Mechanical treatment process for a new defective or used product initially comprising at least one elastomeric material and at least one other material, related recycling installation and process, elastomeric granule(s) obtained.

Abstract

Mechanical treatment process for a new defective or used product initially comprising at least one elastomeric material and at least one other material, related recycling installation and process, elastomeric granule(s) obtained.The invention relates to a mechanical treatment process for a new, defective, or used product initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material, or a combination thereof, for the purpose of its recycling, comprising the following steps: i / mechanical grinding of at least a portion of the product to obtain ground pieces; ii / dry air screening of at least a portion of the pieces resulting from grinding according to step i / ; iii / separation by an airflow of the pieces resulting from step ii / to calibrate said pieces; iv / sorting by mechanical vibration on an air cushion of the calibrated pieces according to step iii / to obtain essentially at least one elastomeric granule(s). Figure for the abstract: Fig. 1.

Description

Title of the invention: Mechanical treatment process for a new defective or used product initially comprising at least one elastomeric material and at least one other material, Related recycling installation and process, Elastomeric granule(s) obtained. technical field

[0001] The present invention relates to the field of recycling defective or used new products which are made up of several materials including at least one elastomeric material.

[0002] By "new defective product", we mean here and within the framework of the invention, a new product but which has not been used or, where applicable, a product resulting from a production offcut.

[0003] By "used product", we mean here and within the framework of the invention, a product which has already been used and which is therefore post-consumer.

[0004] More specifically, the invention relates firstly to a process and an associated installation for the mechanical treatment of such products before the recycling of the elastomeric material(s) initially present in the products.

[0005] The elastomeric material(s) that are primarily concerned by the process are rubbers, polyurethane (PU), thermoplastic elastomers, such as thermoplastic polyurethane (TPU) and ethylene-vinyl acetate (EVA).

[0006] A preferred application is the processing of used sporting goods, such as tennis balls or sports shoe soles.

[0007] Although described with reference to this preferred application, the invention can be implemented for any type of other new, defective or used products comprising at least one elastomeric material.

[0008] Examples of products resulting from the process include sports flooring, acoustic insulation products, flooring for use as parquet underlayment, mixed elastomer / thermoplastic alloy parts, motor vehicle accessories, tennis soles and balls... Previous technique

[0009] Recent studies report that approximately 400 million tennis balls are used worldwide each year. Such high consumption is determined by several factors, including the fact that a tennis ball has a short lifespan due to the pressure loss it is subjected to and the rapid wear of its constituent materials, particularly the surface felt.

[0010] The deterioration of the outer felt layer varies according to the conditions of use of the tennis ball, with reference to the characteristics of the playing surface, the strings of the rackets and the climatic conditions of use.

[0011] As is known, a tennis ball is made from multiple non-biodegradable and non-compostable materials. These materials include mixtures of rubber, carbon black, sulfur and other substances, bonded together by a vulcanization process, onto which are glued two felt films, made from a mixed material of wool and synthetic fibers, necessary to allow better adhesion of the strings of a racket and increase their friction with the air, thus making them more controllable.

[0012] Due to the mixed composition and the bond between the inner and outer layers, the recycling of tennis balls is currently difficult and almost non-existent, which generates several tons of waste to be sent to landfills or energy recovery plants for disposal.

[0013] Various attempts to treat these used tennis balls have been made.

[0014] Patent EP4183286B1 thus proposes a method for manufacturing soles for sports shoes which consist of grinding up used tennis balls, reducing them into fragments of predetermined dimensions and selecting these to add to a rubber compound in a proportion of 3 to 25% to finally mold a sole from this mixture.

[0015] US patents 11135796B2 and 9114580B2 disclose methods for manufacturing shoe soles that involve the use of recycled materials such as thermoplastic elastomers TPE or ethylene-vinyl acetate (EVA) to be incorporated into the raw materials normally used in the production of shoe soles.

[0016] In practice, it is observed that the soles obtained are not satisfactory.

[0017] Indeed, if the recycled material to be used is of the type which does not bond mechanically and / or chemically to the new elastomer material(s) intended to make up a shoe sole, then the quality and durability of the latter are not satisfactory.

[0018] Moreover, the processes described are really only usable for a specific type of used product / article, essentially used tennis balls as indicated above.

[0019] However, there is a need to be able to recycle many other used products / articles, or those from production scraps, or even new ones that have not been put on the market because they are defective.

[0020] That being said, just like tennis balls, almost all of these products are composed of several layers and / or components of different materials, including at least one elastomer.

[0021] Publication [1] proposes an economically viable automated material recycling process for mixed post-consumer footwear waste, comprising an air separation unit that separates granulated shoe particles based on size and weight differences. Experimental studies on three different types of post-consumer footwear products show that it is possible to recover four usable material streams: leather, textiles, foams, and rubbers. For each of the recovered materials, there are a variety of applications such as surface materials, insulation panels, and underlay products. However, as the authors themselves indicate in their conclusion, their process does not achieve a degree of purity for the materials that would make them suitable for new, high-value-added products.

[0022] Thus, to date, there is no truly universal industrial process which would allow obtaining a maximum of usable materials for the production of a new product / article from a used or new multi-layer and / or multi-component product.

