BITUMINOUS COMPOSITION COMPRISING A THERMAL CONVERSION RESIDUE OF PLASTIC

Abstract

BITUMINOUS COMPOSITION COMPRISING A THERMAL CONVERSION RESIDUE OF PLASTIC The present invention relates to a bituminous composition comprising: a) at least one bitumen base, b) at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, said at least one residue having a penetrability at 25°C, measured according to EN 1426, less than or equal to 200 1 / 10 mm. Figure for the abstract: none

Description

Title of the invention: BITUMINOUS COMPOSITION COMPRISING A THERMAL CONVERSION RESIDUE OF PLASTIC

[0001] The present invention belongs to the field of bitumens. In particular, the present invention relates to a bituminous composition incorporating a distillation residue of a hydrocarbon product obtained by thermal conversion of plastic waste. The invention also relates to a process for preparing a bituminous composition according to the invention, as well as its use for road and / or industrial applications.

[0002] Bitumen is the main hydrocarbon component used in the field of road construction or civil engineering. It is used, for example, for the production of road surfaces or as a waterproofing membrane. Bitumen is generally obtained from residues from the atmospheric and / or vacuum distillation of crude oil.

[0003] Oil resources are, however, limited. Indeed, "proven reserves" of oil reached more than 200 billion tonnes of oil equivalent (TOE) in 2018 worldwide, according to experts from British Petroleum (who have been taking stock of the resource since 1980). Although significant, these reserves could only cover 50.2 years of annual consumption at the rate of 2017. These figures are confirmed by the French Alternative Energies and Atomic Energy Commission (CEA) and the International Energy Agency (IEA). It is therefore necessary to limit our oil consumption as much as possible.

[0004] Furthermore, and in order to maintain and / or improve the characteristics, in particular the mechanical properties, of a conventional bitumen, it is known to use bitumen / polymer compositions in which the bitumen (formed from one or more types of bitumen) is mixed with one or more functional polymers, in particular styrene and butadiene elastomers, these elastomers being chemically crosslinked in situ, possibly using a coupling or crosslinking agent, for example sulfur or at least one of its precursors. Optimized mechanical characteristics are indeed crucial for certain road surfacing applications. In the vast majority of cases, however, these polymers are synthesized from petroleum. The preparation of bitumen / polymer compositions therefore has the effect of further increasing our consumption of petroleum.

[0005] In order to reduce our consumption of oil, particularly bitumen, it is now envisaged to integrate more and more of compounds / materials from recycling. This approach consists of promoting the circular economy by limiting the use of fossil resources, particularly bitumen but also polymer in the case of bitumen / polymer compositions.

[0006] In this sense, it is known to recover plastic waste by using it as an initial charge in chemical processes (gasification, pyrolysis, depolymerization, dissolution) or in mechanical processes (crushing). In the initial charge, plastic waste can also be combined with waste from biomass.

[0007] High-temperature pyrolysis processes make it possible to transform plastic waste into several products in varying proportions depending on the nature of the waste used: an oil, a gas mixture, coke.

[0008] The oil resulting from the pyrolysis of the plastic can then be separated into several cuts by all types of separation process known per se:

[0009] • The light naphtha type cut with a distillation interval between 50 and 200°C and a density between 720 Kg / m3 and 750 Kg / m3;

[0010] • The average diesel cut with a distillation interval between 200°C and 300°C and a density between 750 Kg / m3 and 800 Kg / m3;

[0011] • The heavy cut type VGO (“Vaccum Gasoil” in English) with an interval of distillation between 300°C and 450°C and a density between 800 Kg / m3 and 840 Kg / m3;

[0012] • A very heavy cut type VR (Visco-Reduced) with an initial boiling point of at least 450°C and a density between 840 Kg / m3 and 870 Kg / m3.

[0013] There is a need to enhance the value of heavy to very heavy cuts.

[0014] EP 4 124 638 A1 describes bitumen base compositions comprising up to 5% by mass of at least one plastic pyrolysis oil having an initial boiling point of at least 300°C. The compositions obtained have improved properties in terms of TBA variation, compared to bitumen alone.

[0015] However, the pyrolysis oil content is limited to a maximum of 5% by mass. Dependence on petroleum bitumens therefore remains very high.

[0016] There therefore remains a need to provide bituminous compositions whose dependence on fossil resources, in particular bitumen, is significantly reduced compared to the compositions of the prior art.

[0017] In particular, there remains a need for bituminous compositions incorporating a larger proportion of recycled components, compared to the compositions of the prior art. In other words, there remains a need for bituminous compositions whose content of material(s) of fossil origin, in particular bitumen, is significantly reduced compared to the compositions of the prior art.

[0018] In the case of bitumen / polymer compositions, there remains a need for bitumen / polymer compositions (possibly crosslinked) whose content of original material(s) fossil fuel, particularly bitumen and / or polymer, is reduced compared to prior art compositions. Furthermore, oil exploitation is currently responsible for the release of significant quantities of greenhouse gases into the atmosphere, the latter having a significant impact on global warming. The carbon footprint associated with bitumen / polymer compositions is even greater. Indeed, the carbon footprint of pure bitumen is estimated at 0.2 kg of CO2 equivalent per kg of bitumen (estimate made by the Eurobitume association). The carbon footprint of a polymer, particularly a styrene and butadiene elastomer, is currently estimated at between 2.2 and 3.3 kg of CO2 equivalent per kg of polymer, depending on the process used and plant optimization.

[0019] There therefore remains a need for bituminous compositions, in particular bitumen / polymer compositions, with a reduced carbon footprint.

[0020] In addition to reducing dependence on fossil-based materials discussed above, reducing the carbon footprint of bituminous compositions, particularly bitumen / polymer compositions, also involves reducing their application, shaping and usage temperatures.

[0021] There therefore also remains a need for bituminous compositions, in particular bitumen / polymer compositions, the energy requirement associated with their application of which is significantly reduced compared to the compositions of the prior art.

[0022] In particular, there remains a need for bituminous compositions, in particular bitumen / polymer compositions, having both a content of material(s) of fossil origin, and an energy requirement during its application, both significantly reduced compared to the compositions of the prior art. Summary of the invention

[0023] The invention firstly relates to a bituminous composition comprising:

[0024] a) at least one bitumen base,

[0025] b) at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0026] said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm.

[0027] According to one embodiment, the distillation residue b) has a penetrability at 25°C, measured according to standard EN 1426, ranging from 20 1 / 10 mm to 120 1 / 10 mm.

[0028] Preferably, the distillation residue b) is a residue from atmospheric distillation of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

[0029] By "atmospheric distillation" is meant an operation consisting of separating the different components of a liquid mixture according to their temperature evaporation at atmospheric pressure.

[0030] Preferably, the distillation residue b) has a boiling point at 10% by mass, measured according to standard ASTM D7169:20, greater than or equal to 350°C, preferably ranging from 400°C to 600°C, typically ranging from 410°C to 550°C.

[0031] Advantageously, the distillation residue b) has a ring and ball softening temperature (RBT), measured according to standard EN 1427, greater than or equal to 60°C, more preferably ranging from 60°C to 120°C, typically ranging from 65°C to 100°C.

[0032] Advantageously, the composition of the invention has a content of residue b) ranging from 0.1% to 30% by mass, relative to the total mass of the composition, preferably from 0.5% to 25% by mass, more preferably from 1% to 20% by mass.

[0033] According to one embodiment, the composition of the invention further comprises at least one elastomer, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0034] Preferably, according to this embodiment, the composition of the invention is a crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition as defined above.

[0035] The invention also relates to a process for preparing a bituminous composition according to the invention, said process comprising the following successive steps:

[0036] 1) bringing into contact at least:

[0037] - a bitumen base,

[0038] - a distillation residue of a hydrocarbon product obtained by conversion thermal resistance of plastics, said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm,

[0039] - optionally, an elastomer,

[0040] 2) the mixture of components

[0041] Preferably, the bitumen base and the distillation residue are preheated, preferably separately, to a temperature ranging from 90°C to 230°C, preferably from 120°C to 200°C, more preferably from 150°C to 180°C.

