WO2025181232A1

WO2025181232A1 - Process for recycling a solid material w comprising ethylene vinyl acetate

Info

Publication number: WO2025181232A1
Application number: PCT/EP2025/055334
Authority: WO
Inventors: Miika FRANCK; Achim Loeffler; Arno Volkmann; Daniel KOEPKE
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2024-02-28
Filing date: 2025-02-27
Publication date: 2025-09-04
Anticipated expiration: 2026-08-28

Abstract

The present invention relates to a process for recycling a solid material W comprising ethylene vinyl acetate, a recycling unit for carrying out said process and a use of one or more products obtained by said process for preparing a polymer, such as ethylene vinyl acetate.

Description

Process for recycling a solid material W comprising ethylene vinyl acetate

Waste streams containing ethylene vinyl acetate (EVA), rubber, polyurethanes, and other polymers, namely from shoes, are highly complex and hard to recycle. In many applications these materials are glued together. A sport shoe may comprise a polyethylene terephthalate (PET) upper part, potentially with leather portions, an insole of polyurethane and textile, a midsole of EVA and an outsole made of thermoplastic polyurethane (TPU) or rubber. At present only a very low amount of the shoes is recycled as most of them are disposed in a landfill due to their complex compositions. The mere disposal in landfill of waste materials, such as sport shoes and sport shoe soles, has a negative impact on the environment as well as on the carbon footprint. Therefore, there is a need to develop an economical and energy efficient process delivering valuable materials with high technical features to render the industry more sustainable, such as the shoe industry.

It has been found in the present invention that it is possible to develop a recycling process which is economical and energy efficient while delivering valuable materials which comprise high technical features. Indeed, according to the process of the present invention, pyrolysis oils with good quality can be obtained, namely low oxygen content, low aromatics content and in good yields, permitting reduced number of subsequent treatment steps for then producing new polymers such as EVA. The recycling process according to the present invention renders the production of EVA more sustainable, being crucial for the environment, since it has been proven that its recycling from waste material is feasible with valuable products at the end.

Therefore, the present invention relates to a process for recycling a solid material W comprising ethylene vinyl acetate, the process comprising

(i) providing the solid material W comprising polymers, the polymers comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate, wherein W comprises the ethylene vinyl acetate in an amount 01 expressed in weight-% based on the weight of W;

(ii) sorting the solid material W provided according to (i) in at least two different streams, obtaining

- a stream S1 , depleted in the one or more polymers other than ethylene vinyl acetate compared to W, comprising ethylene vinyl acetate, and - a stream S2 comprising one or more polymers other than ethylene vinyl acetate and optionally ethylene vinyl acetate, wherein S1 comprises the ethylene vinyl acetate in an amount C2 expressed in weight-% based on the weight of S1 , with C2 > C1 ;

(iii) subjecting the stream S1 obtained according to (ii) to pyrolysis conditions into a pyrolysis reactor R_P, obtaining a pyrolysis oil O(p), with (iii) comprising

(111.1) feeding S1 obtained according to (ii) into R_P;

(111.2) heating S1 fed into R_P according to (iii.1) to a temperature in the range of from 300 to 800 °C, obtaining a gas stream G1;

(111.3) removing G1 obtained according to (iii.2) from R_P and subjecting G1 to condensation conditions in a separation unit SU, obtaining a stream L2 comprising the pyrolysis oil O(p).

Preferably the one or more polymers other than ethylene vinyl acetate are selected from the group consisting of rubber, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyurethane (PU), thermoplastic polyurethane (TPU), and mixtures of two or more thereof, more preferably selected from the group consisting of rubber, polyethylene terephthalate (PET) and polyvinyl chloride (PVC).

Optionally the solid material W further comprises one or more polyolefins, such as polyethylene (PE), and/or polypropylene (PP).

Preferably the solid material W is a solid waste material, wherein said waste material preferably is shoe waste solid material, more preferably shoe sole waste material.

In the context of the present invention, the terms “shoe” and “shoe sole” refer preferably to sport shoe or sport shoe sole.

Preferably, the shoe waste material includes pre-consumer shoe waste material and post-consumer shoe waste material. In the context of the present invention, the term “pre-consumer shoe waste material” refers to shoe waste material obtained from the manufactures (such as scraps or defect shoes), retailers, and so on.

In the context of the present invention, the term “shoe sole material” refers to materials from a shoe insole, a shoe outsole and/or a shoe midsole.

Preferably W comprises at most 1 weight-%, more preferably at most 0.5 weight-%, of textile material, for example from the top portion of a shoe.

Steps (i) Preferably (i) comprises

(1.1) providing a solid waste material WO comprising solid shoe material, more preferably shoe sole material, comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate;

(1.2) fragmenting WO provided in (i.1) to pieces, obtaining a solid material W comprising pieces of WO.

Preferably fragmenting according to (i.2) comprises one or more of lacerating, cutting, shredding, grinding, granulating, and comminuting.

Optionally, the process further comprises subjecting the solid material W to coupled size separation, namely by sieving, sifting and/or screening, for removing polymers or compounds other than ethylene vinyl acetate prior to (ii).

Optionally, prior to (i.2) or after (i.2) and prior to (2), polymers other than ethylene vinyl acetate can be removed by selective dissolution of said specific polymer in suitable solvent/solvent mix.

Preferably, the length of the pieces obtained according to (i.2) varies from a piece to another and is in the range of from 1 to 20 mm, more preferably in the range of from 3 to 15, more preferably in the range of from 5 to 10, the length of the pieces being the Feret diameter of the pieces.

Optionally, the process further comprises, prior to (ii), passing W through a metal removal unit to remove metals if any in W.

Thanks to the metal removal unit, such as using magnetic separator, eddy current unit, eddy current and/or induction sensor(s), the metals can be detected and ejected from the stream comprising W.

Optionally, prior to the sorting according to (ii), the process further comprises passing W through a density separation unit, such as air classifier. Said density separation unit preferably removes one or more of metals, hard plastics and dust if present.

Preferably sorting according to (ii) comprises manually sorting or automated sorting, more preferably automated sorting.

Preferably sorting according to (ii) comprises optical sorting, more preferably hyperspectral or infrared sorting, more preferably near-infrared sorting or mid-infrared sorting. In the context of the present invention, the expression “optically sorting” refers to an automated process of sorting solid products using cameras and/or lasers.

Preferably sorting according to (ii) comprises air-based automated sorting.

Preferably the air-based automated sorting is performed by using one or more of a zigzag column, an air-cascade, an aspirator and a vibrating air-table, more preferably one or more of an air-cascade and a vibrating air-table.

Preferably S1 comprises the ethylene vinyl acetate in an amount C2 being of at least 20 weight- %, more preferably at least 30 weight-%, more preferably in the range of from 40 to 100 weight- %, more preferably of from 50 to 100 weight-%, based on the weight of S1.

Preferably, the stream S1 comprises PU and/or TPU in an amount of at most 25 weight-%, more preferably of at most 10 weight-%, more preferably at most 5 weight-%, more preferably of at most 2 weight-%, based on the weight of S1.

Preferably, the stream S1 comprises PET in an amount of at most 5 weight-%, more preferably of at most 2 weight-%, based on the weight of S1.

Preferably S1 is substantially free, more preferably free of leather. In other words, preferably at most 0.5 weight-%, more preferably at most 0.1 weight-%, more preferably at most 0.01 weight- % of S1 consists of leather.