[0023] The aim of the present invention is therefore to propose such a process which allows, mechanically and without water, efficient and practical, the production of a recycled product with high quality and durability, for example exhibiting high abrasion resistance and / or high mechanical properties, such as tensile strength, tear resistance, etc., and / or maintaining over time a set of specifications, in particular imposed by a manufacturer of said product. Description of the invention

[0024] To this end, the invention relates, according to one of its aspects, to a method for the mechanical treatment of a defective or used new product initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material or a combination thereof, with a view to its recycling, comprising the following steps:

[0025] i / mechanical grinding of at least part of the product so as to obtain ground pieces of a unit size less than or equal to a first predetermined threshold value;

[0026] he / where applicable, magnetic separation of the pieces in magnetic material from the other bulk pieces resulting from the grinding according to step i / ;

[0027] i2 / where applicable, before or after step il / , metallic separation of the pieces in non-magnetic metallic material from other bulk pieces resulting from grinding according to step i / ;

[0028] ii / dry air screening of at least a portion of the pieces of textile material and / or other pieces of bulk elastomer of density less than or equal to the first predetermined threshold value of those from grinding according to step i / or where appropriate from step il / or i2 / ;

[0029] iii / separation by an airflow of the pieces resulting from a density greater than the first threshold value of step ii / so as to calibrate said pieces to a unit size less than or equal to a second threshold value;

[0030] iv / sorting by mechanical vibration on an air cushion of the pieces calibrated according to step iii / so as to obtain essentially at least one elastomer granule(s) with pieces of unit size less than or equal to a third threshold value.

[0031] Advantageously, steps i / to iv / are carried out continuously.

[0032] Preferably, the first unit size threshold value according to step i / is equal to 40mm.

[0033] Preferably the second unit size threshold value according to step iii / is equal to 6 mm.

[0034] Preferably, the third unit size threshold value according to step iv / is less than or equal to 6 mm, preferably 4 mm, preferably between 1 and 6 mm, preferably between 1 and 4 mm.

[0035] According to an advantageous embodiment, the process comprises, after step iv / , a step v / of micronization of the elastomer granule(s), preferably so as to obtain micronized particles of unit size less than or equal to 500 pm, preferably still between 100 and 500 pm.

[0036] The mechanical treatment process can be carried out for a sports article based on natural or synthetic textile, or not, as a product, such as a used tennis ball, a used or new sports shoe.

[0037] The product may contain, as a textile, wool fibers, nylon fibers, including polyamide (PA), acrylic fibers, polyethylene terephthalate (PET) fibers, elastane fibers, thermoplastic polyurethane (TPU) fibers, cotton fibers, flax fibers or a combination of said fibers.

[0038] The invention also relates to an installation for the continuous mechanical processing of a new, defective or used product initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material or a combination thereof, for the purpose of its recycling, comprising:

[0039] - a mechanical grinding device for at least part of the product so as to to obtain crushed pieces of a unit size less than or equal to a first predetermined threshold value;

[0040] - where applicable, a magnetic separation device for the pieces of material magnetic separation of other loose pieces from the grinding device;

[0041] - where applicable, a metallic separation device for the pieces of material non-magnetic metallic from the other bulk pieces from the grinding device;

[0042] - a dry screening apparatus for separating at least some of the pieces into textile material and / or other bulk elastomer pieces from the grinding apparatus or, where applicable, from the eddy current separation device or the magnetic separation device

[0043] - an air density separator for separating the pieces from the device dry screening, so as to calibrate said pieces to a unit size less than or equal to a second threshold value;

[0044] - a mechanical vibration table with an air cushion for sorting calibrated pieces resulting from the screening apparatus so as to obtain essentially at least one elastomer granule(s) with unit size less than or equal to a threshold value.

[0045] The invention also relates to an elastomer granule(s), obtained from a new or used product initially comprising at least one elastomer material and at least one other material chosen from a textile material, a ferrous metallic material, the purity level of which is greater than 87%, preferably greater than 95%, preferably even greater than 99%.

[0046] When the granulate is a rubber granulate, the purity rate is greater than 93%, preferably greater than 95%, preferably even greater than 99%.

[0047] When the granule is an ethylene vinyl acetate (EVA) granule, the purity level is greater than 87%.

[0048] The invention also relates to a recycling process comprising, after step iv / or where appropriate after step v / of the mechanical treatment process as described above, a step vi / of devulcanization of the elastomer(s) of the granulate pieces and / or of micronization of the elastomer(s) granulate pieces, so as to obtain an intermediate material.

[0049] According to an advantageous embodiment, the process includes, after step vi / , a step of reincorporating the recycled intermediate material into a new matrix of said (said) elastomer(s).

[0050] The invention finally relates to a new article / product incorporating at least one elastomer element(s) obtained by the devulcanization and / or micronization process as described above.

[0051] Thus, the invention essentially consists of a purely mechanical treatment process which, by a judicious choice of sequences of separation steps and related technical means, makes it possible to obtain, from a wide variety of types of used multi-layer and / or multi-component products or products from production scraps or defective new products never used, an elastomer granule(s) with a very high purity rate.

[0052] This very high purity rate will make it possible to guarantee a transformation of said aggregate while maintaining, or at the very least degrading, its chemical and mechanical properties.

[0053] Thanks to this, the products / articles which will be manufactured by incorporating at least one elastomer element(s) obtained from the process, are of very good quality.

[0054] Furthermore, the judicious selection of equipment and devices in an installation according to the invention allows for reduced energy consumption. Thus, the invention enables control over the life cycle assessment (LCA) of the used products that are processed. This makes it possible to improve the environmental impact.