[0042] The invention also relates to the use of a bituminous composition according to the invention, as a binder for preparing a surface coating, a hot mix, a cold mix, a cold-poured mix, an emulsion gravel or a wearing course, said binder being associated with aggregates and / or recycled millings.

[0043] The invention further relates to a bituminous coating comprising a bituminous composition according to the invention, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

[0044] The invention also relates to the use in a bituminous composition, in particular in a bitumen / polymer composition, of at least one residue of dis tillation of a hydrocarbon product obtained by thermal conversion of plastics, said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm, and an initial boiling temperature, measured according to standard ASTM D7169:20, less than or equal to 500°C, to reduce the content of compounds of fossil origin, in particular bitumen and / or elastomer, in said composition.

[0045] The invention also relates to the use in a bituminous composition, in particular in a bitumen / polymer composition, of a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said distillation residue having a penetrability at 25°C, measured according to standard EN 1426, of less than or equal to 200 1 / 10 mm, to reduce the hot viscosity of said composition.

[0046] The invention finally relates to the use in a bituminous composition, in particular in a bitumen / polymer composition, of a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said distillation residue having a penetrability at 25°C, measured according to standard EN 1426, of less than or equal to 200 1 / 10 mm, to reduce the processing temperature of said bituminous composition.

[0047] The inventors have discovered that it is possible to further reduce the content of material(s) of fossil origin in a bituminous composition, in particular in a bitumen / polymer composition, by integrating a particular residue, obtained by distillation of a hydrocarbon product, itself obtained by thermal conversion of plastic (waste). In particular, the inventors have discovered that it is possible to integrate such a residue into a bituminous composition, in particular in a bitumen / polymer composition, without significantly affecting the properties of the final material. The final material has properties that are substantially equivalent, or even improved, compared to those of bituminous compositions free of said residue.

[0048] The inventors have also discovered, surprisingly, that the incorporation of said residue into a bitumen / polymer composition makes it possible to improve the mechanical properties, in particular to increase the softening temperature of said bitumen / polymer composition. It is thus possible, at a constant polymer content, to further improve the mechanical properties of a bitumen / polymer composition by incorporating said residue. It is also possible, at equivalent mechanical properties, to reduce the polymer content by incorporating said residue. This second option is advantageous in that it makes it possible to further reduce the proportion of materials of fossil origin in the compositions.

[0049] The inventors have also surprisingly discovered that the incorporation in a bituminous composition of such a residue makes it possible to improve the hot properties of said bituminous composition, in particular to reduce its hot viscosity. This particular technical effect is advantageous in that it makes it possible to reduce the processing temperature of the bituminous composition. This reduction in the processing temperature then results in a reduction in the energy consumption associated with the application of the composition, and thus in a reduction in the carbon footprint of the final coating.

[0050] In particular, the inventors have discovered that the incorporation into a bituminous composition, in particular into a bitumen / polymer composition, of such a residue makes it possible to significantly reduce the hot viscosity of said bituminous composition, without degrading its cold properties. Detailed description of the invention

[0051] In the remainder of the description, and unless explicitly indicated otherwise, the quantities of the various components present in a bituminous composition according to the invention are given in % by mass, relative to the total mass of the composition (hereinafter referred to as % m / m).

[0052] Similarly, and unless explicitly indicated otherwise, the standards mentioned in the remainder of the description correspond to the standard in force on July 1, 2023.

[0053] The term "boiling point" used refers to the boiling point generally used in the oil and gas industry. Boiling points are measured at atmospheric pressure. The initial boiling point is defined as the temperature value when the first vapor bubble is formed. The final boiling point is the highest temperature that can be reached during a standard distillation. At this temperature, no more vapor can be entrained in the condensation units. The determination of the initial and final boiling point is known per se. Depending on the boiling range of the mixture, they can be determined using various standardized methods such as ASTM D2887:2019 for the boiling range distribution of petroleum fractions by gas chromatography.

[0054] For compositions containing heavier hydrocarbons, ASTM D7169:2020 or D2892-20:2020 may also be used. Distillate boiling ranges may also be advantageously measured using ASTM D7500:2019.

[0055] The invention firstly relates to a bituminous composition comprising:

[0056] a) at least one bitumen base,

[0057] b) at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastic waste. Bitumen base

[0058] The bitumen(s) used to prepare a bituminous composition according to the invention are called “bitumen base”.

[0059] Among the bitumens that can be used according to the invention, mention may firstly be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. In the context of the invention, the bitumen(s) used are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and / or vacuum distillation of oil. These bitumens can optionally be visbroken and / or deasphalted and / or rectified in air. It is common practice to carry out vacuum distillation of atmospheric residues originating from the atmospheric distillation of crude oil.This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a feedstock usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of oil. This process makes it possible to obtain a blown, or semi-blown, or oxidized, or air-rectified, or partially air-rectified bitumen.

[0060] Different bitumens obtained by the refining processes can be combined in the compositions according to the invention, to obtain the best compromise, in terms of technical performances. In conventional processes for mixing different bitumens, the operation is carried out at temperatures between 100°C and 200°C, preferably between 140°C and 200°C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The temperature and duration of heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594. Blown bitumens can be manufactured in a blowing unit, by passing a flow of air and / or oxygen through a starting bitumen or bitumen mixture. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.

[0061] Generally, blowing is carried out at high temperatures, of the order of

[0062] 200 to 300°C, for relatively long periods typically between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted according to the desired properties of the blown bitumen and according to the quality of the starting bitumen.

[0063] Among the bitumens that can be used according to the invention, mention may also be made of recycling bitumens.

[0064] Bitumens may be hard grade bitumens (such as grades 10 / 20 and 20 / 30) or soft grade bitumens (such as grade 160 / 220) as defined by standard EN 12591.

[0065] The invention is particularly suitable for cases where the bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from bitumens of grade 35 / 50, 20 / 30 and 10 / 20.

[0066] The bitumen bases that can be used in the context of the invention preferably have a penetrability, measured at 25°C according to standard EN 1426, of 5 to 330 1 / 10 mm, preferably between 10 and 220 1 / 10 mm, more preferably from 10 to 120 1 / 10 mm. In a well-known manner, the so-called “needle penetrability” measurement is carried out using a standardized test NF EN 1426 at 25°C (P25). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1 / 10 mm). Needle penetrability, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.

[0067] Preferably, the bitumen composition according to the invention comprises at least 40% by mass of bitumen, relative to the total mass of the bitumen composition, preferably at least 50% by mass, more preferably at least 60% by mass, advantageously at least 70% by mass, more advantageously at least 80% by mass, even more advantageously at least 85% by mass.

[0068] Advantageously, the bituminous composition of the invention comprises from 60% to 99.9% by mass, relative to the total bitumen composition, preferably from 65% to 99% by mass, more preferably from 70% to 95% by mass, advantageously from 80% to 90% by mass.

[0069] Residue from the distillation of thermal conversion of plastics

[0070] The composition of the invention further comprises at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste.

[0071] Common industrial methods for recycling hydrocarbons from plastic include thermal conversion liquefaction of plastic waste that might have ended up in a landfill or incinerator, followed by a purification step including hydrotreatment and removal of contaminants using a variety of purification processes such as distillation.

[0072] The liquefaction of plastic waste can be carried out in particular by pyrolysis or by hydrothermal treatment. The thermal conversion step transforms the plastics and most of their additives and contaminants into gaseous chemical products, while most non-volatile contaminants or additives end up in the solid by-product, the chars or ash. In principle, all types of plastic waste can be converted. However, a preliminary step of sorting non-organic waste is desirable. Purification of the output material can also be useful because several hetero-elements (i.e., elements other than carbon and hydrogen, e.g., oxygen) can be volatilized.