Preferably S1 comprises at most 30 weight-%, more preferably at most 20 weight-%, more preferably at most 10 weight-%, of oxygen (O), calculated as the element , based on the weight of the solid material W, the O content being determined as described in Analytics 1.4 herein.

Preferably S1 comprises at most 10 weight-%, more preferably at most 5 weight-%, more preferably at most 2 weight-%, of nitrogen (N), calculated as the element, based on the weight of the solid material W, the N content being determined as described in Analytics 1.3 herein.

Preferably S1 comprises at most 3 weight-%, more preferably at most 1 weight-%, more preferably at most 0.5 weight-%, of sulfur (S), calculated as the element, based on the weight of the solid material W, the S content being determined as described in Analytics 1.2 herein.

Preferably S1 comprises at most 1 weight-%, more preferably at most 500 wppm (weight-ppm), more preferably at most 50 wppm, more preferably of at most 20 wppm, of chlorine (Cl), calculated as the element, based on the weight of the solid material W, the total Cl content being determined as described in Analytics 1.2. herein.

Optionally S1 comprises, in addition to ethylene vinyl acetate, rubber and/or one or more polyolefins. For example, rubber can be present in an amount up to 80 weight-%. In the context of the present invention, it is possible that S1 further comprises solids, such as carbon black, inorganic fillers such as TiC>2, CaCCh, etc.

Preferably S2 is substantially free of, more preferably free of EVA.

Preferably feeding S1 in R_P according to (iii.1) is performed via a dosing unit, the dosing unit being preferably one or more of a screw, an extruder and a rotary valve.

It is also conceivable that S1 is fed via pneumatic conveyor or liquid injector into the pyrolysis reactor RP.

Further, (iii.1) may further comprise pre-heating S1, more preferably in an extruder by internal friction or by a heat exchanger. Preferably, the heat exchanger uses electricity of the combustion energy from the pyrolysis gas or other heat sources.

Preferably the pyrolysis reactor RP is selected from the group consisting of a fluidized bed, a moving bed, an entrained flow, an auger, a screw reactor, an extruder, a stirred tank reactor, a rotary kiln, a tribochemical reactor, and a mechanochemical reactor.

Preferably the fluidized bed is bubbling, turbulent, fast or circulating.

Preferably the pyrolysis according to (iii) is performed in the pyrolysis reactor Rp under an atmosphere exempt of oxygen.

Preferably the pyrolysis reactor R_P is ventilated with nitrogen, or a recycled pyrolysis gas.

Preferably the pyrolysis according to (iii) is performed by thermal cracking (absence of catalyst) or catalytic cracking, more preferably thermal cracking.

Preferably the temperature into RP according to (iii.2) is in the range of from 350 to 750 °C, more preferably in the range of from 450 to 650 °C.

Preferably SU comprises at least one condenser, scrubber or quench.

Preferably the separation unit SU used in (iii.3) comprises one or more separation sub-units.

Preferably the separation sub-units are arranged in series. Preferably the separation sub-unit is a condenser, a scrubber or a quench, more preferably a condenser.

Preferably the stream L2 has an oxygen (O) content lower than the O content of the solid material W.

Preferably (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a subunit SSU1 and a sub-unit SSU2, for condensing, more preferably at a temperature in the range of from 0 to 80°C, obtaining a first oil 01 from SSU1 and a second oil 02 from SSU2, wherein L2 comprises 01 and/or 02 as the pyrolysis oil 0(p).

This is illustrated in Figure 1. Preferably (iii.3) comprises

(111.3.1) removing G1 obtained according to (iii.2) from R_P;

(111.3.2) passing G1 removed from RP according to (iii.3.1) in a first separation sub-unit SSU1 , comprised in SU, at a temperature in the range of from 35 to 100°C, obtaining an oil 01 and a gas stream G11 ;

(111.3.3) passing G11 obtained according to (iii.3.2) in a second separation sub-unit SSU2, comprised in SU and located downstream of SSU1 , at a temperature in the range of from 0 to 25°C, obtaining an oil 02 and a gas stream G3;

(111.3.4) combining 01 obtained according to (iii.3.2) and 02 obtained according to (iii.3.3), obtaining L2 comprising the pyrolysis oil 0(p).

Preferably the gas stream G3 obtained according to (iii.3) is subjected to a washing step. Preferably the washing step comprises contacting the gas stream G3 with a solution comprising a base, preferably one or more of NaOH, KOH, K2CO3, Na2CO3, alkaline earth metal hydroxides such as calcium hydroxide (Ca(0H)2), Ca(OH)2/CaO and NH3, or an acid, such as hydrochloric acid (HCI), sulfur dioxide (SO2), hydrogen cyanide (HCN), sulfuric acid (H2SO4), nitric acid (HNO3) or phosphoric acid (H3PO4).

Alternatively, preferably (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a subunit SSUT and a sub-unit SSU2’, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L1 comprising acetic acid from SSUT and the stream L2 comprising the pyrolysis oil 0(p) from SSU2’.

This is illustrated in Figure 2. According to said alternative, preferably (iii.3) comprises

(iii.3. ) removing G1 obtained according to (iii.2) from R_P;

(iii.3.2’) passing G1 removed from RP according to (iii.3. ) in a first separation sub-unit SSUT, comprised in SU, at a temperature above 110 °C, more preferably in the range of from above 110 to 130°C, more preferably in the range of from above 110 to 120°C, obtaining the stream L1 comprising acetic acid and one or more compounds other than acetic acid, and a gas stream G11’; (iii.3.3’) passing G1 T obtained according to (iii.3.2’) in a second separation sub-unit SSU2’, comprised in SU and located downstream of SSU1’, at a temperature of at most 100 °C, more preferably in the range of from 0 to 80 °C, more preferably in the range of from 0 to 30 °C, obtaining the stream L2 comprising O(p), also called “low boiling hydrocarbons” and a gas stream G3.

Alternatively, preferably (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a subunit SSU1”, a sub-unit SSU2” and a sub-unit SSU3”, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L0 from SSU1”, a stream L1 comprising acetic acid from SSU2” and the stream L2 comprising the pyrolysis oil O(p) from SSU3”.

According to said alternative, preferably (iii.3) comprises

(iii.3.1 ”) removing G1 obtained according to (iii.2) from R_P;

(iii.3.2”) passing G1 removed from RP according to (iii.3. T) in a first separation sub-unit SSU1”, comprised in SU, at a temperature above 130 °C, more preferably in the range of from above 130 to 180°C, obtaining the stream L0 comprising hydrocarbons, also called “high boiling hydrocarbons”, and a gas stream G21 ;

(iii.3.3”) passing G21 obtained according to (iii.3.2’) in a second separation sub-unit SSU2”, comprised in SU and located downstream of SSU1”, at a temperature in the range of from 110 to 130 °C, more preferably in the range of from 110 to 120°C, obtaining the stream L1 comprising acetic acid and one or more compounds other than acetic acid, also called “middle boiling hydrocarbons”, and a gas stream G22;

(iii.3.4”) passing G22 obtained according to (iii.3.3’) in a third separation sub-unit SSU3”, comprised in SU and located downstream of SSU2”, at a temperature of at most 100 °C, more preferably in the range of from 0 to 80 °C, more preferably in the range of from 0 to 30 °C, obtaining the stream L2 comprising the pyrolysis O(p), preferably also called “low boiling hydrocarbons” and a gas stream G3.