[0055] The advantages of the invention compared to state-of-the-art mixed material treatment solutions are numerous, among which we can mention: - the possibility of treating a very wide variety of types of used multi-layer and / or multi-component products, or products from production scraps or new ones never used, with the guarantee of a very high elastomer purity level; - obtaining new articles / products from an element incorporating highly pure recycled elastomer.

[0056] The used products that can be treated by the process according to the invention are numerous and varied.

[0057] Examples include shoes, skates, so-called "bonbouts" heels, boots, climbing shoes, mattresses, tennis balls and balls in general (golf, football, etc.), EVA foams, inner tubes, especially for bicycles, all production scraps from these products, sports shoes (football, rugby, etc.), gloves, diving suits, electrical cable sheaths, seals, thermoplastic elastomer parts, household items, furniture, gardening and DIY items, carpets and floor coverings, belts, mattresses for example made of styrene-butadiene latex (SBR, English acronym for "Styrene-Butadiene Rubber"), production scraps for example made of butyl and conveyor belts.

[0058] Rubbers that can be treated include natural rubber (NR), BR rubbers (Anglo-Saxon acronym for "Butadiene Rubber"), SBR ("Styrene Butadiene Rubber"), IR (synthetic polyisoprene), IIR ("Butyl Rubber") "), BIIR ("Bromobutyl Rubber"), CIIR ("Chlorobutyl Rubber"), NBR ("Nitrile Rubber"), EPDM ("Ethylene Propylene Diene Monomer") or a mixture of these.

[0059] The recycled products that can be obtained from the process according to the invention are numerous and varied.

[0060] Examples include shoe soles, tennis balls, sports flooring, acoustic insulation panels or elements, flooring used as underlay for parquet flooring, parts made of elastomeric / thermoplastic alloys, motor vehicle accessories...

[0061] Other advantages and features of the invention will become clearer from the detailed description of examples of implementation of the invention given by way of illustration and not limitation with reference to the following figures. Brief description of the drawings

[0062] [Fig-1] [Fig.1] represents a synoptic diagram of a continuous installation putting into implements the mechanical treatment process according to the invention.

[0063] [Fig.2] [Fig.2] is a photographic reproduction of a rubber granule and felt obtained at the outlet of the installation according to the invention from used tennis balls.

[0064] [Fig.3] [Fig.3] illustrates, in the form of curves, the thermogravimetric analysis of aggregates from different compositions from completely different bales.

[0065] [Fig.4] [Fig.4] shows the infrared spectroscopy analysis curves at Fourier transform of aggregate obtained at the outlet of the installation according to the invention from used tennis balls.

[0066] [Fig. 5] [Fig. 5] illustrates in the form of curves the composition of different devulcanizates obtained by devulcanization from granules of the [Fig.3] in a twin-screw extruder.

[0067] [Fig. 6A], [Fig. 6B] Figures 6A and 6B are photographic reproductions of devulcanizate forms obtained by a twin-screw extruder.

[0068] [Fig.7] [Fig.7] is a photographic reproduction of mixture shapes of devulcanized material obtained as shown in figures 6A and 6B with a virgin rubber base.

[0069] [Fig.8] [Fig.8] is a photographic reproduction of a rubber granule obtained at the outlet of the installation according to the invention from used complex shoes.

[0070] [Fig.9] [Fig.9] illustrates, in the form of curves, the thermogravimetric analysis of aggregates from different compositions derived from different complex footwear.

[0071] [Fig.10] [Fig.10] is a photographic reproduction of a micronized sample obtained at starting from a rubber granule according to [Fig.8].

[0072] [Fig. 11] [Fig. 11] illustrates, in the form of curves, the thermogravimetric analysis of micronized products derived from different compositions of different complex footwear.

[0073] [Fig. 12] [Fig. 12] shows the infrared spectroscopy analysis curves at Fourier transform of micronized material obtained from aggregate obtained at the outlet of the installation according to the invention from complex shoes.

[0074] [Fig. 13] [Fig. 13] is a photographic reproduction of a sole obtained with a mixture of micronized material with a virgin rubber base.

[0075] [Fig. 14] [Fig. 14] is a photographic reproduction of the light fraction, comprising a high proportion of leather and foams, of a rubber granule obtained at the outlet of the installation according to the invention from used cupsoles shoe soles.

[0076] [Fig. 15] [Fig. 15] is a photographic reproduction of the heavy fraction, without leather, rubber granules according to [Fig. 14].

[0077] [Fig. 16] [Fig. 16] illustrates, in the form of curves, the thermogravimetric analysis of aggregates from different compositions derived from different cupsoles of shoes.

[0078] [Fig. 17] [Fig. 17] is a photographic reproduction of a micronized sample obtained at part of a rubber granule according to [Fig. 15].

[0079] [Fig. 18] [Fig. 18] illustrates, in the form of curves, the thermogravimetric analysis of micronized from different compositions derived from different cupsoles of shoes.

[0080] [Fig. 19] [Fig. 19] shows the infrared spectroscopy analysis curves at Fourier transform of micronized granulate obtained from granulate obtained at the outlet of the installation according to the invention from cupsole shoes.

[0081] [Fig.20] [Fig.20] shows photographic reproductions respectively of a granules and a micronized product obtained from cupsoles.