[0073] Plastic waste is a complex and heterogeneous material, due to several factors. First of all, plastic as a material refers to many different polymers with different chemical properties that can be separated from each other before recycling or alternatively recycled as a complex mixture. The main polymers present in plastic from municipal solid waste are polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP) and polystyrene (PS). Other polymers mainly include polyurethanes, polyamides (PA), polycarbonates, polyethers and polyesters other than PET. In addition, many additives different from the basic polymers are introduced during the production phase to adjust or improve the properties of the plastic or to meet specific requirements.These include functional additives (stabilizers, antistatic agents, flame retardants, plasticizers, lubricants, glidants, curing agents, foaming agents, biocides, antioxidants, etc.), dyes and pigments, fillers (e.g., glass fibers, talc, carbon fibers, carbon nanotubes), commonly used in plastic packaging, as well as additives such as flame retardants, frequently used in plastics for electronics. In addition, several metal compounds are intentionally added during plastic production (often in the form of oxides, carbonates, acids, etc.). Additives containing heteroelements other than metals are also used in the manufacture of plastics, e.g., halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0074] Silicone polymers, which are organic materials containing silicon, are often used in plastic formulations. Due to their surface characteristics, the applications of silicones range from silicone rubbers, used as sealants for joints, to silicone surfactants for cosmetic products, while they are increasingly used in the plastics sector, as process-enhancing additives (manufacturing aids), and for the modification of polymers.

[0075] In addition to these heteroelements, used plastic waste may have been contaminated during its life by remains of liquids with which it has been in contact (beverages, personal care products, etc.) and food which may also contaminate plastic. Finally, some plastic waste may be present in the form of partially decomposed waste, such as partially burned plastic.

[0076] Finally, since plastics are contaminated by oxygenated compounds, plastic oils resulting from liquefaction by pyrolysis may also contain oxygenated compounds such as aldehydes or ketones.

[0077] For the purposes of the invention, the term "hydrocarbon product obtained by thermal conversion of waste" or "hydrocarbon product" means the liquid products obtained after thermal conversion, in particular after thermal pyrolysis, of plastic waste or plastic waste. The thermal conversion process, in particular pyrolysis, must be understood as a non-selective thermal cracking process.

[0078] According to a preferred embodiment, the hydrocarbon product used for the preparation of the residue of the invention is obtained by pyrolysis of waste, in particular by pyrolysis of plastic waste.

[0079] The residue incorporated into the bituminous composition of the invention corresponds to the residue obtained from the distillation of the hydrocarbon product obtained by thermal conversion of plastic waste.

[0080] The residue incorporated in the bituminous composition of the invention may be obtained by direct distillation and / or by vacuum distillation of said hydrocarbon product. When obtained by atmospheric distillation, the residue of the invention simply corresponds to the residue of the distillation carried out at atmospheric temperature and pressure. A vacuum manufacturing process corresponds, for its part, to the succession of an atmospheric distillation and a vacuum distillation, the feedstock feeding the vacuum distillation corresponding to the residues obtained at the end of the atmospheric distillation. Thus, when obtained by vacuum distillation, the residue of the invention corresponds to the residue obtained at the end of the vacuum distillation process.

[0081] Preferably, the residue incorporated into the composition of the invention is a residue obtained by vacuum distillation of the hydrocarbon product defined above.

[0082] The residue of the invention typically has a penetrability at 25°C, measured according to standard EN 1426, of less than or equal to 200 1 / 10 mm.

[0083] Preferably, the residue of the invention has a penetrability at 25°C, measured according to standard EN 1426, greater than or equal to 20 1 / 10 mm, more preferably greater than or equal to 30 1 / 10 mm, even more preferably greater than or equal to 35 1 / 10 mm.

[0084] More preferably, the residue of the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 20 to 200 1 / 10 mm, preferably from 25 to 150 1 / 10 mm, even more preferably from 30 to 120 1 / 10 mm.

[0085] Preferably, the residue of the invention has a ring and ball softening temperature (RBT), measured according to standard EN 1427, greater than or equal to 60°C, more preferably ranging from 60°C to 120°C, typically ranging from 65°C to 100°C.

[0086] Preferably, the residue of the invention has a Cleveland flash point, measured according to the ASTM D 92 standard, greater than or equal to 150°C, more preferably greater than or equal to 200°C, typically ranging from 200°C to 350°C, for example from 230°C to 340°C.

[0087] In a known manner, distillation is carried out by gradually heating a product. In the case of a pure compound, the entire product is distilled at a constant temperature. Conversely, in the case of a mixture, fractions with different boiling temperatures are evaporated gradually. These boiling temperatures increase during distillation.

[0088] Preferably, the residue of the invention has an initial boiling temperature, measured according to standard ASTM D7169:20, less than or equal to 500°C, more preferably ranging from 100°C to 500°C, more preferably from 200°C to 480°C.

[0089] Preferably, the residue of the invention has a final distillation point, measured according to standard ASTM D7169:20, less than or equal to 1000°C, more preferably less than or equal to 900°C.

[0090] More preferably, the residue of the invention has a final boiling point, measured according to the ASTM D7169:20 standard, ranging from 150°C to 1000°C, more preferably from 200°C to 900°C.

[0091] For the purposes of the invention, the term "boiling temperature at X% of product Y" means the boiling temperature of the remaining part of product Y once X% by mass of the starting product has been evaporated.

[0092] Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to standard ASTM D7169:20, greater than or equal to 300°C, more preferably greater than or equal to 350°C, typically greater than or equal to 400°C.

[0093] Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to standard ASTM D7169:20, less than or equal to 550°C, more preferably less than or equal to 500°C.

[0094] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 350°C, more preferably greater than or equal to 400°C, typically greater than or equal to 410°C.

[0095] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to the ASTM D7169:20 standard, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0096] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 380°C, more preferably greater than or equal to 400°C, typically greater than or equal to 430°C.

[0097] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to standard ASTM D7169:20, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0098] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 400°C, more preferably greater than or equal to 430°C, typically greater than or equal to 450°C.

[0099] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to standard ASTM D7169:20, less than or equal to 650°C, more preferably less than or equal to 600°C.

[0100] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 450°C, more preferably greater than or equal to 460°C, typically greater than or equal to 470°C.

[0101] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to standard ASTM D7169:20, less than or equal to 700°C, more preferably less than or equal to 650°C.

[0102] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 450°C, more preferably greater than or equal to 500°C, typically greater than or equal to 510°C.

[0103] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to standard ASTM D7169:20, less than or equal to 750°C, more preferably less than or equal to 730°C.

[0104] Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 475°C, more preferably greater than or equal to 500°C, typically greater than or equal to 510°C.

[0105] Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to standard ASTM D7169:20, less than or equal to 775°C, more preferably less than or equal to 750°C.

[0106] Preferably, the residue of the invention has a final boiling temperature (i.e. boiling temperature at 100% by mass), measured according to the ASTM standard D7169:20, greater than or equal to 500°C, more preferably greater than or equal to 550°C, typically greater than or equal to 600°C.

[0107] According to one embodiment, the residue of the invention has a content of calcium element Ca, greater than or equal to 1 ppm, more preferably greater than or equal to 1.5 ppm, typically ranging from 1 to 1000 ppm. The calcium content is typically determined by calcination of the material, followed by acidification of the ash obtained and analysis of the solutions by ICP-OES.

[0108] According to one embodiment, the residue of the invention has a content of phosphorus element P greater than or equal to 10 ppm, more preferably greater than or equal to 15 ppm, typically ranging from 10 to 200 ppm. The phosphorus content is typically determined by acid digestion in a closed microwave instrument due to its volatility. The resulting solution is then analyzed by ICP-OES following conventional acid conditions.

[0109] According to one embodiment, the residue of the invention has a content of silicon element Si greater than or equal to 5 ppm, more preferably greater than or equal to 10 ppm, typically ranging from 10 to 750 ppm. The silicon content is typically determined by X-ray fluorescence (XRF) after homogenization of the material and appropriate calibration.

[0110] According to one embodiment, the residue of the invention has a chlorine element Cl content greater than or equal to 10 ppm, more preferably greater than or equal to 20 ppm, typically ranging from 10 to 1,500 ppm. The chlorine content is typically determined by ion chromatography coupled with a combustion system (C-IC) after appropriate calibration.

[0111] According to one embodiment, the residue of the invention has an initial melting temperature, measured by thermal analysis (DSC), during a second heating ramp between -80°C and 180°C at 10°C / min, greater than or equal to -40°C, preferably ranging from -35 to -5°C, even more preferably ranging from -25 to -10°C.

[0112] According to one embodiment, the residue of the invention has a final melting temperature, measured by thermal analysis (DSC), during a second heating ramp between -80°C and 180°C at 10°C / min, less than or equal to 110°C, preferably ranging from 75 to 110°C, even more preferably ranging from 80 to 110°C.