In the context of the present invention, the term “high boiling hydrocarbons” refers to hydrocarbons having a boiling point higher than the boiling point of acetic acid, preferably higher than 130 °C. In the context of the present invention, the term “low boiling hydrocarbons” refers to hydrocarbons (pyrolysis oil) having a boiling point lower than the boiling point of acetic acid, preferably a boiling point lower than 105°C, more preferably lower than 100 °C. In the context of the present invention, the term “middle boiling hydrocarbons” refers to hydrocarbons having a boiling point around the boiling point of acetic acid, preferably a boiling point between 110 and 130°C. Preferably the process further comprises recycling LO obtained according to (iii.3) , in particular (iii.3.2”), into RP; or

- subjecting LO to partial oxidation in a partial oxidation reactor GR; or

- subjecting LO to cracking in a cracker unit C, more preferably the process further comprises recycling LO obtained according to (iii.3), in particular (iii.3.2”), into RP; or

- subjecting LO to partial oxidation in a partial oxidation reactor GR.

Optionally the process further comprises subjecting LO to one or more purification stages prior to be cracked in C or partially oxidized in GR.

Preferably the process of the present invention further comprises

- subjecting L1 obtained according to (iii.3), in particular (iii.3.2’) or (iii.3.3”), to one or more purification stages, obtaining a purified stream L1 ’ comprising acetic acid and a stream G23 comprising the one or more compounds other than acetic acid.

Preferably the process further comprises recycling G23 into RP; or

- subjecting G23 to partial oxidation in a partial oxidation reactor GR; or

- subjecting G23 to cracking in a cracker unit C, more preferably the process further comprises recycling G23 into RP; or subjecting G23 to partial oxidation in a partial oxidation reactor GR.

Preferably the O content of the pyrolysis oil O(p) comprised in L2 obtained according to (iii) is in the range of from 0 to 15 g/100 g of the pyrolysis oil, more preferably in the range of from 0 to 5 g/100 g of the pyrolysis oil, more preferably in the range of from 0 to 2 g/100 g of the pyrolysis oil, the O content being determined as in Analytics 1 .4.

Preferably the N content of the pyrolysis oil O(p) comprised in L2 obtained according to (iii) is in the range of from 0 to 5 g/100 g of the pyrolysis oil, more preferably in the range of from 0 to 3 g/100 g of the pyrolysis oil, more preferably in the range of from 0 to 1 g/100 g of the pyrolysis oil, the N content being determined as in Analytics 1.3.

Preferably the S content of the pyrolysis oil O(p) comprised in L2 obtained according to (iii) is in the range of from 0 to 8000 ppm, more preferably in the range of from 0 to 5000 ppm, more preferably in the range of from 0 to 200 ppm, the S content being determined as in Analytics 1.2.

Preferably the Cl content of the pyrolysis oil O(p) comprised in L2 obtained according to (iii) is in the range of from 0 to 200 ppm, more preferably in the range of from 0 to 150 ppm, more preferably in the range of from 0 to 50 ppm, the Cl content being determined as in Analytics 1.2.

Preferably the pyrolysis oil O(p) has an aromatic content in the range of from 0 to 10 weight-%, more preferably from 0 to 7 weight-%, based on the weight of hydrocarbons in O(p), the aromatic content being determined as in Analytics 1.5.

Therefore, according to the process of the present invention, pyrolysis oils with good quality can be obtained, namely low oxygen content, low aromatics content and in good yields, permitting reduced number of subsequent treatment steps for then producing new polymers such as EVA. Further, it has also been demonstrated that acetic acid can also be recovered after the pyrolysis which permits then to prepare even more feedstock for the preparation of highly valuable products. The recycling process according to the present invention renders the production of EVA more sustainable, being crucial for the environment, since it has been proven that its recycling from waste material is feasible with valuable products at the end. For example, it has been shown that from end-of-life EVA containing shoes thanks to the present process it is possible to recycle them, to produce re-EVA from recycled-hydrocarbons, recycled-acetic acid which can then be used to produce new shoes.

Step (iv)

Optionally the process further comprises

(iv) subjecting the pyrolysis oil O(p) comprised in L2 obtained according to (iii) to one or more purification stages, obtaining a stream L2P comprising a purified pyrolysis oil O(pp) depleted in one or more halogenated organic compounds and/or one or more organic compounds comprising conjugated double bonds compared to O(p).

Preferably the one or more purification stages comprises one or more of dehalogenation, hydrogenation and thermal treatment.

Preferably the pyrolysis oil O(p) is further treated to remove halogens, for example by hydrotreatment. Defined in the context of the present invention and as known in the art, a hydrotreatment (or hydroprocessing) is a catalytic reductive process for upgrading hydrocarbons. The objective of the hydrotreatment being to add hydrogen while simultaneously removing undesired heteroatoms such as but not limited to N, P, O, S, Si, F, Cl, Br, I, present in the pyrolysis oil and to reduce the amount of double bonds and if necessary aromatics. Such treatments are well known in the art and disclosed in “CHAPTER TWO - Distillate Hydrotreating”, Refinery Refining Processes Handbook, 2003, Pages 29-61. The hydrotreatment can be followed by a hydrocracking step. Further, it is conceivable that after the hydrotreatment/hydrocracking, the pyrolysis oil is further distillated to separate the oil in different fractions.

Step (v)

Preferably the process further comprises

(v) subjecting at least a portion of the pyrolysis oil O(p) comprised in L2 obtained according to (iii), or at least a portion of the purified pyrolysis oil O(pp) comprised in L2P obtained according to (iv) to

(v.1) cracking, obtaining a stream L3 comprising cracked hydrocarbons; and/or

(v.2) partial oxidation, obtaining a syngas stream L4 comprising CO and H₂.

Preferably cracking according to (v.1) is performed in a cracker. More preferably the cracker is supplied by gas or electrically, more preferably electrically, more preferably from renewable sources.

In the context of the present invention, the stream L3 is a gaseous stream.

Preferably cracking according to (v.1) is performed at a temperature in the range of from 400 to 1000 °C, more preferably in the range of from 500 to 900 °C.

The cracking is preferably performed according to processes know in the art such as those cited in Ullmann’s Encyclopedia of Industrial Chemistry, Ethylene, Ch. 5.1 , pages 469-475.

Preferably partial oxidation according to (v.2) is performed in a gasifier, such an entrained flow reactor and/or a fluidized bed reactor. The partial oxidation is preferably performed according to processes known in the art.

Step (vi)

Optionally the process of the present invention further comprises

(vi) preparing a polymer A, comprising using one or more of the stream L2 obtained according to (iii.3), the stream L3 obtained according to (v) as described herein, and the stream L1 obtained according to (iii.3) as described herein.

Preferably the polymer A is ethylene vinyl acetate.

Preferably the process further comprises reacting L1 , preferably LT, with ethylene in the presence of a catalyst, obtaining vinyl acetate. Vinyl acetate is preferably prepared according to processes known in the art, such as the Wacker process.

Ethylene vinyl acetate is preferably prepared according to processes known in the art. For example such as disclosed in DE3615563A1 , DE2617412A1, AT343354B, DE2524230A1 , DE2854151A1.