[0082] [Fig. 21] [Fig. 21] is a photographic reproduction of a sole pad shoe obtained with a mixture of devulcanized material from cupsoles with a virgin rubber base. Detailed description

[0083] Throughout this application, the terms "front" and "back", "inlet" and "outlet" are to be understood in relation to the direction of flow of material in the installation according to the invention.

[0084] In the various tables, the acronyms used, ML, MH, Ts2 and T90, respectively designate the minimum torque, the maximum torque, and the time for the pair units above ML, the time for 90% of the crosslinking to have occurred.

[0085] A continuous mechanical processing installation 1 according to the invention is shown in [Fig.1].

[0086] At the input of installation 1, one or more new defective or used products initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material or a combination thereof are supplied.

[0087] A first mechanical grinding device 2 allows at least a portion of the product to be mechanically ground so as to obtain ground pieces with a unit size less than or equal to a first predetermined threshold value. Typically, this first threshold value may be 40 mm. By way of example, this device 2 may be a slow-speed, two- or four-axis grinder, such as equipment from the UNTHA brand, marketed under the reference RS 100.

[0088] These pieces, ground once, feed a magnetic separation device 3. Thus, any pieces of magnetic material are separated from the other bulk pieces from the grinding device 2. As an example, this device 3 can be a permanent magnet, a magnetic strip or a magnetic roller, such as equipment from the STEINERT brand, marketed under the reference MTP or UME.

[0089] At the output of this device 3, a metal separation device 4 allows any pieces of non-magnetic metallic material to be separated from the other bulk pieces coming from the grinding device 3. As an example, this device 4 can be an eddy current separator or an induction sensor system, such as equipment from the STEINERT brand, marketed under the reference EDDYC or NES 50 100 E 50095.

[0090] A dry screening device 5 is fed with the loose pieces so as to calibrate said pieces to a unit size less than or equal to a second threshold value. Typically, this second threshold value may be equal to 6 mm. This device 5 may be a rotary screen or trommel. By way of example, this device 6 may be a trommel or rotary screen, such as equipment from the TRENNSO brand, marketed under the reference "screen drum".

[0091] The pieces from this screening apparatus 5 then feed into an air density separator 6. This separator 6 makes it possible to separate at least some of the pieces made of textile material and / or the other pieces made of bulk elastomer. For example, this separator 5 can be an air separator, known as a zigzag separator, such as a HERBOLD or TRENNSO TECHNIK brand equipment, marketed under the reference TZS.

[0092] Ultimately, a mechanical vibration table with an air cushion 7, also called a density table, allows the calibrated pieces from the screening device 6 to be sorted so as to obtain essentially at least one elastomer granulate with a unit size less than or equal to a third threshold value. Typically, this value is less than or equal to 6 mm, preferably 4 mm, preferably between 1 and 6 mm, and preferably between 1 and 4 mm. The table 7 can be a density vibrating table, such as equipment from the TRENNSO brand, marketed under the reference TTS300, 600, or 900.

[0093] Each aggregate can be used to carry out a recycling process with a step of devulcanization of the telastomer(s) of the pieces of the aggregate and / or of micronization of the pieces of the elastomer(s) aggregate, so as to obtain an intermediate material.

[0094] This recycled intermediate material is advantageously reincorporated into a new matrix of said (said) elastomer(s).

[0095] The inventors carried out various tests on different types of input products. Used tennis balls

[0096] A first series of tests was carried out on used tennis balls, composed of 20% felt and 80% rubber.

[0097] At the outlet of installation 1, a granule with a unit size of 1 to 4 mm or 1 to 5 mm is obtained, with a rubber purity rate of 99%, as shown in [Fig.2],

[0098] This is therefore almost completely free of its textile fibers since only 1% by mass of textile remains in the rubber granules. The mechanical treatment according to the invention can be applied to all types of bales, that is to say, those containing all types of textiles, natural as well as synthetic, for example, wool, nylon, acrylic fibers, polyethylene terephthalate (PET) or even cotton and blends of fibers together.

[0099] Tennis balls are most often made of natural rubber (mostly) with, depending on the ranges and qualities, an addition of synthetic rubber in a mixture (IIR, BR, SBR, EPDM etc).

[0100] Also, the inventors were able to observe these different compositions, in thermogravimetric analysis.

[0101] Fig. 3 illustrates the thermogravimetric analysis of fifteen compositions from completely different bullets.

[0102] It appears from this [Fig.3] that the filler contents vary from 5.61% to 77.36%. Several types of fillers are present, such as kaolin, magnesium carbonate (MgCO3), calcium carbonate / chalk (CaCO3), carbon black, etc.

[0103] This is confirmed by Fourier transform infrared spectroscopy analyses, as shown in [Fig.4].

[0104] The degradation peaks are almost all different in terms of area, but the peaks appear to occur at the same temperatures, which shows that the elastomers are certainly the same, used in different proportions. It is noted that all the balls contain natural rubber (NR) with the degradation peak occurring at 385°C, but also synthetic rubbers, which degrade at higher temperatures (425°C and above).

[0105] There is therefore a possibility of compatibility between the materials during devulcanization.

[0106] The inventors thus carried out a devulcanization of the various aggregates obtained using twin-screw extruders with optimized parameters in terms of feed rate, screw speed, temperature profile, etc., depending on the nature of the material(s) to be processed, in order to control the specific energy and shear level applied. This also makes it possible to achieve Mooney viscosities adapted to the demand and the type of application intended.