[0113] Advantageously, the bituminous composition of the invention has a content of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics ranging from 0.1% by mass to 30% by mass, relative to the total mass of bituminous composition, preferably ranging from 0.5% to 25% by mass, more preferably from 1% to 20% by mass.

[0114] According to one embodiment, the bituminous composition of the invention comprises more than 5% by mass of distillation residue of a hydrocarbon product as defined above. Preferably, according to this embodiment, the bituminous composition of the invention comprises from 5% to 30% by mass of residue, more preferably from 7.5% to 25% by mass, typically from 10 to 20% by mass, relative to the total mass of the bituminous composition. Elastomer

[0115] According to one embodiment, the bituminous composition according to the invention further comprises at least one elastomer. In this case, the bituminous composition of the invention is a bitumen / polymer composition. It may be crosslinked or not crosslinked.

[0116] The elastomer is advantageously a block copolymer or a mixture of block copolymers.

[0117] Preferably, the block copolymer comprises at least 2 consecutive blocks.

[0118] It is preferably chosen from block copolymers of formula SBS, in which each S independently represents a block based on monovinyl aromatic hydrocarbon monomers, B represents a block based on butadiene monomers, in which the S blocks represent, together, at least 15% by moles of the total number of moles of the block copolymer, said block copolymers have a weight-average molecular mass ranging from 40,000 to 500,000 g.mol1 and have a content of vinyl groups greater than or equal to 5% by moles, preferably greater than or equal to 10% by moles, more preferably greater than or equal to 20% by moles, relative to the total number of moles of the block copolymer.

[0119] For the purposes of the invention, the term “block” means a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature.

[0120] The monovinylaromatic hydrocarbon monomers from which the S blocks of the block copolymers defined above are derived may independently be any monovinylaromatic hydrocarbon compound known for use in the preparation of block copolymers such as: styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof.The preferred monovinyl aromatic hydrocarbon compound according to the present invention is styrene, which is used as a substantially pure monomer or as a major component in mixtures with minor proportions of another structurally related vinyl aromatic monomer, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, i.e., in proportions of not more than 10% by weight. The use of substantially pure styrene is particularly preferred in the present invention.

[0121] The block based on butadiene monomers B entering into the composition of the co- The above-mentioned block polymers are based on substantially pure butadiene monomers or include minor proportions, up to 10% by weight, of structurally related conjugated dienes. Preferably, the polybutadiene is purely made from butadiene monomers.

[0122] With respect to the block copolymers of the present invention, the terms "molecular weight" or "molecular mass" or "average molar mass" are expressed in g.mol-1. The molecular masses mentioned in the description and the claims can be measured by gel permeation chromatography (GPC) (or SEC for "Size Exclusion Chromatography" in English). GPC is a liquid chromatography method in which the polymers are separated according to their hydrodynamic volume, which is then converted into weight-average molecular mass (Mw) and / or number-average molecular mass (Mn). GPC can be conventional or triple detection depending on the conversion method used.

[0123] In conventional GC, the hydrodynamic volume is converted by means of an external calibration. The standards used are generally linear polystyrene or polymethylmethacrylate standards. In the case of the block copolymers of the present invention, the molecular masses are measured according to a polystyrene calibration. The molecular mass of the polymers measured by GC is thus a molecular mass in styrene equivalents. The detector used is preferably a combination of a UV (ultraviolet) detector and an RI (refractive index difference) detector.

[0124] In triple detection GC, the system is equipped with 3 detectors: an RI detector, a light scattering detector and a viscosity detector (viscometer). The molecular mass values ​​are obtained directly (without requiring a calibration curve) by processing the results obtained from each of the detectors. The block copolymer of formula SBS used in the present invention has a weight-average molecular mass Mw, measured by gel permeation chromatography with polystyrene standard, ranging from 40,000 to 500,000 g.mol *.

[0125] Preferably, the block copolymer of formula SBS used in the present invention has a weight-average molecular mass Mw, measured by gel permeation chromatography with polystyrene standard, less than or equal to 400,000 g.mol *, more preferably less than or equal to 250,000 g.mol *, even more preferably less than or equal to 200,000 g.mol1 and advantageously less than or equal to 150,000 g.mol *.

[0126] Preferably, the block copolymer of formula SBS used in the present invention has a weight-average molecular mass Mw, measured by gel permeation chromatography with polystyrene standard, greater than or equal to 50,000 g.mol *, more preferably greater than or equal to 65,000 g.mol *, still more preferably greater than or equal to 75,000 g.mol *, and advantageously greater than or equal to 100,000 g.mol *.

[0127] When 1,3-butadiene is polymerized via a 1,2-addition mechanism, the result is a pendant vinyl group relative to the polymer backbone. As indicated above, the block copolymer of formula SBS used in the present invention has a vinyl group content greater than or equal to 5 mol%, preferably greater than or equal to 10 mol%, more preferably greater than or equal to 20 mol%, relative to the total number of moles of copolymer. This vinyl content, determined by coupling 13C NMR (carbon nuclear magnetic resonance) and 1H NMR (proton nuclear magnetic resonance) spectroscopy techniques, makes it possible to characterize the polymer.

[0128] The block copolymer of formula SBS used in the present invention preferably has a vinyl group content greater than or equal to 5 mol%, preferably greater than or equal to 10 mol%, more preferably greater than or equal to 20 mol%, relative to the total number of moles of SBS copolymer, more preferably greater than or equal to 25 mol%.

[0129] The block copolymer of formula SBS used in the present invention preferably has a vinyl group content of less than or equal to 50 mol%, relative to the total number of moles of SBS copolymer, more preferably less than or equal to 40 mol%, and even more preferably less than or equal to 35 mol%.

[0130] The block copolymer of formula SBS used in the present invention preferably has a vinyl group content greater than or equal to 5% by mass relative to the total mass of the copolymer, more preferably greater than or equal to 10% by mass, and even more preferably greater than or equal to 20% by mass.

[0131] The block copolymer of formula SBS used in the present invention preferably has a vinyl group content of less than or equal to 50% by mass relative to the total mass of the copolymer, more preferably less than or equal to 40% by mass, and even more preferably less than or equal to 30% by mass.

[0132] The vinyl content in block B is preferably greater than or equal to 5% by mass relative to the total mass of the condensed polybutadienes units present in block B, more preferably greater than or equal to 10% by mass, even more preferably greater than or equal to 20% by mass.

[0133] The vinyl content in block B is preferably less than or equal to 50% by mass relative to the total mass of the condensed polybutadienes units present in block B, more preferably less than or equal to 45% by mass, even more preferably less than or equal to 40% by mass.

[0134] The units obtained by the polymerization of 1,3 butadiene according to a 1,2-addition mechanism or according to a 1,4-addition mechanism have the same molar mass. Thus, the contents of vinyl groups present in block B expressed in mass or in moles are equivalent.

[0135] Preferably, the vinyl groups are distributed along the B block in a statistical manner. This characteristic results directly from the process implemented for the synthesis of the copolymer.

[0136] The S blocks present in the block copolymer of formula SBS represent, together, at least 15 mol%, relative to the total number of moles of block copolymer of formula SBS, preferably at least 16 mol%.

[0137] Preferably, the S blocks represent, together, from 15% to 50% by mole, relative to the total quantity of moles of block copolymer of formula SBS, more preferably from 16% to 30% by mole, even more preferably from 16% to 25% by mole, and advantageously from 16% to 20% by mole.

[0138] Preferably, the monovinyl aromatic hydrocarbon content (advantageously styrene) of the block copolymer of formula SBS, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), is greater than or equal to 25% by mass, more preferably greater than or equal to 28% by mass, even more preferably greater than or equal to 30% by mass, relative to the total mass of the block copolymer of formula SBS.

[0139] Preferably, the monovinyl aromatic hydrocarbon content (advantageously styrene) of the block copolymer of formula SBS, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), ranges from 25% to 40% by mass, even more advantageously from 28% to 35% by mass, relative to the total mass of the block copolymer of formula SBS.

[0140] According to a first variant, the elastomer is essentially made up of one or more block copolymer(s) of formula SBS.