Optionally the process further comprises after (iii) or (iv) or (v):

(vii) converting a product stream L2 obtained according to (iii.3), or L2P obtained according to (iv), L3 obtained according to (v.1) as defined herein, L4 obtained according to (v.2) as defined herein, or L1 obtained according to (iii) as defined herein, obtaining a monomer, polymer or polymer product.

Preferably the monomer is a di- or polyol; preferably butandiol; aldehyde; more preferably formaldehyde; di- or polyisocyanate; more preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylenediisocyanate (HDI) or isophoronediisocyanate (I PDI); amide; more preferably caprolactam; alkene; preferably styrene, ethene and norbornene; alkyne, (di)ester; more preferably methyl methacrylate; mono or diacid; preferably adipic acid or terephthalic acid; diamine; more preferably hexamethylenediamine, nonanediamine; or sulfones; more preferably 4,4'-dichlorodiphenyl sulfone.

Preferably the polymer is and/or the polymer product comprises polyamide (PA); more preferably PA6 or PA66; polyisocyanate polyaddition product; more preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (P A), polystyrene (PS), poly acrylonitrile butadiene styrene (ABS), poly styrene acrylonitrile (SAN), poly acrylate styrene acrylonitrile (ASA), polytetrafluoroethylene (PTFE), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1 ,4-isoprene), poly(trans-1 ,4-isoprene), polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate coterephthalate (PBAT), polyester (PES), polyether sulfone (PESU), polyhydroxyalkanoate (PHA), poly- 3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyether ether ketone (PEEK), poly(p- phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymer or mixture thereof.

Preferably the polymer or polymer product is a granulate, strand, rod, plate, pipe, foil, layer, film, sheet, fiber, filament, coating, extruded and/or molded article, soft foam, half-rigid foam and/or rigid foam. Preferably the polymer and/or the polymer product is/are or is/are a part of:

- a part of a car; more preferably cylinder head cover, engine cover, housing for charge air cooler, charge air cooler flap, intake pipe, intake manifold, connector, gear wheel, fan wheel, cooling water box, housing, housing part for heat exchanger, coolant cooler, charge air cooler, thermostat, water pump, radiator, fastening part, part of battery system for electromobility, dashboard, steering column switch, seat, headrest, center console, transmission component, door module, A, B, C or D pillar cover, spoiler, door handle, exterior mirror, windscreen wiper, windscreen wiper protection housing, decorative grill, cover strip, roof rail, window frame, sunroof frame, antenna panel, headlight and taillight, engine cover, cylinder head cover, intake manifold, airbag, cushion, or coating;

- a cloth; more preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket;

- an electrical part; more preferably electrical or electronic passive or active component, circuit board, printed circuit board, housing component, foil, line, switch, plug, socket, distributor, relay, resistor, capacitor, inductor, bobbin, lamp, diode, LED, transistor, connector, regulator, integrated circuit (IC), processor, controller, memory, sensor, microswitch, microbutton, semiconductor, reflector housing for light-emitting diodes (LED), fastener for electrical or electronic component, spacer, bolt, strip, slide-in guide, screw, nut, film hinge, snap hook (snap-in), or spring tongue;

- a consumer, agricultural product or pharmaceutical product; more preferably tennis string, climbing rope, bristle, brush, artificial grass, 3D printing filament, grass trimmer, zipper, hook and loop fastener, paper machine clothing, extrusion coating, fishing line, fishing net, offshore line and rope, vial, syringe, ampoule, bottle, sliding element, spindle nut, chain conveyor, plain bearing, roller, wheel, gear, roller, ring gear, screw and spring dampers, hose, pipeline, cable sheathing, socket, switch, cable tie, fan wheel, carpet, box or bottle for cosmetics, mattress, cushion, insulation, detergent, dishwasher tabs or powder, shampoo, body wash, shower gel, soap, fertilizer, fungicide, or pesticide;

- a packaging for the food industry; more preferably mono- or multi-layer blown film, cast film (mono- or multi-layer), biaxially stretched film, or laminating film; or

- a part of a construction; more preferably a rotor blade, insulating material, frame, housing, wall, coating, or separating wall.

Preferably the content of the obtained product stream according the present invention in the monomer, polymer and/or polymer product is 1 weight-% or more, more preferably 2 weight-% or more, more preferably 5 weight-% or more, more preferably 15 weight-% or more, more preferably 30 weight-% or more, more preferably 40 weight-% or more, more preferably 60 weight- % or more, more preferably 80 weight-% or more, more preferably 90 weight-% or more, more preferably 95 weight-% or more; and/or preferably the content of the obtained product stream according the present invention in the monomer, polymer and/or polymer product is 100 weight-% or less, more preferably 95 weight- % or less, more preferably 90 weight-% or less, more preferably 50 weight-% or less, more preferably 25 weight-% or less, more preferably 10 weight-% or less; and preferably the content is 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.

The present invention further relates to a recycling unit for carrying out the process according to the present invention, the unit comprising a means for sorting the solid material W in at least two different streams based on their chemical compositions; a pyrolysis reactor R_P; an inlet means for introducing S1 into R_P; an outlet means for removing G1 from R_P; a separation unit SU; an inlet means for introducing G1 into SU; an outlet means for removing a stream L2 comprising a pyrolysis oil O(p) from SU.

Preferably the recycling unit further comprises a purification unit, an inlet means for introducing L2 into the purification unit and an outlet means for removing a stream L2P comprising a purified pyrolysis oil O(pp) depleted in one or more halogenated organic compounds and/or one or more organic compounds comprising conjugated double bonds compared to O(p).

Preferably the separation unit SU comprises

SSU1 , SSU2 being located downstream of SSU1 , an inlet means for introducing G1 in SSU1 , an outlet means for removing 01 from SSU1 , an outlet means for removing G11 from SSU1, an inlet means for introducing G11 into SSU2, and the outlet means for removing L2 from SSU2 and an outlet means for removing G3 from SSU2.

Alternatively, preferably the separation unit SU comprises

SSU1’, SSU2’ being located downstream of SSU1’, an inlet means for introducing G1 in SSU1’, an outlet means for removing L1 from SSU1’, an outlet means for removing G11 from SSU1’, an inlet means for introducing G11 into SSU2’, the outlet means for removing L2 from SSU2’ and an outlet means for removing G3 from SSU2’. Alternatively, preferably the separation unit SU comprises

SSU1”, SSU2” and SSU3”, SSU2” being located downstream of SSU1” and SSU3” being located downstream of SSU2” an inlet means for introducing G1 in SSU1”, an outlet means for removing L0 from SSU1”, an outlet means for removing G21 from SSU1”, an inlet means for introducing G21 into SSU2”, an outlet means for removing L1 from SSU2”, an outlet means for removing G22 from SSU2”, an inlet means for introducing G21 into SSU3”, the outlet means for removing L2 from SSU3” and an outlet means for removing G3 from SSU3”.

The sub-units are preferably disclosed in the foregoing.

Optionally the recycling unit further comprises a purification means PU1 , an inlet means for introducing L1 into PU1, an outlet means for removing LT from PU1 , an outlet means for removing G23 from PU1.

Preferably the recycling unit further comprises a cracker, an inlet means for introducing at least a portion of L2, or of L2P removed from the purification unit described herein, into the cracker, and an outlet means for removing from said reactor a stream L3 comprising cracked hydrocarbons.

Preferably the recycling unit further comprises a partial oxidation reactor, an inlet means for introducing L2, or of L2P removed from the purification unit described herein, into the partial oxidation reactor, and an outlet means for removing from said reactor a stream L4 comprising CO and H₂.

