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EP-4735517-A1 - PROCESS FOR THE PRODUCTION OF HYDROCARBON RESINS FROM POLYSTYRENE RESIDUES AND TIRE RESIDUES

EP4735517A1EP 4735517 A1EP4735517 A1EP 4735517A1EP-4735517-A1

Abstract

The invention relates to a process for producing hydrocarbon resins from the microwave-assisted pyrolysis of a feedstock of styrene compounds and a feedstock comprising rubber chips, to the resin produced by said process, and to a rubber composition comprising a resin of said kind.

Inventors

  • LECOQ, Aurélie
  • MAISONNEUVE, Lise
  • RIFFARD, Fanny
  • SUTTER, MARC
  • TOULEMONDE, Paul-Aymé
  • DOUCET, JOCELYN
  • ENFERADI KERENKAN, Amir
  • LAVIOLETTE, JEAN-PHILIPPE

Assignees

  • COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
  • Pyrowave Inc.

Dates

Publication Date
20260506
Application Date
20240625

Claims (10)

  1. [Claim 1] A process for producing hydrocarbon resins from a charge of styrenic compounds and a charge comprising rubber chips, said process comprising at least ■ a. A step of preparing the charge of styrenic compounds so as to be able to feed this charge into the pyrolysis step; bl. A step of pyrolysis by microwave of the charge of styrenic compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds; cl. A step of separating the gaseous effluent from step b1) into at least one stream rich in light compounds, one stream rich in aromatics and one stream rich in heavy compounds b2. A step of microwave pyrolysis of the feedstock comprising rubber chips carried out at a temperature of between 300 and 900°C, making it possible to obtain a gaseous effluent, a pyrolysis oil and a solid effluent, said pyrolysis oil comprising at least 1.5% by weight of C Cia J c2 olefinic monomers. A step of separating the pyrolysis oil from step b2) into at least one raffinate, an intermediate fraction and an extract, the intermediate fraction having a boiling point at atmospheric pressure, measured according to ASTM D86-23, of between 140 and 280°C and comprising at most 10% by weight of heteroatoms d. A resin synthesis step comprising a polymerization section supplied at least by a stream from step cl) and by the intermediate fraction from step c2), followed by a finishing section and producing a polymerized effluent e. A treatment step comprising a section for separating the polymerized effluent from step d) into a solvent-rich effluent and a resin-rich effluent, and a drying section supplied by the resin-rich effluent in order to produce a stream of hydrocarbon resins.
  2. [Claim 2] A method according to the preceding claim in which the charge of styrenic compounds is a charge of styrenic compounds from plastic waste comprising at least 90% by weight of polystyrene.
  3. [Claim 3] Method according to the preceding claim in which the rubber chips comprise at least 50 pce of diene elastomer, preferably at least 60 pce of diene elastomer.
  4. [Claim 4] Process according to any one of the preceding claims, in which the charge of styrenic compounds is gradually heated during step a) to a temperature between 100°C and 300°C, preferably between 150°C and 300°C and more preferably between 200°C and 300°C.
  5. [Claim 5] Process according to any one of the preceding claims, in which the pyrolysis step b1) comprises a pyrolysis reactor operated at a temperature ranging from 300°C to 900°C and preferably ranging from 300 to 800°C and a pressure ranging from 0.8 bar to 7.5 bar.
  6. [Claim 6] A process according to any preceding claim in which separation step cl) is carried out by distillation.
  7. [Claim 7] Process according to any one of the preceding claims, in which the mass ratio of flow from step cl) to the intermediate fraction from step c2) feeding step d) is adjusted so that the resin obtained has a molar ratio of aliphatic H to aromatic H ranging from 40/60 to 95/5, preferably ranging from 50/50 to 90/10, more preferably ranging from 55/45 to 90/10.
  8. [Claim 8] Process according to any one of the preceding claims in which the polymerization section of step d) of resin synthesis is also supplied with a stream of solvent chosen from aliphatic, aromatic, halogenated solvents and their mixtures.
  9. [Claim 9] Process according to any one of claims 1 to 8 supplied only by the charge of styrenic compounds and the charge comprising rubber chips, the solvent necessary in step d) being provided by at least one flow from step c2) and/or at least a fraction of the pyrolysis oil from step bl).
  10. [Claim 10] Process according to the preceding claim in which at least a fraction of the pyrolysis oil from step b1) feeds step d) of resin synthesis.