[0107] Using extruders typically with 27 mm and 60 mm screw diameters, homogeneous materials with a satisfactory Mooney value, typically ranging from 40 to 75, depending on the extrusion conditions and screw profile, were obtained. This is satisfactory for these recycled materials to be blended with virgin materials for the manufacture of shoe soles and other applications.

[0108] Figure 5 illustrates, in the form of curves, the materials obtained after devulcanization by the twin-screw extruder. It can be seen that, after devulcanization, the recovered material is of homogeneous composition.

[0109] The composition of the devulcanizate is stabilized, both in samples taken after devulcanization in the laboratory and at an industrial scale. The loading rate is around 40% for the 5 samples.

[0110] The degradation peaks are all superimposed at the same temperature and of equivalent area, which further underlines that the composition has been smoothed by devulcanization.

[0111] The devulcanized material may be in the form of granules, flakes, reeds, ribbons, strips, bars or plates, etc.

[0112] Table 1 summarizes the characteristics of the composition of the devulcanized material obtained with all the characterization tests.

[0113] [Tables 1] Devulcanizate Elastomers Proportion 56% Nature NR / SBR (BR not excluded) Plasticizers and extractables Proportion 4% Mineral residue Proportion 40% Mineral fillers Chalk, kaolin Crosslinking Sulfur, ZnO, AS...

[0114] Figures 6A and 6B show examples of shapes obtained by devulcanizing tennis balls at different scales by a twin-screw extruder, with or without different types of dies.

[0115] The inventors then carried out tests on reincorporating the devulcanized material into different rubber bases. Table 2 below shows the different properties of three different bases, respectively labeled Base 1, Base 2, and Base 3. These bases are typically intended for use in the manufacture of shoe soles.

[0116] [Tables2] Bases Base 1 Base 2 Base 3 Composition % natural rubber (NR) 0 50 50 % synthetic rubber (BR, SBR) 100 50 50 Density (g / cm3) 1.07 1.10 1.11 Mechanical Properties Rheology (MDR 10 min / 160°C) ML (dN.m) 1.2 2.81 2.71 MH (dN.m) 15.2 20.1 26.7 Ts2 (min) 1.38 1.19 2.89 T90 (min) 3.53 3.19 4.69 Shore A Hardness 75 67 72 Tensile Modulus M100 (MPa) 3.4 3.3 4.6 M200 (MPa) 5.8 6 8.6 M300 (MPa) 8.3 9.1 Elongation (%) 399 375 224 Abrasion (mm3) 48 65 130

[0117] In these bases 1, 2 and 3, the devulcanized material from the twin-screw extruder was added at different mixing rates (reincorporation).

[0118] Table 3 below indicates the different properties of three different mixtures, i.e. one of the Base 1, Base 2 and Base 3 mixed with the devulcanized material, respectively noted as Mixture 1, Mixture 2, Mixture 3.

[0119] [Tables3] Mixtures Mixture 1 Mixture 2 Mixture 3 Bases Base 1 Base 2 Base 3 Composition % devulcanized material 24.836 23.600 49.740 Density (g / cm3) 1.12 1.14 1.19 Properties Rheology (MDR 10 min / 160°C) ML (dN.m) 0.83 1.36 1.56 MH (dN.m) 10.43 13.38 14.82 Ts2 (min) 1.02 0.84 1.14 T90 (min) 2.33 1.89 1.91 Mechanical properties Shore A hardness 61 58 57 Tensile strength (MPa) 11.09 13.38 8.99 Tensile modulus Ml00 (MPa) 3.4 3.3 4.6 M200 (MPa) 5.8 6 8.6 M300 (MPa) 8.3 9.1 Elongation (%) 548.6 524.9 424.2 Angular Tear (N / mm) 38.81 36.58 26.07 Abrasion (mm³) 93 145 228

[0120] It appears from this table 3 that the reincorporation of this devulcanized material from the rubber of tennis balls obtained from a granule at the output of the mechanical treatment process according to the invention followed by a passage in a twin-screw extruder made it possible to obtain interesting properties in a rubber-based master mixture.

[0121] It also appears that the rheological properties are comparable, showing that the materials (virgin base and 50% devulcanized material blend) behave similarly during curing. The mechanical properties are close, and abrasion resistance and hardness can be improved by adapting the vulcanization system. This confirms the significant potential of this recycled material for incorporation into materials intended for the manufacture of shoe soles or any other article / product whose rubber blend is compatible with the composition of the devulcanized granulate from tennis balls.

[0122] Figure 7 shows the appearance of the different mixtures 1, 2 and 3 tested. It can be seen that the material is completely smooth and free from surface defects or undevulcanized granules, demonstrating the good quality of the recycled raw material obtained. Used complex shoes

[0123] A second series of tests was carried out on used complex shoes (running, trail, etc.), often composed of a mixture of natural and synthetic rubbers BR, SBR, IIR, potentially BIIR / CIIR, NBR and other possible compounds, with minor thermoplastic elastomers. The most frequently found filler was silica.

[0124] At the outlet of installation 1, a unit size granule of 1 to 4 mm or 1 to 5 mm or 1 to 6 mm is obtained, with a purity rate of rubber (+TPR) equal to 93.3%, as shown in [Fig.8].