The present invention further relates to a process comprising : using the unit according to the present invention to obtain a purified pyrolysis oil, a monomer, polymer or polymer product.

The present invention further relates to a use of the pyrolysis oil O(p) obtained according to the process of the present invention and/or of the acetic acid obtained according to the present invention, for the production of ethylene vinyl acetate.

The present invention further relates to a use of the pyrolysis oil O(p) obtained according to the process of the present invention as the feedstock of a cracker.

The present invention further relates to a use of the pyrolysis oil O(p) obtained according to the process of the present invention as the feedstock of a partial oxidation reactor.

The present invention further relates to a process for preparing ethylene vinyl acetate from a solid material W comprising ethylene vinyl acetate comprising

(a) performing the process according to the present invention, obtaining a pyrolysis oil; (b) subjecting the pyrolysis oil obtained according to (a) to at least two subsequent treatments comprising at least one cracking and at least one polymerization, obtaining a product P comprising ethylene vinyl acetate.

(A) performing the process according to the present invention, obtaining acetic acid;

(B) subjecting acetic acid obtained according to (A) to two or more subsequent chemical treatments, obtaining a product P comprising ethylene vinyl acetate.

The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any one of embodiments 1 to 3", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

1. A process for recycling a solid material W comprising ethylene vinyl acetate, the process comprising

(i) providing the solid material W comprising polymers, the polymers comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate, wherein W comprises the ethylene vinyl acetate in an amount C1 expressed in weight-% based on the weight of W;

- a stream S1, depleted in the one or more polymers other than ethylene vinyl acetate compared to W, comprising ethylene vinyl acetate, and

- a stream S2 comprising one or more polymers other than ethylene vinyl acetate and optionally ethylene vinyl acetate, wherein S1 comprises the ethylene vinyl acetate in an amount C2 expressed in weight-% based on the weight of S1, with C2 > C1; (iii) subjecting the stream S1 obtained according to (ii) to pyrolysis conditions into a pyrolysis reactor R_P, obtaining a pyrolysis oil O(p), with (iii) comprising

(111.1) feeding S1 obtained according to (ii) into R_P;

(111.2) heating S1 fed into R_P according to (iii.1) to a temperature in the range of from 300 to 800 °C, obtaining a gas stream G1 ;

2. The process of embodiment 1 , wherein the one or more polymers other than ethylene vinyl acetate are selected from the group consisting of rubber, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyurethane (PU), thermoplastic polyurethane (TPU), and mixtures of two or more thereof, preferably selected from the group consisting of polyethylene terephthalate (PET) and polyvinyl chloride (PVC).

3. The process of embodiment 1 or 2, wherein the solid material W is a solid waste material, wherein said waste material preferably is shoe waste solid material, more preferably shoe sole waste material.

4. The process of any one of embodiments 1 to 3, wherein (i) comprises

(i.1 ) providing a solid waste material W0 comprising solid shoe material, preferably shoe sole material, comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate;

(i.2) fragmenting W0 provided in (i .1 ) to pieces, obtaining a solid material W comprising pieces of W0.

5. The process of embodiment 4, wherein fragmenting according to (i.2) comprises one or more of lacerating, cutting, shredding, grinding, granulating, and comminuting.

6. The process of any one of embodiments 1 to 5, further comprising, prior to (ii), passing W through a metal removal unit to remove metals if any in W.

7. The process of any one of embodiments 1 to 6, wherein sorting according to (ii) comprises manually sorting or automated sorting, preferably automated sorting.

8. The process of any one of embodiments 1 to 7, wherein sorting according to (ii) comprises optical sorting, preferably hyperspectral or infrared sorting, more preferably near-infrared sorting or mid-infrared sorting. 9. The process of any one of embodiments 1 to 7, wherein sorting according to (ii) comprises air-based automated sorting.

10. The process of any one of embodiments 1 to 9, wherein S1 comprises the ethylene vinyl acetate in an amount C2 being of at least 20 weight-%, preferably at least 30 weight-%, more preferably in the range of from 40 to 100 weight-%, more preferably of from 50 to 100 weight-%, based on the weight of S1.

11. The process of any one of embodiments 1 to 10, wherein feeding S1 in R_P according to (iii.1) is performed via a dosing unit, the dosing unit being preferably one or more of a screw, an extruder and a rotary valve.

12. The process of any one of embodiments 1 to 11, wherein the pyrolysis reactor R_P is selected from the group consisting of a fluidized bed, a moving bed, an entrained flow, an auger, a screw reactor, an extruder, a stirred tank reactor, and a rotary kiln.

13. The process of any one of embodiments 1 to 12, wherein the pyrolysis according to (iii) is performed in the pyrolysis reactor R_P under an atmosphere exempt of oxygen.

14. The process of any one of embodiments 1 to 13, wherein the pyrolysis according to (iii) is performed by thermal cracking (absence of catalyst) or catalytic cracking, preferably thermal cracking.

15. The process of any one of embodiments 1 to 14, wherein the temperature into R_P according to (iii.2) is in the range of from 350 to 750 °C, preferably in the range of from 450 to 650 °C.

16. The process of any one of embodiments 1 to 15, wherein the separation unit SU used in (iii.3) comprises one or more separation sub-units.

17. The process of any one of embodiments 1 to 16, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a sub-unit SSU1 and a sub-unit SSU2, for condensing, preferably at a temperature in the range of from 0 to 80°C, obtaining a first oil 01 from SSU1 and a second oil 02 from SSU2, wherein L2 comprises 01 and/or 02 as the pyrolysis oil O(p).

18. The process of any one of embodiments 1 to 16, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a sub-unit SSU1’ and a sub-unit SSU2’, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L1 comprising acetic acid from SSU1’ and the stream L2 comprising the pyrolysis oil O(p) from SSU2’.

19. The process of any one of embodiments 1 to 16, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a sub-unit SSU1”, a sub-unit SSU2” and a sub-unit SSU3”, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L0 from SSU1”, a stream L1 comprising acetic acid from SSU2” and the stream L2 comprising the pyrolysis oil O(p) from SSU3”.

20. The process of embodiment 18 or 19, further comprising

- subjecting L1 obtained according to (iii.3), in particular (iii.3.2’) or (iii.3.3”), to one or more purification stages, obtaining a purified stream LT comprising acetic acid and a stream G23 comprising the one or more compounds other than acetic acid.

21. The process of any one of embodiments 1 to 20, further comprising

22. The process of any one of embodiments 1 to 21 , further comprising

(v.1) cracking, obtaining a stream L3 comprising cracked hydrocarbons; and/or

(v.2) partial oxidation, obtaining a syngas stream L4 comprising CO and H2.

23. The process of any one of embodiments 1 to 22, further comprising

(vi) preparing a polymer A, comprising using one or more of the stream L2 obtained according to (iii.3), the stream L3 obtained according to (v) as described in embodiment 22, and the stream L1 obtained according to (iii.3) as described in embodiment 18 or 19.

