procédé de récupération de polyamides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102023000012114 2023-06-13
IT102023000012114A IT202300012114A1 (it) 2023-06-13 2023-06-13 Procedimento di recupero di poliammidi

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WO2024257006A4 WO2024257006A4 (fr) 2025-02-27

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IT (1) IT202300012114A1 (fr)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB563078A (en) * 1940-10-24 1944-07-28 Du Pont Solutions of polyamides
JP5110704B2 (ja) * 2008-05-28 2012-12-26 学校法人 関西大学 脂肪族ポリアミド繊維基布複合体からの脂肪族ポリアミドの再生方法
CN114800943A (zh) * 2022-05-20 2022-07-29 嘉兴学院 一种废旧地毯的回收方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB563078A (en) * 1940-10-24 1944-07-28 Du Pont Solutions of polyamides
JP5110704B2 (ja) * 2008-05-28 2012-12-26 学校法人 関西大学 脂肪族ポリアミド繊維基布複合体からの脂肪族ポリアミドの再生方法
CN114800943A (zh) * 2022-05-20 2022-07-29 嘉兴学院 一种废旧地毯的回收方法

Also Published As

Publication number Publication date
WO2024257006A4 (fr) 2025-02-27
IT202300012114A1 (it) 2024-12-13
EP4728001A1 (fr) 2026-04-22

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