[0125] This material is therefore almost entirely free of its textile fibers, EVA (or e-TPU, PU, ​​PEBAX) foams, and other lighter foams (polyether PU type) in the granules. A purity level of 93.3% rubber (+TPR) was measured for used complex footwear. This leaves 6.7% by mass of other materials. All types of footwear, including sneakers (cupsoles, vulcanized, complex (running, trail)), hiking shoes, climbing shoes, boots, soccer cleats and other sports footwear, flip-flops and sandals, etc., can be treated by the mechanical treatment process according to the invention.

[0126] Once the purified rubber (and TPR) granules are obtained, they could be reincorporated as is into shoe soles, but the inventors believe that the resulting properties would not be optimal, particularly with large granules having a lower specific surface area and therefore less anchoring capacity in the matrix. Coarse granules also lead to a certain degree of inhomogeneity. Each granule has its own formula and determines the properties of the area of ​​the shoe where it is found.

[0127] To verify this, the inventors carried out thermogravimetric analyses on different compositions.

[0128] Fig. 9 illustrates the thermogravimetric analysis of ten compositions from complex shoe soles.

[0129] It is clear from this [Fig.9] that the compositions are all different, whether in terms of the nature of the elastomers used or the rate of filling (very wide range between 8.94% and 32.35%).

[0130] The inventors considered micronizing the granule in order to achieve an increase in the specific surface area and a homogenization of the material.

[0131] Fig. 10 shows an aspect of a micronized particle size of less than 500 qm that was obtained.

[0132] Fig. 11 illustrates the thermogravimetric analysis of four micronized compositions from the global micronized complex deposit.

[0133] It appears from this [Fig.1 1] that the composition is stable at the level of the elastomers and the charge ratios.

[0134] The particle size distribution of a composition is detailed in Table 4 below.

[0135] [Tables4] Micronized value (qm) Average size 345.7 Diameter dlO 147.4 Diameter d50 336.15 Diameter d90 553.75

[0136] Fig. 12 shows the Fourier transform infrared spectroscopy analyses of such a micronized sample.

[0137] All the analyses carried out on the micronized material as well as on the initial input products make it possible to establish the most probable composition according to table 5 below.

[0138] [Tables5] Micronized Elastomers: 80% (52% without fillers) Nature: NR / BR / SBR / IIR(BIIR) Plasticizers and extractables (including TPE): 20% Mineral residue: 28% Mineral fillers: Chalk, kaolin Crosslinking: Sulfur, ZnO, AS...

[0139] The percentage of plasticizers and extractables (including TPE / TPR) was determined by dissolution in solvents.

[0140] The resulting miconisates are therefore suitable for reincorporation into compatible rubber blends, thermoplastic alloys or any other application complying with applicable standards.

[0141] The inventors carried out, in particular, a reincorporation into rubber bases and studied the properties of the mixtures as a function of the reincorporation rate and the nature of the bases

[0142] In bases 1, 2, 3, the micronized material was added at different mixing rates (reincorporation).

[0143] Table 6 below indicates the different properties of three different mixtures, i.e. one of Base 1, Base 2 and Base 3 mixed with the micronized material, respectively noted as Mixture 4, Mixture 5, Mixture 6.

[0144] [Tableauxô] Mixtures Mixture 4 Mixture 5 Mixture 6 Bases Base 1 Base 2 Base 3 Composition % micronized material 25 25 50 Density (g / cm3) 1.09 1.09 1.13 Properties Rheology (MDR 10 min / 160°C) ML (dN.m) 1.09 1.52 2.97 MH (dN.m) 10.48 13.11 14.22 Ts2 (min) 1.92 1.35 2.66 T90 (min) 4.71 2.87 4.63 Mechanical properties Shore A hardness 65 60 65 Tensile modulus M100 (MPa) 2.24 1.9 2.13 M200 (MPa) 3.84 3.59 3.97 M300 (MPa) 5.75 5.98 6.24 Elongation (%) 457.3 482.1 307.4 Angular Tear (N / mm) 40.36 36.97 31.86 Abrasion (mm3) 69 99 113

[0145] It appears from this table 6 that with a reincorporation of up to 50% reincorporation, a specification of a shoe sole manufacturer is met.

[0146] The material is easily reincorporated into the mixtures.

[0147] A final appearance of a shoe sole with a tested mixture 6 is shown in [Fig. 13]. It can be seen that the fineness of the micronized material allows for a very smooth and homogeneous appearance.

[0148] Used single-brand cup and vulcanized soles

[0149] A third series of tests was carried out on used cupsoles, often composed of a mixture of natural and synthetic rubbers, primarily NR, BR, and SBR. The materials also contain mineral fillers, plasticizers, vulcanizing agents, protective agents, and various additives. This list is not exhaustive. As this product comes from heterogeneous deposits, the stability of its composition cannot be guaranteed.

[0150] On average, the main elastomers are NR, BR and SBR.

[0151] At the outlet of installation 1, a unit-sized aggregate of 1-4 mm is obtained, with a rubber purity rate of 99.6%, as shown in figures 14 and 15, respectively for the light fraction and the heavy fraction (without leather).

[0152] Of the 279.12 kg of mixture, the installation yields 204 kg of separated rubber, 75 kg of leather and foams (and very little lost rubber), and the remainder corresponds to the fraction recovered in the filter of 0.12 kg.