24. The process of any one of embodiments 1 to 22, further comprising after (iii) or (iv) or (v):

(vii) converting a product stream L2 obtained according to (iii.3), or L2P obtained according to (iv), L3 obtained according to (v.1 ) as defined in embodiment 22, L4 obtained according to (v.2) as defined in embodiment 22, or L1 obtained according to (iii) as defined in embodiment 18 or 19, obtaining a monomer, polymer or polymer product. The process of embodiment 24, wherein the monomer is a di- or polyol; preferably bu- tandiol; aldehyde; preferably formaldehyde; di- or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylenediisocyanate (HDI) or isophoronediisocyanate (IPDI); amide; preferably caprolactam; alkene; preferably styrene, ethene and norbornene; alkyne, (di)ester; preferably methyl methacrylate; mono or diacid; preferably adipic acid or terephthalic acid; diamine; preferably hexamethylenediamine, nonanediamine; or sulfones; preferably 4,4'-dichlorodiphenyl sulfone. The process of embodiment 24 or 25, wherein the polymer is and/or the polymer product comprises polyamide (PA); preferably PA6 or PA66; polyisocyanate polyaddition product; preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocy- anurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), poly acrylonitrile butadiene styrene (ABS), poly styrene acrylonitrile (SAN), poly acrylate styrene acrylonitrile (ASA), polytetrafluoroethylene (PTFE), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1 ,4- isoprene), poly(trans-1 ,4-isoprene), polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate coterephthalate (PBAT), polyester (PES), polyether sulfone (PESU), polyhydroxyalkanoate (PHA), poly-3-hydroxy- butyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyether ether ketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymer or mixture thereof. The process of any one of embodiments 24 to 26, wherein the polymer or polymer product is a granulate, strand, rod, plate, pipe, foil, layer, film, sheet, fiber, filament, coating, extruded and/or molded article, soft foam, half-rigid foam and/or rigid foam. The process of any one of embodiments 24 to 27, wherein the polymer and/or the polymer product is/are or is/are a part of: a part of a car; preferably cylinder head cover, engine cover, housing for charge air cooler, charge air cooler flap, intake pipe, intake manifold, connector, gear wheel, fan wheel, cooling water box, housing, housing part for heat exchanger, coolant cooler, charge air cooler, thermostat, water pump, radiator, fastening part, part of battery system for electromobility, dashboard, steering column switch, seat, headrest, center console, transmission component, door module, A, B, C or D pillar cover, spoiler, door handle, exterior mirror, windscreen wiper, windscreen wiper protection housing, decorative grill, cover strip, roof rail, window frame, sunroof frame, antenna panel, headlight and taillight, engine cover, cylinder head cover, intake manifold, airbag, cushion, or coating; a cloth; preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket; an electrical part; preferably electrical or electronic passive or active component, circuit board, printed circuit board, housing component, foil, line, switch, plug, socket, distributor, relay, resistor, capacitor, inductor, bobbin, lamp, diode, LED, transistor, connector, regulator, integrated circuit (IO), processor, controller, memory, sensor, microswitch, microbutton, semiconductor, reflector housing for light-emitting diodes (LED), fastener for electrical or electronic component, spacer, bolt, strip, slide-in guide, screw, nut, film hinge, snap hook (snap-in), or spring tongue; a consumer, agricultural product or pharmaceutical product; preferably tennis string, climbing rope, bristle, brush, artificial grass, 3D printing filament, grass trimmer, zipper, hook and loop fastener, paper machine clothing, extrusion coating, fishing line, fishing net, offshore line and rope, vial, syringe, ampoule, bottle, sliding element, spindle nut, chain conveyor, plain bearing, roller, wheel, gear, roller, ring gear, screw and spring dampers, hose, pipeline, cable sheathing, socket, switch, cable tie, fan wheel, carpet, box or bottle for cosmetics, mattress, cushion, insulation, detergent, dishwasher tabs or powder, shampoo, body wash, shower gel, soap, fertilizer, fungicide, or pesticide; a packaging for the food industry; preferably mono- or multi-layer blown film, cast film (mono- or multi-layer), biaxially stretched film, or laminating film; or a part of a construction; preferably a rotor blade, insulating material, frame, housing, wall, coating, or separating wall. The process of any one of embodiments 24 to 28, wherein the content of the obtained H₂ and/or CO according to d) in the monomer, polymer and/or polymer product is 1 weight-% or more, preferably 2 weight-% or more, more preferably 5 weight-% or more, more preferably 15 weight-% or more, more preferably 30 weight-% or more, more preferably 40 weight-% or more, more preferably 60 weight-% or more, more preferably 80 weight-% or more, more preferably 90 weight-% or more, more preferably 95 weight-% or more; and/or wherein the content of the obtained H₂ and/or CO in the monomer, polymer and/or polymer product is 100 weight-% or less, preferably 95 weight-% or less, more preferably 90 weight-% or less, more preferably 50 weight-% or less, more preferably 25 weight-% or less, more preferably 10 weight-% or less; and preferably wherein the content is determined based on identity preservation and/or segregation and/or mass balance and/or book and claim chain of custody models, preferably based on mass balance, preferably the International Sustainability and Carbon Certification (ISCC) standard. A recycling unit for carrying out the process according to any one of embodiments 1 to 22, the unit comprising a means for sorting the solid material W in at least two different streams based on their chemical compositions; a pyrolysis reactor R_P; an inlet means for introducing S1 into R_P; an outlet means for removing G1 from R_P; a separation unit SU; an inlet means for introducing G1 into SU; an outlet means for removing a stream L2 comprising a pyrolysis oil O(p) from SU. The recycling unit of embodiment 30, further comprising a purification unit, an inlet means for introducing L2 into the purification unit and an outlet means for removing a stream L2P comprising a purified pyrolysis oil O(pp) depleted in one or more halogenated organic compounds and/or one or more organic compounds comprising conjugated double bonds compared to O(p). The recycling unit of embodiment 30 or 31 , further comprising a cracker, an inlet means for introducing at least a portion of L2, or of L2P removed from the purification unit described in embodiment 30, into the cracker, and an outlet means for removing from said reactor a stream L3 comprising cracked hydrocarbons. The recycling unit of any one of embodiments 30 to 32, further comprising a partial oxidation reactor, an inlet means for introducing L2, or of L2P removed from the purification unit described in embodiment 30, into the partial oxidation reactor, and an outlet means for removing from said reactor a stream L4 comprising CO and H₂. rocess comprising the step: using the unit according to any one of embodiments 30 to 33 to obtain a purified pyrolysis oil, a monomer, polymer or polymer product. Use of the pyrolysis oil O(p) obtained according to the process of any one of embodiments 1 to 22 and/or of the acetic acid obtained according to any one of embodiments 18 to 20, for the production of ethylene vinyl acetate. 36. Use of the pyrolysis oil O(p) obtained according to the process of any one of embodiments 1 to 22 as the feedstock of a cracker.

37. A process for preparing ethylene vinyl acetate from a solid material W comprising ethylene vinyl acetate comprising

(a) performing the process according to any one of embodiments 1 to 22, obtaining a pyrolysis oil;

(b) subjecting the pyrolysis oil obtained according to (a) to at least two subsequent treatments comprising at least one cracking and at least one polymerization, obtaining a product P comprising ethylene vinyl acetate.

38. A process for preparing ethylene vinyl acetate from a solid material W comprising ethylene vinyl acetate comprising

(A) performing the process according to any one of embodiments 18 to 20, obtaining acetic acid;

It is explicitly noted that the above set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

In the context of the present invention, a term “X is one or more of A, B and C”, wherein X is a given feature and each of A, B and C stands for specific realization of said feature, is to be understood as disclosing that X is either A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this regard, it is noted that the skilled person is capable of transfer to above abstract term to a concrete example, e.g. where 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. In this regard, it is further noted that the skilled person is capable of extending the above term to less specific realizations of said feature, e.g. “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.