[0141] According to a preferred variant, the block copolymer(s) of formula SBS are used in combination with one or more block copolymer(s) of formula SB in which S is a block based on monovinyl aromatic hydrocarbon monomers, preferably based on styrene, and B is a block based on butadiene monomers.

[0142] Preferably, according to this preferred variant, the mixture of copolymers consists mainly of the block copolymer(s) of formula SBS.

[0143] Even more preferably, still according to this preferred variant, the SBS / SB mass ratio ranges from 99.5:0.5 to 80:20 in mass, more preferably from 99.5:0.5 at 90:10 in mass.

[0144] Advantageously, the block copolymers of the invention are in an essentially non-hydrogenated form.

[0145] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula SB in which the blocks S and B are as described above in the definition of the block copolymer of formula SBS.

[0146] Preferably, according to this particular embodiment, the efficiency of the coupling of the elastomer, measured by gel permeation chromatography, is greater than or equal to 50%, more preferably greater than or equal to 75%, even more preferably greater than or equal to 90% and advantageously greater than or equal to 95%.

[0147] Examples of block copolymers of formula S-BS which can be used in the compositions according to the invention as well as their preparation processes are described in particular in US 5,798,401.

[0148] The composition may comprise elastomers other than block terpolymers of formula SBS and block copolymers of formula SB.

[0149] In particular, the composition according to the invention may contain other known bitumen elastomers such as the copolymers S-B1-B2 (styrene-butadiene-butadiene block copolymer in which the two butadiene blocks B1 and B2 have a different vinyl content), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene butadiene rubber), EPDM (modified ethylene propylene diene), polychloroprene, polynorbornene, natural rubber, recycled rubber, polybutene, polyisobutylene, SEBS (copolymer of styrene, ethylene, butylene and styrene). Mention may also be made of elastomers made from styrene monomers and butadiene monomers allowing crosslinking without crosslinking agent as described in documents WO2007 / 058994 and by the applicant in patent application WO2011 / 013073.

[0150] Advantageously, the block copolymers of formula SBS and the block copolymers of formula SB which have been defined above represent, together, at least 50% by mass of the elastomers present in the composition, more preferably at least 70% by mass, and even more preferably at least 90% by mass.

[0151] According to a preferred variant of the invention, the elastomer consists essentially of block copolymers of formula SBS and block copolymers of formula SB.

[0152] The composition may also further comprise other plastomers distinct from the olefinic polymer adjuvant functionalized by at least one epoxide group.

[0153] The bitumen / polymer composition (optionally crosslinked) according to the invention preferably comprises from 0.1% to 20% by mass of elastomer, in particular of a co polymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the bitumen / polymer composition (crosslinked).

[0154] According to one embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 1% to 10% by mass of elastomer, in particular of a copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 2% to 8% by mass, advantageously from 3% to 5% by mass.

[0155] According to an alternative embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 5% to 20% by mass of elastomer, in particular of a copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 10% to 15% by mass.

[0156] The incorporation of a distillation residue as defined above into a bitumen / polymer composition, with a constant polymer content, makes it possible to further improve the mechanical properties of a bitumen / polymer composition by the incorporation of said residue.

[0157] Alternatively, the incorporation of a distillation residue as defined above into a bitumen / polymer composition makes it possible, with equivalent mechanical properties, to reduce the polymer content by incorporating said residue. This second option is advantageous in that it makes it possible to further reduce the proportion of materials of fossil origin in the compositions. In particular, with equivalent mechanical properties, the incorporation of a distillation residue according to the invention makes it possible to reduce the elastomer content in a bitumen / polymer composition by at least 5%, preferably from 5% to 30%, even more preferably from 10% to 20%. Additives

[0158] According to one embodiment, the bituminous composition according to the invention further comprises one or more additional additive(s).

[0159] These additional additives are known to those skilled in the art.

[0160] By way of example, the following additives may be mentioned in particular: a. adhesion promoters and / or surfactants. They are generally chosen from alkylamine derivatives, alkylpolyamine derivatives, alkylamidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture. The amount of adhesion promoters and / or surfactants present in the bitumen / polymer composition is, for example, between 0.2% and 2% by weight, preferably between 0.5% and 1% by weight, relative to the total mass of the bitumen / polymer composition.

[0161] b) waxes of animal or vegetable origin or hydrocarbon waxes, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or paraffins, optionally oxidized. Amide waxes, such as ethylene bis(stearamide), may also be added.

[0162] c) paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are chosen from polyalkylenes. Preferably, the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins may be of petroleum origin or may come from the chemical industry. Preferably, the paraffins are synthetic paraffins resulting from the conversion of biomass and / or natural gas.

[0163] d) melting agents, such as oils based on animal and / or vegetable fatty substances or hydrocarbon oils of petroleum origin. The oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides or in esterified form, for example in the form of methyl ester.

[0164] e) resins of plant origin, such as rosins.

[0165] f) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes and fatty acid amides derived from vegetable or animal oils.

[0166] g) detergent additives and / or corrosion inhibitors, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylpolyamines, polyetheramines and imidazolines.

[0167] h) sliding agents or anti-wear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glyceryl monooleate, and mono- and polycyclic carboxylic acid derivatives.

[0168] i) crystallization modifying additives, paraffin deposition inhibiting additives, pour point lowering additives; low temperature rheology modifiers, such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate (EA / AA / EOVA) terpolymers; ethylene / vinyl acetate / alkyl acrylate terpolymers; graft-modified EVA copolymers; polyacrylates; acrylate / vinyl acetate / maleic anhydride terpolymers; amidated copolymers of maleic anhydride / alkyl (meth)acrylate obtainable by reaction of a copolymer of maleic anhydride / alkyl (meth)acrylate and an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; the amidated α-olefin / maleic anhydride copolymers obtainable by reaction of an α-olefin / maleic anhydride copolymer and an alkylamine or polyalkylamine, the α-olefin being able to be chosen from C10-C50 α-olefins, preferably C16-C20 α-olefins, and the alkylamine or polyalkylamine advantageously having a hydrocarbon chain of 4 to 30 carbon atoms, preferably from 12 to 24 carbon atoms.

[0169] j) antioxidants, for example of hindered phenolic type or amino type, of alkylated para-phenylenediamine type.

[0170] k) metal passivators.

[0171] 1) acidity neutralizers.

[0172] m) additives for lowering the mixing temperature of asphalts and coatings, those for improving the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides.

[0173] n) acids, such as polyphosphoric acid, or diacids, in particular fatty diacids.

[0174] The additives are used in quantities well known to those skilled in the art, depending on the nature of the additive, the bituminous base and the expected properties.

[0175] Preferably, when present, the content of additional additives varies from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.5% by mass, relative to the total mass of the bituminous composition of the invention. Compositions

[0176] According to one embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of: - from 60% to 99.9% by mass of bitumen, - from 0.1% to 30% by mass of one or more residues from the distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste, - optionally, from 0.1% to 20% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon, and - optionally, from 0.1% to 10% by mass of additional additive(s) as described above,

[0177] relative to the total mass of the bituminous composition.

[0178] Preferably, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of:

[0179]

[0180]

[0181]

[0182] - from 65% to 99% by mass of bitumen, - from 0.5% to 25% by mass of one or more residues from the distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste, - optionally, from 1% to 10% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon, and - optionally, from 0.1% to 10% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition. More preferably, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of: - from 70% to 95% by mass of bitumen, - from 1% to 20% by mass of one or more residues from the distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste, - optionally, from 2% to 8% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon, and - possibly, from 0.5% to 5% by mass of additional additive(s) as described above, relative to the total mass of the bituminous composition. Even more preferably, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of: - from 80% to 90% by mass of bitumen, - from 5% to 15% by mass of one or more residues from the distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste, - optionally, from 3% to 5% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon, and - possibly, from 0.5% to 2.5% by mass of additional additive(s) as described above,

[0183] relative to the total mass of the bituminous composition.

[0184] The bituminous composition according to the invention is homogeneous. By "homogeneous" is meant, within the meaning of the invention, that the different components of the composition, namely the plastic pyrolysis distillation residue and any elastomers and / or additives are distributed uniformly in the bituminous matrix.