[0153] The purity level determined at the output is 99.6%. The only impurities found were dual-material granules with one side being rubber and the other leather or foam. The light fraction contained 58% leather, 37.5% foam, and 4.5% rubber residue (very fine granules ~ dust).

[0154] Once the rubber granules are obtained, they could be reincorporated as is into shoe soles, but the inventors believe that the resulting properties would not be optimal, particularly with large granules having a lower specific surface area and therefore less anchoring capacity in the matrix. Coarse granules also lead to a certain degree of inhomogeneity. Each granule has its own formula and determines the properties of the area of ​​the shoe where it is found.

[0155] To verify this, the inventors carried out thermogravimetric analyses on different compositions.

[0156] Fig. 16 illustrates the thermogravimetric analysis of eight compositions from cupsoles shoe soles.

[0157] It is clear from this [Fig. 16] that the compositions are all different, whether in terms of the nature of the elastomers used or the rate of filling (very wide range between 30.91% and 46.01%).

[0158] The inventors considered micronizing the granule in order to achieve an increase in the specific surface area and homogenization of the material.

[0159] Fig. 17 shows an aspect of a micronized particle size of less than 500 µm that was obtained.

[0160] Figure 18 illustrates the thermogravimetric analysis of seven compositions that were taken from the ten aggregates and then from micronized samples of the mixed deposit

[0161] It appears from this [Fig. 18] that the composition is stable at the level of the elastomers and the charge ratios.

[0162] Several particle sizes are possible, typically less than 300 pm, 500 pm and 850 pm respectively.

[0163] The particle size distribution of several of these compositions is detailed in Table 7 below.

[0164] [Tables7] Composition Composition 1 Composition 2 Composition 3 Micronization value (µm) Average size 180.1 293.15 421.55 Diameter dlO 73.03 92.11 108.1 Diameter d50 174.1 279.65 377.25 Diameter d90 314.55 509.3 796.5

[0165] Fig. 19 shows the Fourier transform infrared spectroscopy analyses of such a micronized sample.

[0166] All the analyses carried out on the micronized material as well as on the initial input products make it possible to establish the most probable composition according to table 8 below.

[0167] [Tables8] Micronized Elastomers Proportion 51.5% Nature NR / BR / SBR Plasticizers and extractables (including TPE) Proportion 12.5% ​​Mineral residue Proportion 36% Mineral fillers Silica, chalk, TiO2, talc, Crosslinking Sulfur, ZnO, AS...

[0168] The level of plasticizers and extractables was determined by dissolution in solvents.

[0169] The micronisates obtained are therefore suitable for reincorporation into compatible rubber blends, thermoplastic alloys or any other application complying with applicable standards.

[0170] The inventors carried out in particular a reincorporation into rubber bases and studied the properties of the mixtures as a function of the rate of reincorporation and the nature of the bases.

[0171] In bases 1, 2, 3, devulcanized material (granulate) and micronized material with a particle size of less than 500qm were added at different mixing rates (reincorporation).

[0172] Table 9 below indicates the different properties of three different mixtures, i.e. one of Base 1, Base 2 and Base 3 mixed with the devulcanized material (granulate), respectively noted as Mixture 7, Mixture 8, Mixture 9.

[0173] [Tables9] Mixtures Mixture 7 Mixture 8 Mixture 9 Bases Base 1 Base 2 Base 3 Composition % devulcanized material (granulate) 25 25 50 Density (g / cm3) 1.1 1.12 1.15 Properties Rheology (MDR 10 min / 160°C) ML (dN.m) 0.82 1.31 1.5 MH (dN.m) 10.82 13.62 14.47 Ts2 (min) 1.19 1.02 1.77 T90 (min) 3.08 2.43 3.02 Mechanical Properties Shore A Hardness 61 57 59 Tensile Modulus M100 (MPa) 1.99 1.81 1.83 M200 (MPa) 3.68 3.84 4.11 M300 (MPa) 5.63 6.44 6.96 Elongation (%) 514.4 462.7 346.7 Abrasion (mm³) 84 116 168

[0174] Table 10 below indicates the different properties of three different mixtures, i.e. one of Base 1, Base 2 and Base 3 mixed with the micronized material, respectively noted as Mixture 10, Mixture 11, Mixture 12.

[0175] [TableauxlO] Mixtures Mixture 10 Mixture 11 Mixture 12 Bases Base 1 Base 2 Base 3 Composition % micronized material 25 25 50 Density (g / cm3) 1.11 1.12 1.16 Properties Rheology (MDR 10 min / 160°C) ML (dN.m) 1.3 1.79 4.03 MH (dN.m) 12.45 15.13 18.71 Ts2 (min) 1.73 1.26 2.27 T90 (min) 4.02 2.73 3.84 Mechanical Properties Shore A Hardness 64 59 64 Tensile Modulus M100 (MPa) 2.15 1.72 1.98 M200 (MPa) 3.95 3.49 4.12 M300 (MPa) 6.2 6.06 7.5 Elongation (%) 516.15 503.6 396.2 Abrasion (mm3) 56 86 92

[0176] It appears from these tables 9 and 10 that with a reincorporation of devulcanized and micronized materials up to 50% reincorporation, a specification of a shoe sole manufacturer is met.

[0177] The material is easily reincorporated into mixtures. Micronization produces slightly superior properties to devulcanized material, but production rates are higher for devulcanization.