The present invention is further illustrated by the following Examples.

Example section Analytics

1.1 Calorific values (calculation)

If not measured, the calorific values can be approximated as described in the following: The calorific values of combustibles depend on their chemical composition. An empirical correlation for the upper calorific value, that can be used in a wide variety of cases (solid, liquid, and gaseous fuels), was proposed by Channiwala and Parikh [1]:

H_o = 34.91 ■ w_c + 117.83 ■ w_h + 10.05 ■ w_s — 10.34 • w₀ — 1.51 • w_n — 2.11 • w_a Eq. 1

The conversion into the lower calorific value is done according to:

H_u = H_o - 2.441 ■ ( w_H20 + 9 ■ w_h) Eq. 2

The values of H_o & H_u are in MJ/kg and the weight fraction w, of element / in kg/kg.

1.2 Determination of F, Cl, Br, I and S contents: Said contents have been determined according to DIN EN 15408: 2011-05.

1.3 Determination of C, H and N contents: Said contents have been determined according to DIN EN 15407: 2011-05.

1.4 Determination of O content: Said content has been determined according to DIN EN ISO 16993.

1.5 Determination of the aromatic, olefinic and aliphatic fractions in a pyrolysis oil: These fractions have been determined with NMR analysis in ds-THF. To do so, 5-10 mg of a sample is dissolved in d8-THF and filled in a 5mm tube at room temperature. A 400 MHz-spectrometer is used at room temperature (i.e. 298.2 K - about 25 °C).

Example 1 Process for recycling a waste material comprising EVA according to the present invention

Three different feedstocks have been tested for the pyrolysis in this example: Feedstock S1(A) with only pieces of EVA, Feedstock S1(B) with pieces of EVA and rubber from shoe sole (SR in the following) (weight ratio 1 :1) and Feedstock S1(C) with pieces of EVA, rubber from shoe sole and PET (weight ratio 1 (EVA): 1(SR): 0.2 (PET)).

These “virgin” feedstocks represent different streams that can be obtained after sorting according to the process of the present invention, namely after shoe soles have been fragmented into pieces and sorted to obtain S1(A), S1(B) and S1 (C) comprising EVA. The analysis of said feedstock is presented in Table 1 below.

Table 1 Analysis of the feedstocks (Heating Values, ultimate and proximate analysis)

HHV= Higher heating value / LHV= Lower heating value For the pyrolysis experiments, a bench scale pyrolysis system was used. The pyrolysis system comprises a pyrolysis reactor R_P, an electrically heated oven, two condensers and two washing bottles. Firstly, the reactor was filled with the feedstock S1. Then a pressure-test was carried out to ensure that the system was air-tight. Furthermore, the plant volume was flushed before and during the experiments with nitrogen to ensure an oxygen-free atmosphere in the setup. The nitrogen was introduced into the reactor via a capillary, whose opening is located roughly in the axial center of R_P. A 1 m water column was used as overpressure protection (100 mbarg). First, the oven was pre-heated to set point temperature. Then the oven was elevated to enclose the pyrolysis reactor R_P. Subsequently, R_P was heated up to set reaction temperature of about 550°C. The reaction temperature was measured via a NiCrNi-thermocouple, whose tip is in the vicinity of the capillary opening of the N2 supply.

The effluent pyrolysis vapors and gases (stream G1) coming from the pyrolysis reactor R_P was transferred via a heated pipe to the two condensers in which the pyrolysis vapors (G1) are condensed. The condensed pyrolysis vapor is the pyrolysis oil O(p). The temperature of the first condenser was adjusted via a heated water bath to its temperature set-point of about 40-50 °C, while the temperature of the second condenser was adjusted via a cooling bath with ice water to its temperature set-point of about 0°C.

The non-condensable gases (stream G3) were cleaned in two washing bottles. The first washing bottle was filled with a NaOH-solution (1 M NaOH) to capture volatile acidic products. The second washing bottle was filled with distilled water. The off-gas was vented into the air-discharge vent of the digestorium.

After the experiments, the obtained pyrolysis oil O(p) and the obtained char were weighted. The results are shown in Tables 2-4 below.

Table 2 Masses of pyrolysis oil O(p) (01 from condenser 1 + 02 from condenser 2) and char - as well as overall yields

‘calculated by difference: 100 - (L2 yield) - (solids yield)

Table 3 Elemental composition of pyrolysis oil O(p)

Table 4 Analysis of the aromatic, olefinic, and aliphatic fractions in the pyrolysis oil O(p) (L2)

As may be taken from the analysis of the pyrolysis oil obtained according to the recycling process of the present invention, it has been demonstrated that high quality pyrolysis oil can be obtained, in particular with low O content, low aromatics content and in good yields. Therefore, it has been demonstrated that thanks to the recycling process of the present invention it is possible to recover good pyrolysis oil for subsequent use such as the production of new polymers, such as EVA, PU, etc. This process is thus an economical and energy efficient process deliver- ing valuable materials, which comprise high technical features. In contrast, the mere incineration of waste materials, in particular sport shoes and sport shoe soles, has a negative impact on the environment as well as on the carbon footprint. Further, thanks to the inventive process it is possible to obtain acetic acid which can also be used for producing EVA. Hence, the present recycling process renders the production of EVA more sustainable, which is crucial for the environment since it has been proven that its recycling from waste material is feasible with valuable products at the end.

Brief description of the figures

Figure 1 represents a schematic representation of the recycling process according to embodiments of the present invention. The recycling unit for carrying out the process comprises a means MS for sorting the solid material W in at least two different streams based on their chemical compositions; a pyrolysis reactor R_P and a separation unit SU. A solid material W comprising polymers, the polymers comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate, wherein W comprises the ethylene vinyl acetate in an amount C1 expressed in weight-% based on the weight of W, is sorted in two different streams S1 and S2 via the means MS. S1 is depleted in the one or more polymers other than ethylene vinyl acetate compared to W and comprises ethylene vinyl acetate (EVA) and S2 comprising one or more polymers other than EVA and optionally EVA, S1 comprises the EVA in an amount C2 expressed in weight-% based on the weight of S1 , with C2 > C1. The stream S1 is fed into RP and heated therein to a temperature in the range of from 300 to 800 °C, obtaining a gas stream G1. The gas stream G1 is removed from RP and condensed in a separation unit SU. A stream L2 comprising a pyrolysis oil Op is then removed from SU as well as an uncondensed gas stream G3.