[0185] According to one embodiment, the composition according to the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 30 to 300 1 / 10 mm, more preferably from 40 to 200 1 / 10 mm, typically from 45 to 175 1 / 10 mm.

[0186] According to one embodiment, the composition according to the invention has a ring and ball softening temperature, measured according to standard EN 1427, higher than the ring and ball softening temperature of the same composition free from distillation residue.

[0187] Preferably, the composition according to the invention has a ring and ball softening temperature, measured according to standard EN 1427, greater than 40°C, more preferably greater than or equal to 45°C, advantageously ranging from 40°C to 90°C, typically ranging from 45°C to 80°C.

[0188] According to one embodiment, the composition according to the invention has an average dynamic viscosity at 100°C, measured according to standard NF EN 13702 with a shear rate equal to 100 s1, lower than the average dynamic viscosity at 100°C of the same composition free from distillation residue.

[0189] According to one embodiment, the composition according to the invention has an average dynamic viscosity at 140°C, measured according to standard NF EN 13702 with a shear rate equal to 100 s1, lower than the average dynamic viscosity at 140°C of the same composition free from distillation residue.

[0190] According to one embodiment, the composition of the invention comprises a significant proportion of recycled or waste materials. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

[0191] Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials].

[0192] According to one embodiment, the composition has an eco-material content of at least 5% by mass, relative to the total mass of the composition, preferably at least 10%, preferentially at least 15%.

[0193] Process for preparing a bituminous composition according to the invention

[0194] The bituminous compositions of the invention can be prepared by any method known to those skilled in the art. As a general rule, these methods comprise bringing the different components into contact, followed by their mixing, preferably under heating.

[0195] According to a preferred embodiment, the bitumen as well as the distillation residue are heated before mixing, preferably separately.

[0196] Preferably, the bitumen and the distillation residue are heated separately and then mixed while hot. Any elastomer(s) and / or additive(s) are then added to the bitumen / distillation residue mixture without having been previously heated.

[0197] The invention thus relates to a process for preparing a bituminous composition as defined above, said process comprising:

[0198] 1) bringing into contact:

[0199] - at least one bitumen base;

[0200] - at least one distillation residue of a hydrocarbon product, said product hy carbon having been obtained by thermal conversion of plastics,

[0201] - optionally, one or more elastomer(s), in particular as defined above- above,

[0202] - optionally one or more other additive(s), in particular one or more additional additive(s) as described above;

[0203] 2) their mixing under heating.

[0204] According to a preferred embodiment, the bitumen base and the distillation residue are brought into contact while hot, preferably at a temperature ranging from 90°C to 230°C, preferably ranging from 120°C to 200°C, and preferentially ranging from 150°C to 180°C.

[0205] Preferably, according to this embodiment, the method comprises a preliminary step of heating the bitumen base and the distillation residue, separately, before bringing them into contact.

[0206] The heating temperature of the bitumen base depends on its grade. In particular, the bitumen base is heated in accordance with the requirements given in standard NF EN 12594.

[0207] The distillation residue is typically heated to a temperature greater than or equal to its melting temperature. The heated residue is thus in a fluid form so as to facilitate its mixing with the bitumen.

[0208] Advantageously, the method of the invention comprises the following successive steps:

[0209] a) heating the bitumen and the distillation residue, independently,

[0210] b) hot mixing of bitumen and distillation residue,

[0211] c) optionally, the introduction into the mixture obtained in b) of one or more elastomers and / or one or more additives, in particular as described above.

[0212] The mixing of the bitumen and the distillation residue can be carried out at a temperature ranging from 90 to 230°C, preferably ranging from 120 to 200°C, and preferentially ranging from 150 to 180°C. Preferably, during step c), the bitumen / residue mixture obtained at the end of step b) is maintained at a temperature ranging from 90 to 230°C, preferably ranging from 120 to 200°C, and preferentially ranging from 150 to 180°C.

[0213] Such a mixture is produced with stirring, so as to facilitate the dispersion and good distribution of the distillation residue of the invention, and optionally of the elastomer(s) and / or of the other additive(s), in the bitumen / residue mixture which will constitute the matrix of the composition. The conditions are adapted to lead to obtaining a homogeneous mixture and a good distribution of the distillation residue of the invention and possibly the elastomer(s) and / or the other additive(s). Conventionally, the person skilled in the art will adjust the time and power of the stirring, as well as the mixing temperature, in particular as a function of the bitumen, the distillation residue of the invention, and possibly the elastomer(s) and / or the additive(s), to have a molten mixture. Advantageously, the mixing is carried out in such a way as to promote a good distribution of the distillation residue of the invention and the elastomer in the final bituminous composition obtained.

[0214] In general, and in a manner known to those skilled in the art, the bitumen or mixture of bitumens used for the manufacture of the composition is previously heated and stirred, before incorporation of the other constituents of the composition. The incorporation of the distillation residue of the invention, and optionally of the elastomer, is generally carried out while the bitumen is maintained at a temperature belonging to the range from 90°C to 230°C, preferably to the range from 120°C to 200°C, and preferentially to the range from 150°C to 180°C.

[0215] The components may be introduced at the same time or in a sequential manner. Heating is maintained throughout the process, and the heating temperature may be modulated during the process. Agitation may be maintained or interrupted intermittently as needed, or modulated during the process.

[0216] According to particular embodiments, the method according to the invention comprises a homogenization step which makes it possible, in particular, to distribute the elastomer(s) and / or the additives, in said composition. Such a step is in particular a step of mixing the different constituents, with stirring at a speed of 100 to 600 rpm, preferably 200 to 400 rpm and for a duration of 2 to 30 hours, preferably 6 to 24 hours, while the mixture is heated to a temperature belonging to the range from 90 to 230°C, preferably to the range from 120 to 200°C, and preferably to the range from 150 to 180°C.

[0217] In the process according to the invention, one or more bitumen(s), one or more distillation residue(s) as defined above, optionally one or more elastomer(s) and / or one or more additional additive(s) are used, corresponding to the descriptions given previously in the corresponding parts. The crosslinked elastomers are introduced in crosslinkable form into the compositions according to the invention and crosslinked in situ.

[0218] Of course, in the process, the quantities used of bitumen, distillation residue of the invention, or even elastomer(s) and / or additional additive(s), will be adjusted by those skilled in the art to ultimately obtain the desired quantities. in the final composition, and in particular those mentioned in the previous part relating to the compositions according to the invention.

[0219] The characteristics described in the preceding sections also apply to the preparation processes according to the invention. Thus, the components used in the preparation process will preferably be chosen from those previously described and introduced in proportions making it possible to achieve the quantities given for the description of the bituminous compositions according to the invention.

[0220] The bituminous compositions capable of being obtained by such processes also form an integral part of the invention. Applications

[0221] Various uses of the bituminous compositions according to the invention are envisaged. In particular, the bituminous compositions according to the invention can be used as a bituminous binder.

[0222] The bituminous binder or bituminous composition according to the invention can be used to prepare an association with aggregates, in particular road aggregates. With regard to road applications, the invention relates in particular to bituminous coatings as materials for the construction and maintenance of road surfaces and their surfacing, as well as for carrying out all road works.

[0223] By bituminous coating is meant a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers. The bituminous coating comprises a bituminous binder according to the invention, and optionally mineral and / or synthetic fillers, preferably chosen from fines, sand, gravel and recycled millings.

[0224] The aggregates are mineral and / or synthetic aggregates, in particular, recycled millings, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

[0225] The invention also relates to a process for preparing a bituminous coating comprising the hot mixing of a bituminous composition according to the invention, with aggregates, and optionally mineral and / or synthetic fillers.

[0226] The bituminous binder according to the invention can advantageously be used to prepare a surface coating, a hot mix, a cold mix, a cold-poured mix or a gravel emulsion. With regard to road applications, the invention also relates to asphalts as materials for manufacturing and covering pavements.