Description

Process for the production of hydrocarbon resins from polystyrene residues and tire residues Technical field of the invention The present invention relates to the field of processes for producing hydrocarbon resins from recycled residues, to the resins produced by such processes as well as to the compositions comprising these resins, in particular the compositions intended for rubber articles and in particular vehicle tires. Prior art Pneumatic tires, and more generally rubber articles such as conveyor belts and non-pneumatic tires, are complex objects made up of a multitude of components. For example, a pneumatic tire is made up of more than 200 different raw materials, including different families of elastomers, reinforcing fillers, oils, hydrocarbon resins. Within hydrocarbon resins, hydrocarbon resins having a high glass transition temperature (Tg) comprising both aliphatic functions and aromatic functions are used to shift the performance compromises of the mixtures, such as rolling resistance or grip. These resins make it possible, in particular, to modify the Tg of the mixture. Such resins having a high Tg are known from the state of the art and described, for example, in documents WO2016/043851, US9139721 or FR2968006. The compatibility of resins with the elastomeric matrix, and in particular their ability to disperse correctly in the mixture, is essential for them to play their role correctly. The compatibility of the resin with an elastomeric matrix depends, among other things, on properties such as the glass transition temperature and the softening point of the resin, these properties being dependent on the molar mass, the nature and the ratio of aromatic units to aliphatic units of the resin (see for example J. Appl Polym. Sci 2022 139(15) 51950). It is therefore important to be able to vary these parameters in order to address the variety of elastomers used in rubber compositions. Such resins comprising aliphatic and aromatic units are well known in the state of the art, for example in document EP 0 936 229 which teaches the manufacture of hydrocarbon resins from aliphatic and aromatic monomers in cationic polymerization, from petroleum-based streams. While the performance of tires such as rolling resistance and wear resistance are key to limiting the environmental impact of these tires, it is also important to seek to limit as much as possible the use of fossil resources during the manufacture of rubber articles. Document US2013/0281611 describes a rubber composition for a tire that includes a plasticizer derived from the recycling of waste, the plasticizer being used here as a substitute for process oils. Documents WO2022/101562 and WO2022/101563 describe the production of hydrocarbon resins from residues from the pyrolysis of rubber chips. However, these documents do not address the problem of adjusting the microstructure of the resins, and in particular of adjusting the rate of aromatic and aliphatic monomers. Thus, an object of the present invention is to provide a process for producing resins that can be incorporated into a wide variety of elastomeric compositions from bio-sourced and/or recycled resources. Detailed description of the invention The invention relates to at least one method for producing hydrocarbon resins from a feedstock of styrene compounds and a feedstock comprising rubber chips, said method comprising at least ■ a. A step of preparing the feedstock of styrene compounds so as to be able to feed this feedstock into the pyrolysis step; bl. A step of pyrolysis by microwave of the feedstock of styrene compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds cl. A step of separating the gaseous effluent from step bl) into at least one stream rich in light compounds, one stream rich in aromatics and one stream rich in heavy compounds b2. A step of microwave pyrolysis of the feedstock comprising rubber chips carried out at a temperature of between 300 and 900°C, making it possible to obtain a gaseous effluent, a pyrolysis oil and a solid effluent, said pyrolysis oil comprising at least 1.5% by weight of C4-C12 olefinic monomers; c2. A step of separating the pyrolysis oil resulting from step b2) into at least one raffinate, an intermediate fraction and an extract, the intermediate fraction having a boiling point at atmospheric pressure of between 140 and 280°C and comprising at most 10% by weight of heteroatoms d. A resin synthesis step comprising a polymerization section supplied at least by a stream from step cl) and by the intermediate fraction from step c2), followed by a finishing section and producing a polymerized effluent e. A treatment step comprising a section for separating the polymerized effluent from step d) into a solvent-rich effluent and a resin-rich effluent, and a drying section supplied by the resin-rich effluent in order to produce a stream of