Figure 2 represents a schematic representation of the recycling process according to embodiments of the present invention. The recycling unit for carrying out the process comprises a means MS for sorting the solid material W in at least two different streams based on their chemical compositions; a pyrolysis reactor R_P, a separation unit SU comprising a sub-unit SSUT and a sub-unit SSU2’, a purification unit PU1 , optionally a purification unit PU2, a cracker C, a gasifier G, an acid acetic storage unit AAU and optionally a vinyl acetate production unit VAP. The recycling unit can further comprise a shoe production unit SPU and/or a subsequent treatments unit ST for obtaining a polymer A such as EVA for example. A solid material W comprising polymers, the polymers comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate, wherein W comprises the ethylene vinyl acetate in an amount C1 expressed in weight-% based on the weight of W, is sorted in two different streams S1 and S2 via the means MS. S1 is depleted in the one or more polymers other than ethylene vinyl acetate compared to W and comprises ethylene vinyl acetate (EVA) and S2 comprising one or more polymers other than EVA and optionally EVA, S1 comprises the EVA in an amount C2 expressed in weight-% based on the weight of S1, with C2 > C1. The stream S1 is fed into RP and heated therein to a temperature in the range of from 300 to 800 °C, obtaining a gas stream G1. The gas stream G1 is removed from RP and condensed in SSUT to obtain a stream L1 comprising acetic acid and one or more compounds other than acetic acid, and a non-condensed stream G11. The stream G11 is removed from SSUT and introduced into SSU2’ for condensation to obtain a stream L2 comprising a pyrolysis oil Op which is then removed from SU as well as an uncondensed gas stream G3. The stream L1 is removed from SSUT and introduced in a purification unit PU1 to separate the acetic acid from the other compounds such as waxes, etc., to obtain a purified stream LT comprising acetic acid. The acetic acid can be stored in AAU and then sent to ST for producing a polymer A such as EVA. L’1 can also be transferred to VAP for producing vinyl acetate which can then be sent to ST for producing a polymer A such as EVA. Further, the stream L2 can be purified in PU2 prior to be cracked in C or partially oxidized in G. From the gasifier G, a stream L4 is removed comprising CO and H2 which can be sent to ST for producing a polymer A such as EVA. From the cracker C, a stream L3 is removed comprising cracked hydrocarbons which can be sent to ST for producing a polymer A such as EVA. The polymer A (PA) is then removed from ST and can be introduced in a unit for producing shoes SPU. The results of the production will eventually become new waste material W which can then be processed according to the present invention.

Cited literature

- CHAPTER TWO - Distillate Hydrotreating, Refinery Refining Processes Handbook, 2003, Pages 29-61

- Ullmann’s Encyclopedia of Industrial Chemistry, Ethylene, Ch. 5.1, pages 469-475

- DE3615563A1

- DE2617412A1

- AT343354B

- DE2524230A1

- DE2854151A1

Claims

- a stream S2 comprising one or more polymers other than ethylene vinyl acetate and optionally ethylene vinyl acetate, wherein S1 comprises the ethylene vinyl acetate in an amount C2 expressed in weight-% based on the weight of S1, with C2 > C1;

(iii) subjecting the stream S1 obtained according to (ii) to pyrolysis conditions into a pyrolysis reactor RP, obtaining a pyrolysis oil O(p), with (iii) comprising

(111.1) feeding S1 obtained according to (ii) into R_P;

(111.3) removing G1 obtained according to (iii.2) from P and subjecting G1 to condensation conditions in a separation unit SU, obtaining a stream L2 comprising the pyrolysis oil O(p).

2. The process of claim 1 , wherein the one or more polymers other than ethylene vinyl acetate are selected from the group consisting of rubber, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyurethane (PU), thermoplastic polyurethane (TPU), and mixtures of two or more thereof, preferably selected from the group consisting of rubber, polyethylene terephthalate (PET) and polyvinyl chloride (PVC).

3. The process of claim 1 or 2, wherein (i) comprises

(i.1 ) providing a solid waste material W0 comprising solid shoe material, preferably shoe sole material, comprising ethylene vinyl acetate and one or more polymers other than ethylene vinyl acetate; (i.2) fragmenting WO provided in (i.1) to pieces, obtaining a solid material W comprising pieces of WO.

4. The process of claim 3, wherein fragmenting according to (i.2) comprises one or more of lacerating, cutting, shredding, grinding, granulating, and comminuting.

5. The process of any one of claims 1 to 4, wherein sorting according to (ii) comprises optical sorting, preferably hyperspectral or infrared sorting, more preferably near-infrared sorting or mid-infrared sorting; or wherein sorting according to (ii) comprises air-based automated sorting.

6. The process of any one of claims 1 to 5, wherein S1 comprises the ethylene vinyl acetate in an amount C2 being of at least 20 weight-%, preferably of at least 30 weight-%, more preferably in the range of from 40 to 100 weight-%, more preferably in the range of from 50 to 100 weight-%, based on the weight of S1.

7. The process of any one of claims 1 to 6, wherein the separation unit SU used in (iii.3) comprises one or more separation sub-units.

8. The process of any one of claims 1 to 7, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from Rp and passing G1 in SU, SU comprising a sub-unit SSU1 and a sub-unit SSU2, for condensing, preferably at a temperature in the range of from 0 to 80°C, obtaining a first oil 01 from SSU1 and a second oil 02 from SSU2, wherein L2 comprises 01 and/or 02 as the pyrolysis oil O(p).

9. The process of any one of claims 1 to 7, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from Rp and passing G1 in SU, SU comprising a sub-unit SSUT and a sub-unit SSU2’, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L1 comprising acetic acid from SSUT and the stream L2 comprising the pyrolysis oil O(p) from SSU2’; wherein preferably (iii.3) comprises

(iii.3. ) removing G1 obtained according to (iii.2) from R_P;

(Hi.3.2’) passing G1 removed from RP according to (iii.3. T) in a first separation subunit SSUT, comprised in SU, at a temperature above 110 °C, more preferably in the range of from above 110 to 130°C, more preferably from above 110 to 120 °C, obtaining the stream L1 comprising acetic acid and one or more compounds other than acetic acid, and a gas stream G1 T; (iii.3.3’) passing G1 T obtained according to (iii.3.2’) in a second separation sub-unit SSU2’, comprised in SU and located downstream of SSUT, at a temperature of at most 100 °C, more preferably in the range of from 0 to 80 °C, obtaining the stream L2 comprising O(p), and a gas stream G3.

10. The process of any one of claims 1 to 7, wherein (iii.3) comprises removing G1 obtained according to (iii.2) from R_P and passing G1 in SU, SU comprising a sub-unit SSU1”, a sub-unit SSU2” and a sub-unit SSU3”, for condensing, preferably at a temperature in the range of from 0 to 180 °C, obtaining a stream L0 from SSU1”, a stream L1 comprising acetic acid from SSU2” and the stream L2 comprising the pyrolysis oil O(p) from SSU3”.

11. The process of claim 9 or 10, further comprising

12. The process of any one of claims 1 to 11 , further comprising

(v.1) cracking, obtaining a stream L3 comprising cracked hydrocarbons; and/or

(v.2) partial oxidation, obtaining a syngas stream L4 comprising CO and H2.

13. The process of any one of claims 1 to 12, further comprising

(vi) preparing a polymer A, comprising using one or more of the stream L2 obtained according to (iii.3), the stream L3 obtained according to (v) as described in claim 12, and the stream L1 obtained according to (iii.3) as described in claim 9 or 10.

14. A recycling unit for carrying out the process according to any one of claims 1 to 13, the unit comprising a means for sorting the solid material W in at least two different streams based on their chemical compositions; a pyrolysis reactor R_P; an inlet means for introducing S1 into R_P; an outlet means for removing G1 from R_P; a separation unit SU; an inlet means for introducing G1 into SU; an outlet means for removing a stream L2 comprising a pyrolysis oil O(p) from SU.

15. Use of the pyrolysis oil O(p) obtained according to the process of any one claims 1 to 12 and/or of the acetic acid obtained according to any one of claims 9 to 11 , for the production of ethylene vinyl acetate.