[0227] By asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers. An asphalt comprises a bituminous composition as described in the context of the invention and mineral fillers such as fines, sand or gravel and / or synthetic fillers. The mineral fillers are consisting of fines (particles smaller than 0.063 mm), sand (particles between 0.063 mm and 2 mm) and possibly gravel (particles larger than 2 mm, preferably between 2 mm and 4 mm). Asphalts have 100% compaction and are mainly used to make and cover pavements, while asphalts have a compaction of less than 100% and are used to make roads. Unlike asphalts, asphalts are not compacted with a roller during installation.

[0228] The invention also relates to a process for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and / or synthetic fillers.

[0229] Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, in particular for preparing an impregnation layer. With regard to industrial applications of bituminous compositions, mention may be made of the manufacture of anti-noise membranes, insulation membranes, surface coverings, carpet tiles, impregnation layers.

[0230] The invention also relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the content of compounds of fossil origin in said bituminous composition. In particular, the invention relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bituminous composition in order to reduce the bitumen content in said composition. More particularly, the invention relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bituminous composition in order to reduce the bitumen content in said composition by at least 5%, preferably from 5% to 30%, more preferably from 7.5% to 25%, even more preferably from 10% to 20%.

[0231] Also, in the case of a bitumen / polymer composition, the subject of the invention is the use of a distillation residue of a hydrocarbon product as defined above, in order to reduce the bitumen content and / or the polymer content in said bitumen / polymer composition. Preferably, the subject of the invention is the use of a distillation residue of a hydrocarbon product as defined above in a bitumen / polymer composition in order to reduce:

[0232] - at least 5% of the bitumen content in said bitumen / polymer composition, preferably from 5% to 30%, more preferably from 7.5% to 25%, even more preferably from 10% to 20%, and / or

[0233] - at least 5% of the elastomer content in said composition, preferably of 5% to 20%, even more preferably 10% to 15%.

[0234] The invention also relates to the use of a distillation residue as defined above in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the dynamic viscosity when hot, in particular at a temperature greater than or equal to 100°C, of ​​said composition.

[0235] The hot dynamic viscosity of a bituminous composition is typically measured at a temperature greater than or equal to 100°C, conventionally at a temperature of 100°C and / or 140°C. The hot dynamic viscosity of a bituminous composition can be measured according to any method known to those skilled in the art, in particular according to standard NF EN 13702.

[0236] Since the bituminous composition according to the invention has a reduced hot viscosity, it can be fluidized at a lower temperature than the same composition free of distillation residue. Thus, the bituminous composition of the invention is advantageous in that it can be implemented at a lower temperature, compared to the same composition free of distillation residue. This reduction in the implementation temperature therefore results in a reduction in the energy required for the implementation of the compositions of the invention, in particular for the preparation of bituminous coatings, compared to the same composition free of residue of the invention.

[0237] For the purposes of the invention, the term "temperature for implementing a bituminous composition" means the minimum temperature to which a bituminous composition must be heated so that it is sufficiently fluid and / or ductile to be transformed into a final product, in particular to be mixed with aggregates in order to form a bituminous coating. In particular, and in order to be easily pumpable, the composition must typically have a viscosity of approximately 1.5 Pa.s. When preparing a bituminous coating, the composition must typically have a viscosity of approximately 0.2 Pa.s.

[0238] Thus, the invention also relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the processing temperature of said bituminous composition.

[0239] The invention thus relates, more generally, to the use of a distillation residue of a hydrocarbon product as defined above, in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the carbon footprint of said composition.

[0240] By "carbon footprint" of a product, we mean for the purposes of the invention the quantity of carbon (generally expressed in Kg of CO2 equivalent per Kg of product) born necessary for the preparation of said product, this quantity of carbon equivalent taking into account both energy consumption, particularly related to heating, and raw materials. The carbon footprint of a product is typically determined according to any of the ISO 14040 and ISO 14044 standards.

[0241] The invention is advantageous in that the incorporation of the residue of the invention makes it possible to significantly reduce the content of materials of fossil origin in the bituminous compositions. It is also advantageous in that the incorporation of the residue results in several surprising technical effects.

[0242] In particular, the incorporation of the residue of the invention has at least one of the following technical effects: i) increasing the penetrability at 25°C of the composition, ii) increasing the softening temperature of the composition, iii) reducing the hot viscosity of the composition, in particular at 100°C and 170°C, and iv) improving the resistance to aging of the composition.

[0243] In the context of bitumen / polymer compositions, the incorporation of the residue of the invention further has at least one of the following technical effects: i) improving the compatibility of the elastomer with the other constituents and ii) reducing the elastomer content at constant softening temperature.

[0244] The invention is illustrated by the following examples given without limitation. EXAMPLES 1. Materials and methods

[0245] 1.1. Physical properties

[0246] The physicochemical properties of the raw materials and bituminous compositions were evaluated according to the methods detailed in Table 1 below:

[0247] [Tables 1] Property Abbreviation Unit Method of measurement Needle penetration at 25°C P25 1 / 10 mm NF EN 1426 Ring and ball softening temperature TBA °C NF EN 1427 Cleveland flash point Flash TA °C ASTM D92 Boiling point (initial, 5%, 10%, ... final) Teb (X) With X = ini., 5, 10, ..., end) °c ASTM D7169:20 Calcium content Ca ppm (by mass) By calcination of the material, acidification of ash and analysis by ICP-OES. Phosphorus content P ppm (by mass) By acid digestion in a closed microwave instrument and analysis by ICP-OES following classical acid conditions. Silicon content Si PPm (by mass) By X-ray fluorescence (XRF) after homogenization of the material and appropriate calibration. Chlorine content Cl PPm (by mass) By ion chromatography coupled with a combustion system (C-IC) Initial melting temperature TT A ^-melting °C DSC (second heating ramp between -80°C and 180°C at 10°C / min) Final melting temperature TFmelting °C DSC (second heating ramp between -80°C and 180°C at 10°C / min) Viscosity at 100°C V100 mPa.S NF EN 13302 Viscosity at 140°C V140 mPa.S NF EN 13302 Maximum elongation F J-'max in % NF EN 13587 Storage stability the storage stability of the concentrated compositions prepared above is evaluated by measuring the difference in TBA (ATBA) of each composition after 3 days of storage at 180°C Cold properties: BBR test (determination of the flexural rigidity modulus) T°@S=300MPa and T°@m=0.3 °C NF EN 14771. Aging Acceleration Protocol (AAP) - - NF EN 14769

[0248]

[0249]

[0250] 1.2. Raw materials The bituminous compositions were prepared from the following raw materials: - B1 bitumen base with a penetrability at 25°C, measured according to standard NF EN 1426, equal to 86 1 / 10 mm, and a ring and ball softening temperature (RBT), measured according to standard NF EN 1427, equal to 45.8°C, commercially available from TotalEnergies under the reference AZALT® 70-100; - Elastomer: a styrene / butadiene / styrene (SBS) block copolymer was used, with 18.8 mol% styrene and 81.2 mol% butadiene, relative to the total number of moles of copolymer. The vinyl group content is 29.4 mol% relative to the total number of moles of copolymer. The copolymer has a mass molecular weight (Mw) of 131,000 g.mol-1. This copolymer is commercially available from the company KRATON under the name DI 192; Distillation residue RI; Distillation residue R2; Distillation residue R3, - Crosslinking agent: sulfur-rich agent; - Additive: additive to trap hydrogen sulfide emissions (in English "H2S scavenger") The physical characteristics of the different residues RI, R2 and R3 are given in the following table 2: [0251 ] [T ableaux2] Residue RI Residue R2 Residue R3 P25 (in 1 / 10 mm) 45 61 76 TB A (in °C) 82.0 82.7 68.2 Flash point 266 278 272 Teb (ini) 276.0 288.0 345.0 Teb (5%) 495.0 378.0 449.0 Teb (10%) 515.0 432.0 460.0 Teb (15%) 528.0 458.0 468.0 Teb (30%) 565.0 503.0 484.0 Teb (50%) 628.0 549.0 510.0 Teb (70%) 719.0 605.0 591.0 Teb (80%) 740.0 667.0 644.0 Teb (final) >740.0 >738.0 >742.0 Ca content 964 669 1016 P content 65 56 168 Si content 714 286 610 Cl content 1326 377 472 TT J- -^-fusion -30 -18 -26 TFf -1-x fusion 95 94 88

[0252] 1.3. Protocol for the preparation of compositions

[0253] a) polymer-free bituminous compositions

[0254] The bituminous compositions are prepared according to the following protocol:

[0255] The bitumen base is preheated to 130°C for 30 min + / - 15 min. The distillation residue is also preheated, independently, to a temperature higher than the melting temperature of said residue.