[0178] As shown in [Fig.20], it is possible to recolor a clear devulcanizate (left) whereas a micronized gives a more speckled appearance (right).

[0179] The inventors have produced repair pads for specialized shoe repair shops of the brand of shoe soles with the devulcanizate obtained according to the invention.

[0180] Fig. 21 shows an example of skates and the devulcanizate which was used in its production.

[0181] All skates produced have been tested in use and are perfectly suited to users. List of cited references#:

[0182] [1]: Michael James Lee, Shahin Rahimifard “Air-based automated material recycling System for postconsumer footwear produel s" Resources, Conservation and Recycling Volume 69, December 2012, Pages 90-99. https: / / doi.Org / 10.1016 / j.resc onrec.2012.09.008

Claims

Demands

1. A mechanical treatment process for a new, defective, or used product initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material, or a combination thereof, for the purpose of its recycling, comprising the following steps: i / mechanical grinding of at least a portion of the product so as to obtain ground pieces of a unit size less than or equal to a first predetermined threshold value; ii / where appropriate, magnetic separation of the pieces of magnetic material from the other bulk pieces resulting from grinding according to step i / ; ii / where appropriate, before or after step ii / , metallic separation of the pieces of non-magnetic metallic material from the other bulk pieces resulting from grinding according to step i / ;ii / dry air screening of at least a portion of the pieces of textile material and / or other bulk elastomer pieces with a density less than or equal to the first predetermined threshold value of those resulting from grinding according to step i / or, where applicable, from step i1 / or i2 / ; iü / separation by an airflow of the pieces resulting from a density greater than the first threshold value of step ii / so as to calibrate said pieces to a unit size less than or equal to a second threshold value; iv / sorting by mechanical vibration on an air cushion of the pieces calibrated according to step iü / so as to obtain essentially at least one elastomer granule(s) with pieces of a unit size less than or equal to a third threshold value.;

2. Mechanical treatment method according to claim 1, steps i / to iv / being carried out continuously.

3. Mechanical treatment method according to claim 1 or 2, the first unit size threshold value according to step i / being equal to 40mm.

4. Mechanical treatment method according to any one of the preceding claims, the second unit size threshold value according to step iü / being equal to 6 mm.

5. A mechanical processing method according to any one of the preceding claims, the third threshold unit size value according to step iv / being less than or equal to 6 mm, preferably 4 mm, preferably still between 1 and 6 mm, preferably still between 1 and 4 mm.

6. A mechanical treatment process according to any one of the preceding claims, comprising after step iv / , a step v / of micronizing the elastomer granule(s), preferably so as to obtain micronized particles of unit size less than or equal to 500 pm, preferably still between 100 and 500 pm.

7. A method of mechanically treating, according to any one of the preceding claims, a sporting article based on natural or synthetic textile, or not, as a product, such as a used tennis ball, a used or new sports shoe.

8. A mechanical processing method according to any one of the preceding claims, the product containing as textile, wool fibers, nylon fibers, including polyamide (PA), acrylic fibers, polyethylene terephthalate (PET) fibers, elastane fibers, thermoplastic polyurethane (TPU) fibers, cotton fibers, flax fibers or a combination of said fibers.

9. Installation for the continuous mechanical processing of a new defective or used product initially comprising at least one elastomeric material and at least one other material selected from at least one textile material, at least one magnetic metallic material, at least one non-magnetic metallic material or a combination thereof, for the purpose of its recycling, comprising: - a mechanical crushing apparatus for at least part of the product so as to obtain crushed pieces of a unit size less than or equal to a first predetermined threshold value; - where applicable, a magnetic separation device for the pieces of magnetic material from the other bulk pieces from the crushing apparatus; - where applicable, a metallic separation device by eddy current for the pieces of non-magnetic metallic material from the other bulk pieces from the crushing apparatus; - a dry screening apparatus to separate at least part of the pieces of textile material and / or other bulk elastomer pieces from the grinding apparatus or, where applicable, from the eddy current separation device or the magnetic separation device; - an air density separator to separate the pieces from the dry screening apparatus, so as to calibrate said pieces to a unit size less than or equal to a second threshold value; - a mechanical vibration table with an air cushion to sort the calibrated pieces from the screening apparatus so as to obtain essentially at least one elastomer granulate(s) with pieces of a unit size less than or equal to a threshold value.

10. Elastomer granule(s), obtained from a new or used product initially comprising at least one elastomeric material and at least one other material selected from a textile material, a ferrous metallic material, the purity level of which is greater than 93%, preferably greater than 95%, preferably even greater than 99%.

11. Rubber granules according to claim 10, having a purity level greater than 93%, preferably greater than 95%, preferably even greater than 99%.

12. Ethylene vinyl acetate (EVA) granules according to claim 10, having a purity level greater than 87%.

13. A recycling process for at least one elastomer granulate(s) obtained by the mechanical processing according to any one of claims 1 to 8, comprising, after step iv / or where appropriate after step v / , a step vi / of devulcanization of the elastomer(s) of the granulate pieces and / or of micronization of the elastomer granulate pieces, so as to obtain an intermediate material.

14. Recycling process according to claim 13, comprising after step vi / , a step of reincorporating the recycled intermediate material into a new matrix of said (said) elastomer(s).

15. New article / product incorporating at least one elastomer element(s) obtained by the devulcanization and / or micronization process according to claim 13.

Images