[0256] In a 1 kg reactor, the preheated bitumen base is first introduced, then the heated residue. Then, the reactor is placed in a reactor heater with a mixing temperature of 150°C. The mixture is stirred using a glass blade and mechanical stirring at a speed of 200 rpm for 30 minutes.

[0257] b) bitumen / polymer compositions

[0258] The bitumen base (preheated to 130°C for 1 h + / - 0.15 min for a 1 kg container) and the distillation residue, previously heated (same conditions as in the previous protocol) are mixed together at a temperature of 150°C for 30 minutes at a stirring speed of 200 rpm using a glass stirring blade. Half of the scavenger is incorporated: this step is carried out outside the reactor heater, using a Silverson, with it running at a stirring speed of 6,000 rpm. This scavenger is left to act for 10 minutes, still at a speed of 6,000 rpm. Then, the polymer and activated sulfur are added with the Silverson still running. This is left to act again for a period of 10 minutes and at a speed of 6,000 rpm. The whole is then mixed in the reactor heater for 24 hours at 180°C at a speed of 200 rpm with the other half of the scavenger being incorporated 15 minutes before the end of production. 2. Preparation of bituminous compositions

[0259] Bituminous compositions C0 to C8 were prepared according to the protocols defined above.

[0260] The details of the compositions are given in the following table 3.

[0261] [Tables3] CO* Cl C2 C3 C4 C5 C6* C7 C8 Bitumen B1 (in %) 100 90 85 90 90 85 96.25 86.625 86.985 Elastomer (in %) - - - - - - 3.4 3.4 3.0 Residue RI (in %) - 10 15 - - - - - - Residue R2 (in %) - - - 10 - - - - - Residue R3 (in %) - - - - 10 15 - 9.625 9.665 Crosslinking agent (in %) - - - - - - 0.1 0.1 0.1 Additive (in %) - - - - - - 0.25 0.25 0.25

[0262] Compositions C0 to C5 are bituminous compositions free of elastomer. Composition C0 is comparative in that it does not comprise distillation residue according to the invention. Compositions C1 to C5 are according to the invention.

[0263] Compositions C6 to C8 are crosslinked bitumen / polymer compositions. Composition C6 is comparative in that it does not comprise distillation residue according to the invention. Compositions C7 and C8 are according to the invention.

[0264] 3. Evaluation of the properties of bituminous compositions

[0265] The physicochemical properties of the bituminous compositions CO to C8 were evaluated according to the protocols detailed above. The results are reported in the following Table 4.

[0266] [Tables4] CO* Cl C2 C3 C4 C5 C6* C7 C8 P25 (1 / 10 mm) 86 87 85 101 110 131 53 65 61 TBA (°C) 45.8 55.2 58.8 53.9 50.6 55.0 64.0 73.8 68.8 V100 (mPa.s) 3292 1230 788 1105 1043 686 1344 5 5462 4739 V140 (mPa.s) 337 174 - 154 145 113 1147 520 468 Maximum elongation - - - - - - >700 >700 >700 Storage stability_3 days_180°C ATBA (°C) - - - - - - 0.6 0.6 0.4 BBR T°@S= 300MPa (°C) -18.7 - - -20.8 -21.2 -22.0 - - - T°@m=0.3 (°C) -21.3 - - -21.3 -20.5 -20.4 - - - Properties after PA V 25h Remaining penetration (in %) 35% 41% - 32% 34% 31% - - - ATBA (°C) 11.0 8.4 - 9.4 8.2 6.2 - - - Properties after PA V 48h Remaining penetration (in %) 27% 32% - 27 29 34 - - - ATBA (°C) 16.6 13.8 - 14.8 13.8 9.8 - - - Compositions CO to C5 (polymer-free)

[0267] It is observed that compositions C1 to C5 according to the invention have a penetrability at 25°C increased or equivalent to that of composition C0 free of residue. They have an increased softening temperature compared to the residue-free CO composition. They also have a viscosity at 100°C and 140°C significantly reduced compared to those of the CO composition.

[0268] It is also noted that the cold properties of the compositions are not degraded by the introduction of the residue: the results of the BBR test are similar, or even slightly improved.

[0269] Finally, the resistance to aging of the compositions according to the invention is similar or improved compared to the CO composition, both after 25h and 48h of aging. Indeed, the retention of penetrability is equivalent or increased. The variation in softening temperature is always reduced compared to the variation observed for the CO composition. Bitumen / polymer compositions C6 to C8

[0270] It is observed that compositions C7 and C8 according to the invention have increased penetrability at 25°C and softening temperature compared to composition C6* free of residue. They also have significantly reduced viscosity at 100°C and 140°C compared to those of composition C6*.

[0271] It is also observed that compositions C6 to C8 all have a maximum elongation greater than 700%: the maximum elongation of the compositions is therefore not degraded by the presence of the residue. On the contrary, it is observed that composition C8 according to the invention, incorporating the residue of the invention and having an elastomer content reduced by approximately 11%, has a maximum elongation similar to that of comparative composition C6*. The presence of the residue would therefore make it possible, with constant elastic properties, to reduce the elastomer content.

[0272] Finally, compositions C6 to C8 are all stable during storage: the incorporation of the residue therefore does not alter the storage stability of the compositions.

Claims

Claims

1. Bituminous composition comprising: a) at least one bitumen base, b) at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm.

2. Bituminous composition according to claim 1, in which the distillation residue b) has a penetrability at 25°C, measured according to standard EN 1426, ranging from 20 1 / 10 mm to 120 1 / 10 mm.

3. Bituminous composition according to claim 1 or claim 2, in which the distillation residue b) is a residue from atmospheric distillation of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

4. Bituminous composition according to any one of the preceding claims, in which the distillation residue b) has a boiling point at 10% by mass, measured according to standard ASTM D7169:20, greater than or equal to 350°C, preferably ranging from 400°C to 600°C, typically ranging from 410°C to 550°C.

5. Bituminous composition according to any one of the preceding claims, in which the distillation residue b) has a ring and ball softening temperature (RBT), measured according to standard EN 1427, greater than or equal to 60°C, more preferably ranging from 60°C to 120°C, typically ranging from 65°C to 100°C.

6. Bituminous composition according to any one of the preceding claims, having a residue content b) ranging from 0.1% to 30% by mass, relative to the total mass of the composition, preferably from 0.5% to 25% by mass, more preferably from 1% to 20% by mass.

7. Bituminous composition according to any one of the preceding claims, further comprising at least one elastomer, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

8. Crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition according to claim 7.

9. Process for preparing a bituminous composition according to one of any of the preceding claims, said process comprising the following successive steps: 1) bringing into contact at least: - a bitumen base, - a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm, - optionally, an elastomer, 2) mixing the components

10. A process according to claim 9, wherein the bitumen base and the distillation residue are preheated, preferably separately, to a temperature ranging from 90°C to 230°C, preferably from 120°C to 200°C, more preferably from 150°C to 180°C.

11. Use of a bituminous composition according to any one of claims 1 to 8, as a binder for preparing a surface coating, a hot mix, a cold mix, a cold-poured mix, a gravel emulsion or a wearing course, said binder being associated with aggregates and / or recycled millings.

12. Bituminous coating comprising a bituminous composition according to any one of claims 1 to 8, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

13. Use in a bituminous composition, in particular in a bitumen / polymer composition, of at least one distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm, and an initial boiling point, measured according to standard ASTM D7169:20, less than or equal to 500°C, to reduce the content of compounds of fossil origin, in particular bitumen and / or elastomer, in said composition.

14. Use in a bituminous composition, in particular in a bitumen / polymer composition, of a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said distillation residue having a penetrability at 25°C, measured according to standard EN 1426, of less than or equal to 200 1 / 10 mm, to reduce the hot viscosity of said composition.

15. Use in a bituminous composition, in particular in a bitumen / polymer composition, of a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, said distillation residue having a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm, to reduce the implementation temperature of said bituminous composition.